Professional Documents
Culture Documents
ADMIN:
I.W
PVC TECHNOLOGY
Fourth Edition
PVC
TECHNOLOGY
Fourth Edition
W. V. TITOW
M. Phil., Ph.D., C.Chem., F.R.S.C., F.P.R.I., C. Text., A. T.!.
Formerly of the Yarsley Research Laboratories Ltd,
Ashtead, Surrey, England
First edition
Second edition
Reprinted
Third edition
Fourth edition
Reprinted
1962
1966
1967
1971
1984
1986
ISBN-13: 978-94-010-8976-0
e-ISBN-13: 978-94-009-5614-8
DOl: 10.1007/978-94-009-5614-8
WITH 171 TABLES AND 230 ILLUSTRATIONS
This book continues the tradition of the first two editions of the late
W. S. Penn's original PVC Technology, and the extensively revised
third (1971) edition prepared by myself and B. J. Lanham.
In the present edition the original general format, and the arrangement of chapters, have been largely preserved, but virtually nothing
now remains of Penn's own text: a part of the contents is based on
material from the 1971 TitowlLanham version (revised, updated and
mainly rewritten): the rest is new, including, inter alia, several chapters
specially contributed by experts from the plastics industry in the UK
and Europe. The section listing international (ISO) and national (BS,
ASTM and DIN) standards relevant to PVC, which was first introduced (as Appendix 1) in the 1971 edition, proved a popular feature: it
has now been brought up to date and considerably extended. Two
further appendices provide, respectively, comprehensive unit conversion" tables (with additional information on some of the most frequently
encountered units, and the SI units), and a list of many properties of
interest in PVC materials, with definitions, typical numerical values,
and references~to relevant standard test methods.
For various reasons, work on this edition involved more than the
usual quota of problems: I am truly grateful to the Publisher's Managing Editor, Mr G. B. Olley, for his understanding, patience, unfailing
courtesy and friendly encouragement. I am also most appreciative of
the helpful attitude of all other members of the Publisher's staff who
were concerned with the various aspects of processing the manuscript
and bringing the book out.
If my own contribution to the book has any merit, then I would like
to dedicate it-respectfully and affectionately-to all my friends of the
Yarsley Laboratories with whom I was priviledged to share many
happy years, participating in the worthwhile work of a good team.
W.V.T.
v
Acknowledgements
viii
Acknowledgements
Contents
Preface
Acknowledgements
vii
xxix
Chapter 1
Introduction-W. V. TITOW . . . . . . . . . . . . .
1.1 PVC: General Terminology and Relevant Definitions
1.2 Early History and Development of PVC . . . . .
1.3 General Statistics
1.4 Outline of the PVC Sector of the Plastics Industry
1.5 Vinyl CWoride Polymers and Copolymers . . . .
1.5.1 PVC Homopolymers: chemical structure; morphology
1.5.2 Vinyl CWoride Copolymers . . . . . . .
1.5.3 'External' Modification of PVC by Other Polym-
1
1
4
10
12
13
13
19
21
24
24
29
30
Chapter 2
Commercial PVC Polymers-W. V. TITOW
37
ers
ix
Contents
37
41
42
43
46
48
49
55
55
57
59
59
60
61
63
63
65
65
78
79
79
81
83
85
Contents
4.4.1 Nature and Characteristics of Individual Components of a Formulation: PVC polymer; heat
stabilisers; plasticisers; lubricants; polymeric modifiers; fillers; colourants
4.4.2 Interactions and Mutual Effects of Formulation
Components: compatibility effects; synergism;
other mutual effects
4.4.3 Side Effects of Formulation Components: 'secondary functionality' effects; undesirable sideeffects
4.5 Some Special End-use Requirements
4.5.1 Food-contact Applications
4.5.2 Resistance to Weathering
4.5.3 Electrical Insulation
4.6 Examples of Basic Formulations
4.6.1 Film and Sheeting
4.6.2 Calendered Plasticised Vinyl/Asbestos Flooring
4.6.3
4.6.4
4.6.5
4.6.6
4.6.7
4.6.8
4.6.9
(Tile~
Chapter 5
Theoretical Aspects of PlasticisatiOD'--D. L. BUSZARD
5.1
5.2
5.3
5.4
5.5
5.6
General Introduction . . . . . . . . .
Definition of Plasticisers and Plasticisation
Chemical Nature of Plasticisers
Theories of Plasticisation
Stages of Plasticiser Interaction with PVC Polymer
Requirements for PVC Plasticisers
5.6.1 Compatibility and Miscibility: the IL value; solubility parameter 8; clear point temperature;
Flory-Huggins interaction parameter x; Ap/Po
ratio; loop or roll compatibility tests; maximum
torque temperature
xi
86
103
105
106
106
107
107
107
107
109
110
111
112
112
113
114
114
117
117
117
119
120
122
124
125
xii
Contents
132
134
136
138
142
143
Chapter 6
Commercial Plasticisers-D. L. BUSZARD
6.1 Introduction . . . . . . . . . . . .
6.2 Classification of Commercially Available Plasticisers
6.3 Group Characteristics of Major Plasticiser Gasses
6.4 Synonyms and Abbreviations
6.5 Group 1 Plasticisers-Phthalates .
6.5.1 Lower Phthalates . . . .
6.5.2 General-purpose Phthalates
6.5.3 Linear Phthalates
6.5.4 Higher Phthalates
6.5.5 Miscellaneous Phthalates
6.6 Group 2 Plasticisers-Phosphates
6.6.1 Triaryl Phosphates . . .
6.6.2 Trialkyl Phosphates
6.6.3 Mixed Alkyl Aryl Phosphates
6.6.4 Halogenated Alkyl Phosphates
6.7 Group 3 Plasticisers-Trimellitates .
6.8 Group 4 Plasticisers-Aliphatic Diesters
6.9 Group 5 Plasticisers-Polymeric Plasticisers
6.10 Group 6 Plasticisers-Miscellaneous Plasticisers
6.10.1 Epoxy Plasticisers
6.10.2 Chlorinated Paraffins
6.10.3 Monoesters . . . .
6.10.4 Glycol Esters
6.10.5 Hydrocarbon Extenders
6.10.6 Other Miscellaneous Plasticisers
6.11 Storage and Handling of Plasticisers
6.12 Plasticiser Manufacturers
References . . . . . . . . . . . . . .
147
147
147
148
148
152
152
153
153
156
158
159
159
160
161
163
163
163
165
170
170
171
173
173
174
174
175
180
180
Conren~
Chapter 7
Properties of Plasticised PVC-D. L. BUSZARD
7.1 Introduction . . . . . . . . . . . . . .
7.2 Formulation of a Plasticised PVC Compound
7.2.1 The 'Desirability Function'
7.2.2 Computer-assisted Formulating
7.3 Softness and Tensile Properties
.....
7.3.1 Effect of Plasticiser
7.3.2 Compounding at Equal Efficiency
7.4 Low-temperature Properties
7.5 Permanence Properties
7.5.1 Extraction Resistance
7.5.2 Migration Resistance
7.5.3 Volatile Loss
7.5.4 Automotive Fogging
7.5.5 High-humidity Compatibility
7.6 Flame-retardant Properties
7.7 Electrical Properties
7.8 Weathering and Light Stability . . .
7.9 Resistance to Microbiological Attack
7.10 Resistance to Insect and Rodent Attack
7.11 Stain Resistance . . . . . . . . . .
7.12 Toxicity and Health Aspects of Plasticisers
7.12.1 Plasticisers for Food-contact Application
7.12.2 Health and Safety
References . . . . . . . . . . . . . . . . . . .
Chapter 8
FiDers in PVC-I. D. HOUNSHAM and W. V. TITOW
8.1 Introduction . . . . . . . . . . . . . . .
8.2 Mineral Fillers . . . . . . . . . . . . . .
8.2.1 Silicates and Silicas: asbestos; talc; clay
8.2.2 Alkaline-earth Metal Sulphates
8.2.3 Calcium Carbonates
8.3 Calcium Carbonate Fillers-Nature, Properties and Applications . . . . . . . . . . . . . . . . . . . . .
8.3.1 General Types: whiting; ground limestone, marble
and calcite; ground dolomite; precipitated calcium
carbonates
xili
181
181
181
183
183
184
185
185
192
195
196
199
200
202
204
204
206
206
208
209
209
210
210
211
212
215
215
216
216
219
221
224
224
xiv
Contents
8.3.2 Surface Treatments: stearate treatments; organotitanate treatments; proprietary and miscellaneous treatments
8.3.3 Filler Properties and Selection Criteria: maximum
particle size; particle size distribution and mean
particle size; colour (dry brightness); refractive
index; oil (or plasticiser) absorption; dispersion
characteristics; cost.
8.3.4 Applications, and Effects of Filler Loading: flooring; plasticised compounds; rigid PVC
8.4 Functional Fillers
8.4.1 Reinforcing Fillers: asbestos (chrysotile) fibres; inorganic microfibres; glass fibres; carbon fibres;
glass spheres; fine-particle calcium carbonate
8.4.2 Flame-retardant and Smoke-suppressant Fillers
8.4.3 Miscellaneous Functional Fillers: carbon black;
metal powders; wood flour; starch; synthetic
silicas
8.5 Some Filler Suppliers and Trade Names
References . . . . . . . . . . . . . . .
225
228
232
240
240
247
248
251
253
Chapter 9
255
255
256
256
260
261
263
265
270
275
286
Conren~
10.1
10.2
10.3
10.4
Introduction
Choosing a Commercial Stabiliser . . .
The Importance of a Well-balanced Lubricant System
One-pack Systems and the Physical Form of Stabiliser
Products . . . . . . . . . . . . . . . . . . . . .
10.5 Hygiene and Environmental Considerations . . . . .
10.6 UK Stabiliser Manufacturers-Product Ranges and Applications
10.6.1 Associated Lead Manufacturers Ltd
10.6.2 Ciba-Geigy Ltd . . . . . . . . .
.....
10.6.3 Durham Chemicals Ltd
10.6.4 Diamond Shamrock Polymer Additives Division
10.6.5 Victor Wolf Ltd
References . . . . . . . . . . . . . . . . . . . . . "
xv
292
292
294
299
299
300
302
304
305
305
308
311
311
315
328
330
330
335
335
337
339
340
341
342
342
346
348
351
356
356
Chapter 11
Some MisceUaneous Components of PVC Formulations-W.
V. TITOW . . .
11.1 Lubricants . . . . . . . . . . . . . . . . . . . .
359
359
xvi
Contents
359
364
367
370
371
372
375
401
401
403
405
407
410
419
420
422
424
424
427
435
Chapter 12
MisceUaneous Properties of Special Interest in PVC Materials
and Products-W. V. TITOW
12.1 Introduction
439
439
CQnren~
xvli
439
442
442
442
443
452
466
469
483
483
486
487
495
496
498
499
500
501
509
Chapter 13
Industrial Compounding Technology of Rigid and Plasticised
513
513
514
514
519
519
519
519
525
xviii
Contents
530
532
532
547
547
577
603
609
660
660
664
673
673
674
674
Contents
xix
682
689
698
699
703
710
713
713
714
717
719
723
723
724
726
728
728
728
729
734
735
735
736
738
738
738
740
740
xx
Contents
Chapter 16
Sheet 'Thermoforming and Related Techniques for PVC-The
late L. W. TURNER
16.1 Introduction
16.2 Materials Used . . . . .
16.3 Vacuum Forming of Sheet
16.3.1 Principal Methods: negative forming; plugassisted forming; drape forming; bubble forming; snap-back forming
16.3.2 Details of Methods
....
16.3.3 The Moulds
16.3.4 Finishing . . . . . .
16.4 Matched-mould and Related Methods
16.5 Tolerances in Dimensions and Dimensional Stability of
Formed Parts . . . . . . . . . . . . .
16.6 Equipment Suppliers
16.7 Materials Assessment and Design Aspects
16.7.1 Effect on Quality of Draw Ratio and Temperature . . . . . . . . . . .
16.7.2 Thermoformability of CPVC
References . . . . . . . . . . . . . . .
Chapter 17
Blow Moulding of PVC-W. V. TITOW . . . . . . . . . .
17.1 Basic Features and Historical Development of Blow
Moulding
17.2 Blow-moulding Processes and Their Application to
PVC
17.2.1 General Characterisation and Main Features of
Processes and Systems: main characteristics of
extrusion; injection, and dip blow moulding; the
role and effects of stretching in stretch-blow
moulding; processing and equipment arrangements; cooling methods
17.2.2 Industrial Blow Moulding of PVC: some process
and equipment considerations; extrusion blowmoulding equipment; injection blow-moulding
equipment; dip blow-moulding equipment;
sources of information on blow-moulding
743
743
745
745
745
751
753
754
755
756
757
757
759
761
761
763
763
765
765
Contents
equipment . . . . . . . .
17.3 PVC Compositions for Blow Moulding
17.3.1 The Processing Aspect . . .
17.3.2 The End-use Aspect . . . .
17.3.3 PVC Bottle Formulations: PVC polymer; stabiliser system; impact modifiers; lubrication; other
additives . .
17.4 PVC Blow Mouldings
17.4.1 Applications
17.4.2 Properties and Tests
References . . . . . . . . . . .
xxi
784
789
789
792
793
795
795
797
800
Chapter 18
Calendering of PVC-W. V. TITOW
18.1 Introduction
18.2 The Calender . . . . . . . .
18.3 The Calendering Operation: General Features and Their
Effects on the Structure and Properties of Calendered
Sheet
18.4 Calender Lines . . . . . . . . . . . . . . . . . .
18.4.1 General-purpose Line: pre-calender (compounding and feed) section; calendering; the
post-calender train
18.4.2 Special Lines and Arrangements: calendered
flooring lines; lamination on or at the calander
18.5 The Formulation Aspect . . . . . . . . . . .
18.6 Some Faults and Defects of Calendered Sheeting
18.6.1 Simple Dimensional Faults
18.6.2 Structural Defects . . . . . . .
18.6.3 Faults Manifested in Appearance
18.7 Further Processing of Calendered Sheet
18.7.1 Press Finishing
18.7.2 Press Lamination
18.7.3 Surface Treatments: printing; coating; embossing . . . . . . . . . . . . . . . . .
18.7.4 Continuous Lamination
18.8 Properties and Applications of Calendered Materials
References . . . . . . . . . . . . . . . . . . . . .
803
803
804
808
809
809
828
830
833
833
834
835
837
837
837
838
839
840
847
xxii
Contents
Chapter 19
849
849
856
866
867
869
878
879
883
883
884
886
889
890
890
891
893
896
897
898
Chapter 20
901
901
904
910
910
923
930
932
Contents
processing
References
Chapter 21
PVC Pastes: Properties and Formolation-W. V. TITOW
21.1 Introduction
21.2 PVC Pastes: Rheological Properties and Theory . .
....
21.2.1 Viscosity of a Simple Suspension
21.2.2 Main Compositional Factors Influencing the
Apparent Viscosity of PVC Pastes . . . .
21.2.3 Expressions for the Apparent Viscosity of
Pastes . . . . . . . . . . . . . . . . . .
21.2.4 Variation of Paste Viscosity with Rate of Shear,
or with Time at Constant Shear Rate
21.2.5 Gelation and Fusion of PVC Pastes . . . .
21.2.6 The Measurement of Viscosity of PVC Pastes
21.3 Paste Components and Formulation . . . . . . . .
21.3.1 The Polymer: paste polymers; extender polymers
21.3.2 Plasticisers
21.3.3 Stabilisers
21.3.4 Fillers
21.3.5 Thickening Agents (for Thixotropic Plastisols
and Plastigels)
21.3.6 Miscellaneous Paste Components: viscosity depressants; diluents; other minor additives .
21.4 Pastes for Rigid Products: Organosols and Rigisols .
21.4.1 Organosols
21.4.2 Rigisols
References
xxiii
932
936
939
939
940
941
942
943
945
951
960
962
%2
965
969
970
973
975
975
975
976
978
Chapter 22
Preparation, Processing and Applications of Pastes-W. V.
TITOW . . . . . . . .
22.1 Introduction
22.1.1 Preparation . . . . .
22.1.2 Conversion to Products
22.2 Applications
22.2.1 Rotational Casting . .
981
981
981
982
986
986
xxiv
Contents
Chapter 23
PVC Latices-Revised and edited by W. V. TITOW
23.1 Introduction
23.2 Types of PVC Latices
23.2.1 Homopolymer Latices
23.2.2 Unplasticised Copolymer Latices
23.2.3 Plasticised Copolymer Latices .
23.3 Some Properties of Polymeric Products from PVC
Latices
23.3.1 Mechanical Properties
23.3.2 Toxicity Considerations
23.4 Compounding
23.4.1 Latex Property Modifiers: latex stability; wetting agents; thickeners; antifoaming agents; pH
modifiers and buffers
. . . . . . . .
23.4.2 Polymer Property Modifiers: heat stabilisers;
plasticisers; fillers; pigments
23.5 Anti-blocking Techniques
23.6 Applications
23.6.1 Textile Applications: as bonding agents in nonwoven fabrics; for coating or impregnation of
fabrics . . . . . . . . . . . . . . . . . .
988
991
992
996
998
1010
1012
1013
1013
1016
1017
1017
1018
1018
1018
1019
1019
1020
1029
1039
1040
1040
Contents
xxv
1042
1044
1044
1045
Chapter 24
1047
1047
1048
1048
1049
1054
1057
1060
1063
1065
Chapter 25
1067
1067
1069
1069
1078
1080
1080
1085
1092
1092
1093
1094
xxvi
Contents
1094
1095
1095
1101
1103
1104
1104
1106
1107
1110
1111
1111
1112
1113
1114
1115
1116
1117
1117
1117
1118
1118
1118
1118
1120
1121
1121
1122
1125
Contents
xxvii
Appendix 1
1127
1131
1131
1134
1135
1135
1136
1137
1137
1137
1137
1138
1138
1138
1139
1139
1139
1140
1140
1140
1140
1142
1144
1144
1146
1147
1148
1148
1148
1149
xxviii
Contents
1150
1150
1156
1157
1158
1158
1160
1160
1160
1162
1163
1165
1167
1167
1167
1167
Appendix 2
Quantities and Units: The SI System: Unit Conversion
Tables--Compiled by W. V. TITOW
1169
Appendix 3
Some Material Properties of PVC
Componnds-Compiled by W. V. TITOW
Index 1
General
Products
and
1185
. , . . . . . . . . . . . . . . . . . . . . . . 1199
Index 2
Material and Product Trade Names . . . . . . . . . . . . 1223
Index 3
Named Equipment and Processes . . . . . . . . . . . . .
1231
W. V. Trrow
Yarsley
Research
D. L. BUSZARD
Market Development and Technical Service, Plastics Chemicals,
Ciba-Geigy Industrial Chemicals, Tenax Road, Trafford Park,
Manchester, MI71WT, England
P. S. COFFIN
General Manager-Technical, Roeol Ltd, Rocol House, Swillington, Leeds, LS26 2BS, England
P.
FRANZ
HENSCHEL
Miss N.
HERBERT
xxx
I. D. HOUNSHAM
Sales Manager, PVC Division, Croxton and Garry Ltd, Curtis
Road, Dorking, Surrey, RH4 lXA, England
B. J. LANHAM
European Marketing Manager, LNP Plastics Nederland BV., PO
Box 13, Ottergeerde 24, Raamsdonksveer, The Netherlands
The late L. W. TuRNER
Formerly Senior Research Associate, Yarsley Technical Centre Ltd,
Redhill, Surrey, England
CHAPTER 1
Introduction
W. V.
TITOW
W. V. Titow
* These designations (with a space after the first, lower case letter) are
prescribed by two international standards: ISO 2898/1 and ISO 1163/1 (but
current revision proposals include changes from u PVC and p PVC to PVC-U
and PVC-P). The letters iPVC are sometimes used to designate a high-impact
compound.
introduction
the plastics industry the term 'vinyl' is firmly associated with PVC, in
the way just mentioned.
A few other relevant standard definitions may be noted in passing.
Vinyl chloride plastic: 'A plastic based on polymers of vinyl chloride
or copolymers of vinyl chloride with other monomers, the vinyl chloride
being in the greatest amount by mass'. (ISO 472-1979).
Rigid PVC compounds: 'Rigid plastic compounds composed of
poly(vinyl chloride), chlorinated poly(vinyl chloride), or vinyl chloride
copolymers, and the necessary compounding ingredients. The resin
portion of copolymer compounds shall contain at least 80 percent vinyl
chloride. The compounding ingredients may consist of lubricants,
stabilizers, non-poly(vinyl chloride) resin modifiers, and pigments,
essential for processing, property control and colouring.' (ASTM
D 1784-81).
Unplasticised compounds of polymers of vinyl chloride: 'Compounds
based on homopolymers of vinyl chloride, or copolymers with at least
50% of vinyl chloride, or chlorinated poly(vinyl chloride), or mixtures
of such polymers with each other or with other polymers, the principal
ingredient being a polymer of vinyl chloride. These compounds may
also contain fillers, colorants, and such small quantities of other
ingredients as are necessary to facilitate fabrication, such as stabilizers
and lubricants.' (ISO 1163/1-1980(E)).
Non-rigid vinyl chloride polymer and copolymer moulding and
extrusion compounds: Compounds based on '... nonrigid vinyl
chloride polymer and copolymer classes in which the resin portion of
the composition contains at least 90% vinyl chloride. The remaining
10% may include one or more monomers copolymerized with vinyl
chloride or consist of other resins mechanically blended with polyvinyl
chloride or copolymers thereof. These nonrigid vinyl compounds are
defined by a hardness range and include the necessary stabilizers,
plasticizers, fillers, dyes, and pigments to meet the designated
requirements'. (ASTM D 2287-81).
Flexible PVC compounds: 'Compounds ... manufactured from polyvinyl chloride or from a copolymer of vinyl chloride of which the major
constituent is vinyl chloride, or from both. Such materials shall be
W. V. Titow
Introduction
W. V. Titow
1 Introduction
was fully utilised only slowly. The need to modify the rubber extruders
employed for the early production work soon became plain, and
modifications were made, e.g. to enable the material to be fed-in in
granular form, and to provide higher processing temperatures (by
electrical heating). A special ram extruder was employed in Germany
for a time to produce rigid pipe from a PVC billet. 15
Thanks to the work of Kaufman the early history of PVC polymers,
compounds, and processing is well recorded and documented. 15 ,16 The
development of modern PVC-processing equipment and of the many
specialised processes which form such an important part of present-day
PVC technology has paralleled the remarkable expansion of the
production of PVC and the scope and number of its applications.
The 1970s brought two unforeseen events of major significance both
in their initial impact and their lasting effects upon the PVC
industry-the oil crisis of 1973/74 (with its aftermath of continuing oil
price rises), and the finding that vinyl chloride monomer (VCM) is a
carcinogen.
The oil crisis-after first causing a serious temporary shortage of the
oil-derived principal feedstocks for VCM production (ethylene and
acetylene-see also Chapter 2), and hence of PVC polymers (ct. the
drop, c. 1974, of the curves of Fig. 1.1)-resulted in large, and
continuing, increases in polymer prices. These are the outcome of
higher costs of both the feedstocks and the energy (also largely
oil-supplied) used to process them into monomers and thence into
polymers. It may be noted that one of the developments prompted by
this situation has been a refocusing of interest on coal-based raw
materials and processes, with special reference to the acetylene route
to the production of VCM:
HC:=CH + HCI ~ CHr-CHCl
(1)
Ca~
+ CO
(2)
(coke)
Ca~
(3)
=:
E
c
o
"c;l
"t:
+'
01
g3
tI
CIl
1964
Fig. 1.1
,----I
1972
/',/
/'
,/
1976
"
,...
./
/'
/"
"",.
/.~
1984
__ x
/'/'
/'
---
/'
/'
/'/'
/'
-- -- --
/"
1980
~,.-----Japan
/"
,,'/
/'
,/
1968
-----
--~/x--'-~
W~st~rn
Europ~
./
./
/'
:0:::::
00
1 Introduction
The chlorine and hydrogen needed for the HCI used in reaction (1) can
be produced by electrolysis of brine (with caustic soda as a saleable
by-product). Some industrial plants manufacturing VCM and PVC
polymer by this process have been in operation for many years (e.g.
the AECI 'Coalplex' plant at Sasolburg, RSA).
The discovery, in the early 1970s, that exposure to VCM could cause
certain forms of cancer, coupled with the realisation that VCM
concentrations in factory atmospheres and its residual contents in PVC
polymers were comparatively high, had repercussions on PVC polymer
production in several countries. It also caused a serious decline
(especially in the USA and Japan) in the use of uPVC films for food
packaging, and blow-moulded bottles for beverages and oils. The legal
action for 285 million dollars brought in the USA against Borden
Chemical and Goodyear Tire and Rubber Co. (two PVC polymer
producers) by some supermarkets, in respect of 'damage to health' by
PVC film used to wrap meat,17 is an example of the extremes of feeling
in some quarters. Soft PVC was comparatively less affected, as the
dilution effect of large amounts of plasticiser and greater loss in
processing reduced the VCM concentration in the compounds to
relatively low proportions. The considerable effort expended on
investigating and remedying the situation, together with relevant
regulations brought out in the major industrial countries, led to a vast
reduction of VCM contents in both the factory air and PVC polymers
produced by virtually all main manufacturers. The 'clean-up' brought
the content levels down to values now regarded as acceptable on the
basis of data obtained in extensive studies. The subject is discussed in
more detail in Chapter 12 (Section 12.9.1), and also mentioned in
Chapters 2 and 7.
A third topic-albeit of comparatively lesser importance in the PVC
context than the oil crisis and the VCM problem-which has been
receiving increasing attention in recent times is the disposal of plastics
waste and re-usable material. Concern with preservation of resources
and conservation of the environment provides the main incentive in
these two related areas. Dealing with PVC waste involves special
considerations. Selective reclamation, i.e. separation from waste
mixtures with other plastics (which operation is not a straightforward
proposition in itself), and subsequent re-processing are complicated by
the wide variety of PVC formulations, and the increased susceptibility
to heat degradation in re-processing: the main factors in the latter are
the 'heat history' already acquired and the possible presence of
10
W. V. Titow
1 Introduction
11
TABLE 1.1
Consumption of PVC Polymers, by Main Outlet, in Western Europe (Including UK) and the USA in 1970 and 1976
Western Europe
(1000 metric tonnes)
Outlet
1970
Film and sheet (rigid and
flexible)
Calendered
Extruded
Flooring
Calendered
Coated
}
}
430
(21'5%)
1976
}
}
USA
(1000 metric tonnes)
1970
1976
}
}
605
(191%)
259} 341
82 (24,8%)
195
(61%)
113} 147
34 (10'7%)
550
(27'5%)
230
(115%)
785
(24'7%)
335
(10'6%)
215
(15'7%)
186
(13-5%)
682
(31'9%)
150
(7'0%)
Records
40
(2,0%)
78
(2'4%)
64
(4'8%)
68
(32%)
Blow-moulded bottles
110
(5'5%)
235
(7-4%)
32
(23%)
35
(16%)
20
(10%)
235
(11'8%)
82
(2'6%)
505
(159%)
39
(2'8%)
23
(17%)
104
(4'9%)
177
(8'3%)
134
(6'7%)
265
(8'3%)
187
(13'6%)
190
(8'9%)
72
(3-6%)
90
(2'9%)
138
(10,1%)
283
(13-2%)
2000
(1000%)
3175
(100,0%)
1372
(100'0%)
2139
(100,0%)
Total
178
(8'9%)
200 305
105 (14,2%)
75
70
145
(6'8%)
12
W. V. Titow
polymer producers;
compounders;
processors;
companies selling finished goods consisting of or containing
PVC.
Introduction
13
-C-C-
h tl
14
W. V. Titow
,*
(Tf - Tfo)/Tfo
15
1 Introduction
5'8
90000
80000
70000
r{ 60000
5-2
I~
'"
.J
50
5-0+-100000
40000
30000
48
--50000
20000
46
w. v.
16
Titow
and
~CH2-CHCI-CH2-TH-CH2-CHCl~
1 Introduction
17
I
CHz
I
CHCI
18
w.
V. Titow
(b) Morphology
Commercial PVC polymers may be regarded as essentially
amorphous,34 although crystalline material contents of about 2-10%
have been reported on the basis of determinations by X-ray diffraction
methods, thermal analysis (DTA, DSC, TMA) , and density
measurements. 35-37 The crystallinity is associated with the stereoregular (syndiotactic) polymer fraction. 38-40
The glass transition temperatures (Tg ) of commercial homopolymers
lie in the range 80-84C (as determined by DTA, DSC and TMA).34,35
Annealing above the Tg increases crystallinity and also the crystalline
melting temperature (as given by the endothermic peak on DTA
curves).35,37 The density of the crystalline fraction has been reported as
1530 kg m-3 (1,530 g cm-3) and that of totally amorphous (quenched)
polymer as 1337kgm- 3 (1337gcm- 3).35
As would be expected, annealing below the Tg has no effect on
crystallinity: however it can increase the density-this has been
attributed to a reduction of the free volume in the polymer without
ordering of its fine structure. 35 Apparently the kind of short-range
non-crystalline ('domain') order which can develop in some essentially
glassy, but partly crystallisable polymers (bisphenol-A polycarbonate,
polyethylene terephthalate)41-44 on heating below the Tg , does not
arise in PVc.
Relatively highly crystalline PVC polymers (up to about 45%
crystallinity) with high syndiotactic material content, have also been
prepared (by polymerisation at low temperatures or in certain
solvents).24,36,38,45,46 The preparation of fibres and film from such
polymers has been reported47 as well as that of plasticised compounds
(with about 50 phr DOp).38,47 The melting points of the crystalline
polymers can be as high as 265_273C24 ,46 (cf. commercial PVC
polymer-about 210C in the absence of decomposition). The
introduction
19
20
W. V. Titow
1 Introduction
21
Vinyl chloride/ethylene
Refs 40 and 53
Literature/References
Chapter 26
6. Chapter 26
5. Chapter23
2. Chapters 19 and 26
3. Chapters 21 and 22
4. Chapters 12, 24 and 26
2. Chapters 24 and 26. The copolymers used for these applications sometimes contain a
third co-monomer
3. Chapters 23 and 26
1. Chapters 2, 3 and 26
Vinyl chloride/vinyl
acetate (VCNA)
Relevant chapters/Remarks
Copolymer
TABLE 1.2
Vinyl Chloride Copolymers
<t
::;j
:00:::
Surface coatings-E; SL
Vinyl chloride/vinyl
isobutyl ether
Vinyl chloride/acrylic
ester
3. Chapter 23
2. Film and bottles (uPVC) with good transparency, heat weldabihty and impact strength-S
3. Adhesives, finishing agents, coatings-E
1. Window-frame compositions-8
Calendered sheet-S
Vinyl chloride/vinyl
cetyl ether
1. Graft copolymers
Vinyl
chloride/triftuorochloroethylene
Vinyl chloride/EVA
Refs 47,65,66
Ref. 64
v.>
;:s
~.
f2-
;;-
'-
24
w.
V. Titow
1 Introduction
25
26
W. V. Titow
Tgeq
PVC
Fully chlorinated
homopolymer PVC polymer
6567
152-159b
99-123
568
140
80-84
90
65
80
110
732"
170
175
1 Introduction
27
28
W. V. Titow
for the production of pipes and pipe fittings for hot-water installations
(including, increasingly, domestic central heating systems), where the
general similarity of properties to uPVC (including, inter alia,
suitability for jointing by solvent welding) combined with the greatly
increased temperature resistance in service, are particularly advantageous. Other applications include pipes and fittings for potable water
(CPVC is approved for this purpose by several professional and
regulatory bodies 75), pipework and associated products (fittings,
valves, tanks) for chemical plant (the general chemical resistance of
CPVC is comparable with that of uPVC) , extruded profiles, sheets
(including co-extruded CPVClpPVC sheets), some electrical appliances, and constructional applications.
Some examples of commercial CPVC compounds are: the Lucalor
range (Rhone-Poulenc, France), which includes Lucalor RB 1266
specially developed, and recently evaluated, for central heating
systems; the Dekadur compounds (Deutsche Kapillar Plastik, West
Germany) and the CPVC compounds in the Geon range (B. F.
Goodrich, USA). Some of the properties of three Geon compounds
are listed, by way of example, in Table 1.4.
TABLE 1.4
Some Properties of 'Geon' CPVC Compounds
Property
Geon 88933
(high temperature
extrusion and
injection moulding)
Geon 88934
Geon 88935
(extrusion of (profile co-extrusion
pipes and
with pPVC-high
profiles)
ductility compound)
8200
8400
7300
14500
15600
13600
387000
395000
396000
23
20
32
100
102
82
152
157
147
1 Introduction
29
Most other countries also issue their own national standard specifications.
Those standards from the four main sources which relate directly to
PVC are listed (by number and title) in Appendix 1. The list is divided
into sections, grouping the standards by subject and also largely
according to their relevance to the chapters dealing with particular
topics in this book. * In addition, many 'plastics' standards not
specifically or primarily directed to PVC, but nevertheless relevant to
particular aspects of PVC materials, products or technology, are
mentioned in the introduction to Appendix 1, in Appendix 3, and in
various appropriate places in the book.
The numerous references to standard specifications throughout this
* For example, Section 4 of Appendix 1 lists standards dealing with various
aspects of plasticisers, and is thus directly relevant to Chapters 5-7.
30
W. V. Titow
REFERENCES
1. Regnault, V. (1838). Ann. Chim. Phys., 2,69, 151.
2. Drukker, H. L. (1944). Proc. of Symposium on Plastics, Am. Soc. for
Testing Materials, Philadelphia, Pa, USA, pp. 165-77.
3. Domininghaus, H. (1976). Die Kunststoffe und Ihre Eigenschaften,
VDI-Verlag GmbH, Diisseldorf, p. 566.
4. Baumann, E. (1872). Ann. Chim. Phys., 163, 308-12.
5. Tester, D. A. (1973). In Developments in PVC Technology, (Eds J. H. L.
Henson and A. Whelan), Applied Science Publishers, London, Chapter 1.
6. Ostromislensky, 1. (1912). British Patent No. 6299; German Patent
No. 264123.
7. Brydson, J. A. (1975). Plastics Materials, Newnes-Butterworths, London, pp. 248-9.
8. British Patent No. 408969, Carbide and Carbon Chemicals Corp., (1934).
9. US Patent No.1 938662, Du Pont, (1933).
10. British Patent No. 387928, British Thomson-Houston, (1932).
11. Canadian Patent No. 346164 (1934).
12. British Patent No. 388309 (1933); US Patent No. 1932889 (1933).
13. British Patent No. 412442 (1934).
14. German Patent No. 470 149 (1927).
15. Kaufman, M. (1969). Plast. Polym., 37(129),243-51.
16. Kaufman, M. (1969). The History of PVC, Elsevier, London.
17. Anon. (1974). Chern. Engng. News, 52(35),8.
18. Trevitt, E. W. (1976). Polym. Paint Col. J., 166(3918), 193-4.
19. Anon. (1979). Eur. Plast. News, 6(6), 8.
20. Billingham, N. C. and Jenkins, A. D. (1972). In Polymer Science, Vol. 1,
(Ed. A. D. Jenkins), North-Holland Publishing Co., AmsterdamLondon, Chapter 2.
introduction
31
32
w. V. Titow
Introduction
33
77. Brown, R. P. (Ed.) (1981) Handbook of Plastics Test Methods. 2nd Edn,
George Godwin Ltd. and the PRI, London.
..,;; 't
Fig. 1.4(A)
~I
nn:,
11'
I,
wave
[A]
I'l~
I
!
"
"
.Itla:.
number, em- 1
r~"
length, lim
illlEtmmnnmuI:H~:
~H ,I",,'
wave
:to
t.
"...
.'1: I
I,
c;;:
:::;j
:<:::
w
-""
Fig. 1.4(B)
It
..
':i
wave
number. cm-'
Ltd.).
Infra red spectra of plasticised PVC (100 parts Corvic D60111, 60 parts DOP-Bisoflex 81-BP Chemicals
[8]
V1
:::
!:l
Q'
::
Q..
::
CHAPTER 2
\.
CH2 =CH2
02/catalyst + HO
CH2 Cl-CH2 Cl
...,
,,,
I'
pyro YSIS
,,
~------------------------------------------------~
Acetylene route
CHa:CH + HC}
(excess)
catalyst
So-250"C
~ CH2=CHCl
38
W. V. Titow
39
80% of total commercial polymer production), emulsion polymerisation (about 10-15 %), bulk polymerisation, also called mass
polymerisation (about 10%), and solution polymerisation.
The commercial application of the solution process is almost entirely
confined to the manufacture of copolymers for use in surface coatings
(see Chapter 24), centered on one major American producer (Union
Carbide). The amount produced probably represents less than 3% of
the total PVC polymer sold in the USA. Polymerisation is carried out
in a liquid which may either be a solvent for both the monomer(s) and
the polymer, or only for the monomer(s) so that the forming polymer
precipitates out of the system ('precipitation polymerisation'). This can
also happen in initially homogeneous systems above a certain degree of
conversion. Initiators and selected chain-transfer agents are included in
a typical solution polymerisation system. The resulting polymers can be
of high purity, and the method affords good control over molecular
weight.
In a typical suspension polymerisation process a suspension of
monomer dropiets (about 50-150.um) in water is formed by vigorous
agitation in a pressure vessel (autoclave), and the monomer of the
droplets, which contains a monomer-soluble free-radical initiator, is
polymerised at a slightly elevated temperature, under the autogenous
VCM vapour pressure corresponding to the reaction temperature (up
to 15 MPa at 80C). Protective colloids are included in the aqueous
phase to stabilise the suspension throughout, and also buffers to
counteract development of acidity. When 80-90% of the monomer has
been converted to polymer the reaction is stopped by venting-off
excess monomer from the reactor. The resulting slurry of polymer in
water is freed from the remaining monomer by further evaporation,
either in the autoclave itself or in a separate vessel. This process is
known as stripping: to secure effective high degree of removal of
residual VCM, stripping is assisted and completed by steam 'sparging'.
Different variants, both batch-wise and continuous, of this operation
exist, all essentially involving scrubbing the slurry with steam at an
elevated temperature. Continuous, counterflow scrubbing in an
efficient column can reduce the VCM content of the polymer to below
1 ppm. The stripped slurry is centrifuged to remove free water, and the
resulting wet polymer 'cake' is dried by hot air.
Note: In the so-called microsuspension polymerisation the general
composition and physical state of the system are more akin to
40
w. v.
Titow
41
w. V. Titow
42
bility are:
1. chemical composition (i.e. whether homopolymer or copolymer,
and-in copolymers-the chemical nature and proportion of
comonomer(s) present);
2. molecular weight (average and distribution);
3. particle characteristics (size and size distribution, morphology).
The nature and amounts of extraneous impurities and adventitious
functional groups in the polymer chains are also significant in some
contexts.
2.2.1 Composition
43
(t - to)/toc
'0
~~'-'
042
044
047
049
052
055
057
060
062
065
067
070
073
075
078
.::1
50
52
54
57
59
61
64
67
70
73
77
80
83
87
90
~~oS
I\,)
I\,)
~V):::E
::
... Q""l
';> ........ ~
""-<l
0lY)
U <".1,-...
::1
" 00
f-..,
0
.~~
Uo":S
V) ::
cs .......
.S~ . . . .
. . . . <;
:: 0\ ."
E""-~
:::t K lY)
I\,)
...
~.?<".1
0155
0165
0175
0185
0195
0206
0217
0228
0239
025
0264
0275
0285
03
031
1216
1227
1237
1247
1258
1269
1280
1292
1304
1316
1329
1342
1355
1369
1383
~~$ ~~ ~
I\,)
.......
"g Oo~~
~ oS '0 ~ ~
I\,) V)
'<:j
;>Q
]-9
8<".1'"
'r;; ~
I\,)
'be:;
f-..,
45
46
47
48
49
50
51
52
53
54
55
56
44
42
43
tl
.....
::.::
;>
~"I
~
47
49
51
52
53
54
55
57
58
59
60
61
::.::c
;>
.2!~
"1-9
I\,)
~~
....... "I
::
I\,)
lY)
... <;
c~
453
462
471
484
493
501
513
524
536
547
561
572
582
595
605
: .:
I\,)
~.'::1
.2!~::
"101\,)
~"ti~
. :: ~
~"Iu
.,,0'"
eo:: '.
~I\,)Q
~"I""""
E:~'"
.... 0
~~
'0
-,-...
""
49
50
51
52
53
54
55
565
575
585
595
605
615
625
635
~~
::.:: 'i:!
I\,)
I\,)
::
"l
.2!..(:)
~I\,)
c ~
;>0.,
::
;>0.,
u":::~
;>
""~
.::1 U
8-9
025
026
027
028
029
031
032
034
035
037
038
040
042
044
045
~~ ~
1\,)~<".1
008
009
010
0105
011
0115
0120
0125
013
014
0145
015
0155
016
017
~ ........ ~
1\,)~lY)
~ E:~ ~E:~
u":::~
;>
::1U'
CS~
U 0
~::
eol\,)
<".1
::
0
--
.-0"1 '-0"1~
001\,)
::
0
."
275
310
350
380
415
450
495
525
560
600
640
680
720
760
800
~{j
1~
:u .....
........
::~
.g~
.g~
...
100000
70000
54000
40000
~~
.~~
~u
~~
;>
:u
I\,)
~~
"I
I\,)
45500
40000
36000
30000
26000
20000
:::t 0
<;E:
E:~
.......
"I ...
"I
I\,) :::t
..(:)u
~ ~
...
~.~
I\,)~
TABLE 2.1
Some Indices of Molecular Weight of PVC Polymers
(Based in part on table compiled by Matthews and Pearson of leI, first reproduced, with permission, in the previous
editionS)
:-:::
.j:o.
.j:o.
080
083
085
088
091
092
095
098
101
103
106
108
111
113
116
118
121
123
126
128
130
133
135
138
032
033
034
036
037
038
039
040
041
043
044
045
046
047
049
050
051
053
054
056
057
058
06
061
1397
1412
1427
1443
1458
1474
1491
1508
1525
1543
1562
1581
160
162
164
1661
1682
1704
1726
1749
1772
1796
1821
1847
57
58
59
60
61
62
63
64
65
66
67
68
69
70
71
72
73
74
75
76
77
78
79
80
62
63
64
65
66
67
68
69
70
705
71
72
73
74
617
629
641
649
661
671
682
692
702
715
724
733
743
749
758
767
775
783
791
799
807
815
822
830
645
66
675
68
69
70
71
72
73
74
75
76
77
78
047
049
051
053
055
057
059
061
063
065
067
069
071
073
075
077
079
081
083
085
087
089
090
093
0175
018
019
0195
020
0205
021
022
0225
023
0235
024
025
0255
026
027
0275
028
029
0295
030
031
0315
032
840
885
930
975
1025
1070
1120
1175
1230
1300
1350
1420
1490
1570
1650
1720
1810
1900
1980
2070
2170
2260
2360
2460
73000
80000
82000
90000
91500
340000
480000
70000
64000
60000
55000
260000
200000
140000
50000
Zl
'"
<:>
(j
~
~
["
'"....
3
3
The correct current term is logarithmic viscosity number (cf. Chapter 1, Section 1.5.1).
This method involves measurement of the viscosity of 02 g/100 ml solution of PVC polymer in cyclohexanone at 30e.
cThis is the viscosity ratio less unity (TJITJo) -1: see Chapter 1, Section 1.5.1, and Section 2.2.2 herein.
d In this method specific viscosity is calculated from the results of determination on a dilute solution of PVC polymer in
nitrobenzene (04g/100 mI). ASTM D 1243-58T and its subsequent (1966) edition have been superseded by ASTM
D 1243-79, the version currently in force. This gives only one method, whereby the viscosity of 02 g/100 ml solution of ...
PVC polymer in cyclohexanone is determined at 30C, and the logarithmic viscosity number calculated from the results. Vl
94
98
102
105
109
113
117
121
125
130
134
138
142
145
149
153
157
161
165
169
173
177
181
185
w.
46
V. Titow
75
K
+
) _ cK (
In (..,.,1""'0 - 1000 1.5 cK + 1000
1)
Depend on
particle
size
distribution
b The grains are aggregates of spherical primary particles (typically about 0'1-2 f-lm in size) which are the originarIatex
particles. The aggregate grains are formed during drying. Their size may be modified by any subsequent grinding.
Grains made up of clusters of primary particles (microgranules). Typical microgranule size of the order of about 1 f-lm.
2-70
100-150
80-200
Bulk polymerisation
Emulsion polymerisation
120-160
50-250
Suspension polymerisation
Means
Process
TABLE 2.2
Polymer Grain Sizes Typical of the Main Polymerisation Processes, and the Relevant Process Factors
:ti
'"<::l
;0
l)
""
'"
'"
48
w.
V. Titow
2.2.4 Purity
Whilst it is not of quite such fundamental universal significance as the
characteristics mentioned in Sections 2.2.1-2.2.3, polymer purity is
important in many applications. In the normal contexts it is a matter of
the absence (or presence in acceptably low amounts) of extraneous
49
W. V. Titow
50
TABLE 2.3
PVC Polymer Properties-Standard Characterisation Tests
Test methodsa
Property
ISO
ASTM
and
Volatile matter
pH of aqueous extract
ISO 1269
ISO 1264
Thermal stability
Vinyl acetate contentd (of
copolymers)
ISO/R 182
ISO 1159 (hydrolysis of
the acetate groups, and
back-titration)
51
TABLE 2.3-contd.
Property
Test methods
ISO
ASTM
D792
ISO 1270
ISO 4612
ISO 4575 (Severs rheometer)
ISO 2555 (rotating viscometer)
Mentioned in ISO 1060/2
but no ISO methods yet
available
Those shown in this table are the ones specifically listed, respectively, in
W. V. Titow
52
Test method
ISO 60
ISO 60
K value
DIN 53 726
Flowability
ISO 6186
Volume resistivity (Q m
or Qcm)
Heat stability
"Some definitions of standard terms relating to viscosity are given in ISO/R 1628
(currently under revision).
3
b Sometimes also determined (in cm g-I) by the mercury intrusion method of ASTM
D2873.
53
G, 121-57
~ill
~
homcpolymer
suspension-produced
general purpose
(i.e. not for paste)
viscosity number - - - - - - - '
bulk density of O' 56 g rnI- 1
Copolymer for melt processing:
ISO 1060-VCNAC
88-S,
G, 080-75,
17
vinyl chloride/acetate
88% vinyl chloride-derived
suspension-produced
general purpose
viscosity number (80)
bulk density 075 grnl- 1 - - - - - - - - - - - - '
particle size limits (by reference
to numbered 'classes'-here classes 1 and 7)
plasticiser absorption by particles
(X indicates that the value is not specifically designated)
Applications
Apparent densiti
(ISO 60) (g 1- )
Mean particle size
(AECI method) (,urn)
Particle porosity
(plasticiser absorption, ISO 4608) (phr)
Volatile content (AECI
method) (%)
Type
Polymer
properties
530-560
470-520
110-160
24-31
<05
550-580
110-160
16-22
<05
<05
17-24
110-160
60-65
Suspension
66-75
Suspension
Suspension
Rigid, calendered
sheeting (for
packaging)
65-68
Flexible tubing
and cable
compounds
Rigid pipe
<02
110-160
650-750
Copolymer
(suspension)
47-51
VelVA
copolymer
(for flooring)
<05
10-50
350-450
Emulsion (paste
grade)
65-80
Paste polymer
TABLE 2.5
Typical Basic Property Value Ranges of 'Corvic' (AECI) PVC Polymer Grades Recommended for Some Major
Applications
Vl
:0::::
::;j
""'"
55
TABLE 2.6
Country
Trade name
South Africa
Corvic
USA
France
West Germany
B. F. Goodrich
Borden Chemical
Chemische Werke Hiils
Chemopetrol
Chisso Corp.
Conoco Chemicals Co.
Denki Kagaku
Dutch State Mines
Electro Chern.
EVCC
Hoechst
ICI
Kanegafuchi Chemical
Industry
Mitsui Toatsu Chemicals
Inc.
Montedison
USA
USA
West Germany
Czechoslovakia
Japan
USA
Japan
Netherlands
Israel
Holland
West Germany
UK
Airco
Lacqvyl
Vinoflex, Vinidur,
Lutofan
Geon
Borden
Vestolit
Neralit
Nipolit
Conoco
Denkavinyl
Varlan
Epivyl
Various names
Hostalit
Corvic
Japan
Kaneka
Japan
Italy
Norsk Hydro
Produits Chimiques
Ugine Kuhlmann u
Rhone-Poulenc Ind. u
Shell
Shinetsu Chemical Industry
Co.
Shintech Inc.
Singapore Polymer Corp.
Societe Artesienne du
Vinyle b
Solvay et Cie.
Stauffer Chemical Co.
Tenneco Chemicals Co.
Union Carbide Corp.
Wacker Chemie
Norway and UK
Vinychlon
Sicron, Vipla,
Viplavil (copolymer)
Norvinyl
France
France
Netherlands
Ekavyl
Lucovyl
Carina
Japan
USA
Singapore
Shinetsu
Shintech
SPC
France
Belgium
USA
USA
USA
West Germany
Artevyl
Solvic
SCC
Tenneco
Bakelite
Vinnol
57
TABLE 2.7
Some Commercial Polymer Trade Names, Past and Present
Trade
name
Manufacturer
Beetle
Breon
Dacovin
Ekaryl
Etinox
Exon
FPC
Halvic
Irvinil
Kohinor
Lonzavyl
Marvinol
Mirvyl
Pekevic
Pevikon
Plaskon
Pliovic
Quirvyl
Ravinil
Reynosal
Ricon
Ruco
Scon
Trovipor
Vixir
Vygen
Uniroyal Inc.
Rio Rodano SA
Neste Oy
Kema Nord
Allied Chemical Co.
Goodyear Tire & Rubber Co.
Rumianca SpA
ANIC SpA
Reynolds Chemical Co.
Rico Chemical Corp.
Hooker Chemicals
Vinatex Ltd.
Dynamit Nobel
Societa Italiana Resine SpA
General Tire & Rubber Co.
Country
UK
UK
USA
France
Spain
USA
USA
Austria
USA
USA
Switzerland,
West Germany
USA
Spain
Finland
Sweden
USA
USA
Italy
Italy
USA
USA
USA
UK
West Germany
Italy
USA
REFERENCES
1. Hardie, D. W. F. (1964). In Kirk-Othmer Encyclopedia of Chemical
Technology, Vol. 5, 2nd Edn, John Wiley, New York, pp. 171 ff.
2. Anon. (1982). Plast. Rubb. Wkly, (964), 20th November, p. 1.
3. British Patent 1553829, ICI; US Patent 4158092, Hoechst.
58
W. V. Titow
CHAPTER 3
TITOW
3.1 INTRODUCTION
There are two general ways in which a user of PVC compounds, i.e.
the processor who converts them into products, can acquire the
compositions he needs. He can do his own compounding, or he can
buy compounds from a commercial producer, either as stock lines, or
specially compounded to his requirements. In-house compounding by
the processor has traditionally involved own compound manufacture as
a separate operation: in the case of solid compositions (as distinct from
pastes) this normally includes conventional batch-wise production of
powder pre-mixes and dry blends. Industrial compounding technology
of solid compounds and pastes is discussed in detail in Chapter 13. A
paper by Adams 1 provides a useful summary of the advantages of
in-house compounding of solid PVC compositions. Recently equipment has been coming into use which makes possible continuous
preparation of powder compounds at the extruder, so that such
compounding can, in effect, be integrated into the extrusion line.
Several advantages, both technical and economic, are claimed for this
kind of arrangement, including suitability for small-scale operations
with relatively low outputs2 (see also Chapter 19, Section 19.3).
However, many small and medium-sized extrusion operators who do
not wish to, or cannot, invest in such equipment, as well as other
processors in these size categories, use purchased compounds: this
brings the benefits of the commercial compounder's special equipment
and expertise without own capital and staff commitments. Even large
processors who are equipped to produce their own compounds usually
59
60
W. V. Titow
61
Werner and Pfleiderer, Pappenmeier, and others (see also Chapter 13,
Section 13.4.4).
TABLE 3.1
Commercial PVC Compounds: General Outline of Types
General type
Extrusion compounds
Nature of composition
Rigid
Flexible
Injection-moulding
compounds
Rigid
Flexible
Blow-moulding
compounds
Rigid
Flexible
Masterbatches
Powder coating
compoundsb
Mainly flexible
Pastes
Various grades available within each type. See also Tables 3.3-3.7, and relevant
information on the processing and applications of PVC compositions in other chapters.
b Primers required for application of the coating compounds to metal surfaces are
normally available from the compound suppliers.
63
64
W. V. Titow
All these specifications are listed, with dates and titles, in Section
3.1(a) and (b) of Appendix 1 (ISO 1163/1 and 2898/1 are currently
under revision). The DIN designation systems and test are similar to,
but not identical with, the corresponding ISO ones.
The designation systems are based on principles similar to those used
for PVC polymers, as illustrated by the following examples. The
examples also indicate what properties are used for the purposes of
designation.
ISO
DESIGNATIONS
DIN
ASTM
65
Test methods
e.g. ISO 60
}
Powder blends
e.g. ISO 6186
e.g. as in Table 2.4
Melt flow
Impact resistance
Volume resistivity
Durometer hardness, or
BS softness
Powder
blends
or
meltcompounded
pellets
Cable
compounds
3.4.3
Chemical resistance
*
*
*
ISO [[63/1
*"
ASTMD1784
*
*
*
*
:::1
0DIN 53 457 (N mm- 2 )
~
:<:::
DIN 7748
Property
TABLE 3.2
Section A: Standard Tests Used in Characterisation of Unplasticised PVC Compounds
*
*
*
*
*
ASTM D 2287
*
*
*
*
*
*
*
*
*
*
*
*
Plasticiser loss
Plasticiser migration
Resistance to chemicals
ISO 2898/2
Property
a-
;::
;::
~0
'1;l
~
~
i'"
~
~
v"
Density (g cm- 3 )
Tensile strength (MPa)
Compressive strength (MPa)
Flexural strength (MPa)
Young's modulus (MPa)
Coefficient of linear thermal
expansion (per 0c)
Specific heat
(cal g-l C- 1 )
(kJ kg- 1 C- 1 )
Thermal conductivity
(Wm- 1 C- 1 )
Softening temperature
(BS 2782) (0C)
141
41
59
83
2800
78
76
Highimpact
pipe
about 025
about 1
133
134
38
41
48
66
55
93
76
79
3400
2400
2400
about 5 x 10- 5
144
48
Highimpact
for close
tolerance
extrusion
137
55
66
90
3400
Pressure
pipe
fittings
3400
72
139
41
66
General
purpose
2800
72
134
41
55
Highimpact
78
79
73
78
77
73
77
93
3400
66
138
45
16 x 10- 6 16 X 10- 6
137
52
66
93
3400
Pressure
pipe
Extrusion compounds
TABLE 3.3
Section A: Properties GeneraUy D1ustrative of Some Commercial Rigid PVC Compounds
;'!;
:::l
0\
00
Application type
115
115
119
127
125
10-20
90-150
10-20
350-500
20-40
Phthalate
Phthalate
Phthalate
Phosphate
Adipate
Density at
25C
(gcm- 3 )
Viscosity
at 25C
(P)
Main
plasticiser
type
Paste properties
Shore A hardness
(ASTM D 2240)
42-44
47-49
72-74
56--58
96--98
Cold-bend
temp. (0C)
(BS 2782: 1970)
-55
-55
-35
-25
-25
Product properties
Section B: Examples of Some General Types of PVC Paste Represented Among Commercial Stock Lines
t}
;::
;:,
.g
.:
3
3
'";:::
"'"
~
42
46
21
21
19
40
146
83
149
82
147
79
Glossy
finish
48
19
46
22
147
79
Good mould
filling
characteristics
Pressure pipe
fittings
Rigid microcellular
profiles for
building
applications
Development
grade
*0
General
purpose
RI7IU43
MPR/7JI70
RI71U67
Injection-moulding grades
Asterisk indicates property values strongly dependent on the density of the extruded cellular product.
Property dependent on the processing history of the product: the figures quoted are conservative values.
Characteristics
R8/M936
Profiles and
conduit
R8/JI25
Applications
R71J168
Extrusion grades
TABLE 3.4
Section A: 'Welvic (AECI) uPVC Dry Blend and PeDet Compounds for Extrusion and Injection Moulding
(Data reproduced, with permission, from the technical literature of AECI Chlor-Alkali and Plastics Ltd)
::;j
:0:::
Cl
--_._----~
115
45
6 x 10- 5
14 X 10- 4
5 x 10 14
1 x 1012
C- 1
J m m- 2 S-l C- 1
Qcm
Q
BS 4618
AECI
BS2782
BS2782
Typical value
Rockwell R scale
Hardness
Limiting oxygen index
Coefficient of linear
thermal expansion
Thermal conductivity at 23C
Volume resistivity
Surface resistivity
Units
ASTM D 785
ASTM D 2863
Test method
Property
-..l
!}
;:s
l::
~C
r3
"l:I
.,'"
".:
;?!
;?!
""
~
W. V. Titow
72
TABLE 3.5
'Welvic' (AECI) PVC Compoonds for Electric
(Table reproduced, with permission, from the technical
ApplicatkJn
Grade
Use
seclor
C%urs:" Specifica/ion
Softness Hardness Relative
(BSS No.) (Shore A) density
N-Narura/
C-C%urs
CL-Clear
BS2782
Hard dielectric
66 kV cable dielectric
G.P.
High speed, thin wire
insulation
G.P.
G2lU65
GD2lU15 Fast extrusion, filled
G.P.
G3/U6
Cabtyre sheathing,
G3/U87
filled
G4lU7
G.P.
GD2IJI48 Flame retardant
Hame
insulation
retardant
and sheathing
Insulation DI/U21
or
DIIJI91
sheathing GI/U4
GDlIJ034
High tern
perature
insulation
or
sheathing
HIIJ180
H21J2oo
H21J263
H4lU85
Telephones G4lU31
N5/U16
Clear in
sulation
X21J364
JO/1365
X4IJ366
Welding
cable
sheathing Y3/J331
Development
grades
G2IJ301
G2IJ302
H21J246
Y5/J357
Petrol/oil resistant
Low HCI emission
sheathing
Low HCI emission
bedding
Crosslinkable hightemperature
dielectric
Trailing cable
sheathing
Tensile properties
Tensile
Tear E/ongastrength strength lion at
(MPa) (Nmm- J) break
(%)
BS2782 BS6746 BS2782
10
10
9
97
97
97
134
l-41
133
212
209
23-4
104
115
116
240
200
260
N+C
N+C SABS 150-1970
N+C SABS 150-1970
N+C SABS 150-1970
14
20
20
30
94
90
90
83
134
134
148
130
192
205
152
186
99
104
82
72
230
35
40
80
145
128
IH
172
45
63
350
280
330
300
350
21
90
147
178
94
220
N+C US Underwriters
N+C US Underwriters
9
20
97
90
139
135
220
208
122
75
220
280
N+C US Underwriters
18
92
139
190
90
230
N+C US Underwriters
44
74
129
124
63
260
55
45
74
126
186
N+C
54
69
121
117
340
350
CL
24
87
130
232
100
210
CL
35
80
128
211
79
230
CL
45
74
127
186
59
250
N+C
36
79
129
20
90
156
20
90
159
48
72
125
140
330
N+C
All values are typical results measured in ACE)'s Plastics Technical Service Laboratory.
" C%ur: Standard colours are Natural lOS and Black 901. Non-standard colours are available 00 request. Masterbatches are also available for
colouring purposes:
MBIDIOOI
MBIDIOO9
MBID1201
MBIDI302
MBID/404
MBID/451
White
Cream
Yellow
Orange
Red
Pink'
MBID/501
MBID/509
MBID/601
MBID/606
MBID/607
MBlDn03
Golden Brown
Dark Brownt
Dark Greeot
Green
Turquoise
Blue
MBIDI803 Violet
MBID1901 Black
MBID1957 Grey
' Brighter than BS 6746 C Colour
t Darker than BS 6746 C Colour
73
Loss in
Hot
defor.
mass on
ageing
mation
(mgcm- 2 ) (%)
Tensile
.strength
Elonga
97
94
97
98
92
94
04
08
04
97
96
92
99
85
100
90
100
98
97
Limiting
n
fIJ:x
ASTM
Cold bend
temperature
('C)
te~eratu,e
'C)
Volume
resistivity
at2lfC
(Oem)
BS2782
BS2782
BS2782
Cold flex
(%)
Surface
finish
Recommended
extrusion
temperatures
('C)
tion at
break
SABS
SABS
1501970 1501970
BS6746
BS6746 D28631976
40
3 x 1014 Glossy
6 x 1014 Satin
4 x 1014 Glossy
-30
29
39
-40
-25
10
15
8
10
06
06
07
39
50
44
68
-50
-40
5
-10
-12
-9
23 x 1014
13 x 1014
12 x 1014
4 x 1013
Glossy
Glossy
Satin
Glossy
145/150115511601165
145/150115511601165
145/1501155/1601165
1401145/1501155/160
100
100
10
07
70
-32
-45
-10
-15
2 x 1013 Satin
28 x 1013 Glossy
140/145/1501155/160
135/1401145/150/155
98
94
06
36
-30
-5
2 x 1014 Satin
94
100
99
96
02
055
39
38
-35
-40
15
-5
155/160/165/1701175
145/1501155/160/165
96
90
07
42
-35
-I
8 x 1014 Glossy
145/150/155/1601165
6 x 1013
Glossy
1401145/150/155/160
35 x 1013 Glossy
135/1401145/1501155
90
100
06
100
100
12
70
-40
-30
33
28
25
-45
-22
-40
-20
-50
87
90
053
-40
-35
44
1501155/1601165/170
1501155/16011651170
1501155/1601165/170
145/1501155/16011651170
28
x 1010
Glossy
130/135/1401145/150
20
x 1013
Glossy
1401145/1501155/160/165
x 1012
91
108
055
50
-40
-2
45
Glossy
140/145/1501155/160
93
100
059
65
-45
-8
12 x 1012 Glossy
135/140/145/1501155
Glossy
1401145/150/155/160
29
Satin
135/1401145/1501155
28
Satin
135/140114511501155
70
33 x lO" Glossy
145/1501155/160/165
74
W. V. Titow
TABLE 3.6
'Welvic' (AECI) PVC Compounds
(Table reproduced, with permission, from the technical
Apptication sector
Use o
Grade
Colours: b
N=Natural
C= Colours
B= Black
Specifications
Softness Hardness
(BSSNo.) (ShoreA)
BS2782
Relative
density
BS2782
Crystal-non-toxic
EX31U49 Food
Clear
37
78
123
G. P. extrusionopaque
GIIU4
G2JU65
Profiles
Profiles
Profiles
Profiles
Garden and mining hosing
Garden and mining hosing
Profiles
Profiles and waterstop
Profiles
N+C
N+C
N+C
N+C
N+C
N+C
N+C
N+C
N+C
9
20
30
35
35
35
97
90
83
133
134
130
1-45
126
135
128
1-41
126
Profiles
Profiles
Profiles
Profies
Clear
Clear
Clear
Clear
G.P. extrusioncrystal
G31U6
G31U87
G31J194
G31J196
G41U7
G41U88
G61U9
X2JJ364
X31J365
X41J366
X6IJ346
SABS645
40
46
80
80
80
77
73
60
66
24
35
45
63
87
74
64
130
128
127
126
N+C
99
167
20
90
131
99
137
131
130
80
Rawlplug extrusion
GO/J088
Rawlplugs
Antistatic extrusion
N2JU46
Antistatic hosing
Outdoor weathering
WO/U54
WllUl
W2JU2
N+C
N+C
N+C
5
10
21
97
89
Y3/J331
Y31J182
Fuel hosing
Fuel hosing
Clear
N+C
35
36
79
80
127
129
Oil/grease resislant
Y6IU56
N+C
60
66
145
Low temperature
Y51J165
Refrigeration
Gaskets
N+C
N+C
56
68
131
Clear
42
75
PetroUoil resistant
hosing outer
Clear
SABS645
and 1086
122
sheathing
All values are typical results measured in ACEI's Plastics Technical Laboratory.
a When specific contact with a foodslUff is involved. the advice of ACE]'s Plastics Technical Service Laboratory should
be
75
Tear
strength
(Nmm- t )
8S2782
8S6746
Elongation
at break
(%)
8S2782
Loss in
mass
on age;nj
(mgcm- )
Hot
deformation
(%)
8S6746
8S6746
300
184
45
73
260
350
330
300
290
04
06
07
10
14
17-2
124
131
63
73
53
350
310
400
07
09
09
232
211
106
145
100
79
59
33
210
230
250
350
053
055
059
09
234
205
186
131
161
116
101
72
39
50
68
77
64
70
76
84
44
50
65
88
Cold
bend
('C)
Cold
flex
temperature
('C)
8S2782
8S2782
temperature
Recommended
extrusion
temperatures
('C)
-45
-7
Glossy
1351140114511501155
-25
-40
-40
-32
-50
8
-10
-9
-10
-15
Glossy
-45
-35
-45
-15
-30
-34
Satin
Glossy
1501155116011651170
145/1501155/1601165
140114511501155/160
1401145115011551160
1401145/1501155/160
140/145/150/155/160
135/140114511501155
135/140114511501155
12511301135/140/145
-35
-40
-45
-45
8
-2
-8
-20
Glossy
Glossy
Glossy
Glossy
1401145/1501155/160
140/145115011551160
1351140/145/150/155
120112511301135/140
170
103
Surface
finish
Satin
Glossy
Satin
Glossy
Glossy
Glossy
Satin
1601165/1701175/180
Satin
145/150115511601165
207
227
207
132
117
105
260
260
320
04
04
05
32
38
40
-30
-30
-35
10
5
-5
Glossy
Glossy
Glossy
160116511701175/180
150/155116011651170
145/1501155/1601165
184
77
300
15
61
-50
-10
Glossy
Glossy
140/145/1501155/160
140/145/150/1551160
Satin
120/125/130/1351140
Satin
125/13011351140/145
Glossy
135/140114511501155
108
-30
350
110
37
230
10
20%
78
-40
-18
63
70
80
87
90
95
Il/Jl09
I2IJl01
131J102
151J104
15/1341
I6IJl05
1611329
17/Jl06
191J130
1811293
19/U109
191J108
B&C
B&C&Cl
B&C&Cl
B&C&Cl
B&C
B&C&CI
B&C&Cl
B&C&CI
B&C
B&C&O
B&C&O
B&C&CI
13
65
17/J220
B only
25
50
60
70
75
80
15/U75
I6IJl23
171J162
171M965
I8IJl63
52
53
54
57
64
61
80
71
69
66
95
86
63
71
66
61
59
57
121
118
119
117
120
121
125
124
122
123
131
126
138
126
127
134
123
133
Colours
Relative
Recommended Softness Hardness
B=Black
grade
density
(BSS No.) (Shore A)
C= Colours
(Natural at 23"'C)
C/=Clear
B&C
B&C
B&C
B&C
B&C
ParticularsQ
General type
99
93
103
98
n5
130
157
149
130
145
157
180
107
13-l
149
no
105
100
Tensile
strength
(MPa)
240
410
230
380
280
245
290
295
290
260
260
250
315
340
330
360
400
360
Elongation
at break
(%)
-40
-50
-36
-35
-35
-35
-35
-25
-29
-25
-25
-24
-8
-15
-20
-20
-25
-30
-35
-35
-3
-5
-27
-10
-20
-25
-25
-30
-15
-20
-30
-24
-25
-35
-34
-35
1
1
1
1
1
Cold
Cold
Loss of
bend
flex
mass at
temperature temperature l()(f'C
(%)
("CJ
("CJ
TABLE 3.7
'Welvic' (AECI) PVC Compounds for Flexible Injection Moulding and Footwear
(Table reproduced, with permission, from the technical literature of AECI Chlor-Alkali and Plastics Ltd)
required
~~~SeBSaf~~~~t~~s.
17/J367
17/1336
1811368
19/1356
B&C
B&C
N4IJ354
B only
B&C
B&C
N31J34O
MI8I1353
B&C
B only
MI8IJ278
B&C
1211351
MI61J270
B&C
B&C
MI4IJ274
B&C
40
80
95
70
73
40
32
20
80
80
54
77
57
52
61
60
77
82
90
57
57
69
l'24(0'7)b
121
1-17
1-17
1-16
128
130
134
1'20(07)
1'20(07)
123(07)
95
90
55
35
57
60
200
375
220
330
310
135
150
350
-35
-40
-33
-35
-35
-25
-29
-25
-25
-10
-...l
-...l
All values are typical results measured in AECI"s Plastics Technical Service Laboratory. Test methods according to BS 2782: 1970.
Q Where specific contact with a foodstuff is involved, the advice of AECI's Plastics Technical Service Laboratory should be sought. The approval of the finished article is the fabricator's
Iesponsibility.
Properties quoted for microcellular compounds are approximate values. Densities in parenthesis are minimum blown values using suitable equipment.
Development
grades
Microcellular
78
w.
V. Titow
REFERENCES
1. Adams, H. J. (1976). 34th ANTEC SPE Proceedings, pp. 330-2.
2. Weber, M. (1983). Plastics and Rubber International, 8(5),32-4.
3. Titow, W. V. and Lanham, B. J. (Eds), (1971). PVC Technology, 3rd Edn
Applied Science Publishers, London, pp. 62-3.
CHAPTER 4
TITOW
4.1 INTRODUCTION
As has been mentioned in Chapter 1, PVC resins-whether homopolymers or copolymers-must be modified by the incorporation of
appropriate additives for satisfactory processing and end-use performance. The necessary modifications are more varied and extensive than
those practised with any other polymer of major industrial importance,
but so also is the applicational versatility of PVC in the form of the
resulting materials.
In this chapter the terms 'composition' and 'compound' are used
generically for the material which results when PVC resin is combined
with the necessary additives, and the operations involved in making a
composition are collectively called 'compounding'.
Note: Compounding may consist of, or include as one of its stages,
mixing and/or melt-compounding. The former term applies
either to the blending together of the constituents to produce a
solid composition in the form of a free-flowing powder or
powder agglomerate (either of these may be referred to as
'pre-blend' or 'dry blend', depending on the context), or to
their mixing to form a liquid composition, i.e. a paste, latex,
or solution. Melt-compounding is the operation (commonly
carried out on a mixed pre-blend) whereby the constituents of
a composition are intimately combined with the resin in the
melt, under heat and shear: the resulting compound is
normally pelletised (granulated).
79
w.
80
V. Titow
1------ --------,
Compounding
: Physical forms:
r---..L---,
Composition
L..-_.,....----J--
powd(lr agglom(lrat(l
(pr(lbl(lnd; dry bl(lndJ
:
(b) P(lII(lts; granulat(l
I Liquid: (a) Past(l
I
(b) Lat(lx
I
(c) Solution
1-
------1
Proc(lssing
IProd"~
:
1
I
I
I
Furth(lr proc(lsslng
t.I
IS(lcondary product 1
----------J
81
(i)
82
W. V. Titow
83
w. V. Titow
84
required, and for this the volume content of each component of the
formulation is worked out from the weight content and density values.
These points are illustrated by the following example of a simple
plasticised compound (an extrusion compound of BS softness about
20):
Component
Parts by weight
(g)
Density
(gem- J )
Parts by volume
(em3)
1000
500
70
10
1580
140
099
381
093
7143
5050
184
108
12485
PVC polymer
Plasticiser
Stabiliser
Lubricant
135
1-10
n
1-1n
OOOln
OOOlln
Volume cost
(perem3)
135 x OOOln = 000135n
110 x OOOlln = 0001 21n
85
PVC polymer
Plasticiser
Stabiliser
Lubricant
Weight
proportion
(kg)
Cost per kg
100
500
70
10
1580
040
050
040
025
C
Cost in formulation
()
(A
x B)
()
40
25
28
025
6805
86
w. v.
Titow
In general, the higher the molecular weight of the polymer (and hence
its K value and viscosity number-see Chapters 1 and 2) the better
many mechanical properties of the composition but the more difficult
its processing (because the ease of fusion and melt flow decreases with
increasing molecular weight). The choice of the molecular weight
grade (K value) of a commercial polymer to be used in a particular
formulation is normally a compromise between what is the most
desirable for processing on one hand and service properties on the
other. The processing considerations become less critical with
adequately plasticised compositions, so that polymers of higher K
value can be used in those-typically 65 to 71 t (ICI range 60-65, Fig.
4.2), as against 54 to 65t (ICI range 50-60) in uPVC (with the lowest
molecular weight polymers used in those rigid compositions where the
easiest melt flow is required, e.g. in some injection-moulding and
bottle-blowing compounds). The molecular weight distribution of the
polymer also affects physical properties and processing: it is normally
maintained within certain limits in a given commercial polymer grade.
KIND (PROCESS TYPE)
Except for the special case of formulating PVC solutions for surface
coatings, for which polymer produced by the solution process will
normally be used (see Chapters 2 and 24), the choice will be between
suspension polymers, mass (bulk) polymers or emulsion polymers (i.e.
PVC resins produced by those three polymerisation processes-see
Chapter 2). For PVC paste compositions emulsion polymers are used
87
80
70
50
60
70
80
Fig. 4.2 The relationship between ICI K value and K value determined by
viscosity measurement on a solution of 05 g PVC resin in 100 ml cyclohexanone (ct. Chapter 1, Fig. 1.2, and Chapter 2, Table 2.1)
88
W. V. Titow
89
21).
QUALITY
Note: ISO 472-1979 defines 'fish-eye' as 'a small globular mass which
has not blended completely into the surrounding material and
is particularly evident in a transparent or translucent material'. In PVC polymer fish-eyes (also called gels) are hard,
particulate specks of polymer which are not dispersed in
processing and thus remain as discrete inhomogeneities in the
finished product. A standard method of determining the
number and size of fish-eyes in general-purpose PVC resins is
given in ASTMD3596-77 (see also ASTMD3351-74: Gel
count of plastic film).
Low-grade polymer can be used, in admixture with a standard grade
or even alone, in formulations for the cheaper kinds of injectionmoulding compositions, usually fairly heavily filled, used for the
production of cheap moulded footwear (sandals, slipper soles) and
toys. High-grade polymer is necessary for such uPVC products as
transparent ('clear') packaging film and bottles, and in plasticised
compositions for clear medical products (e.g. containers and tubing for
saline drip sets), clear, flexible hose and packaging film (e.g.
'clingwrap') .
(b) Heat Stabilisers
Whilst the main mechanisms involved in the complex process of
thermal degradation of PVC and its counteraction by stabilisers are
90
W. V. Titow
Several lead salts and some lead 'soaps' (notably lead stearates) are
widely used as stabilisers in PVC (the soaps partly for their lubricant
properties). Lead compounds are the oldest general-purpose stabilisers, comparatively cheap, and capable of imparting good long-term
stability. They have always dominated the electrical insulation
applications of pPVC compounds, because lead chloride, formed when
a lead stabiliser reacts with HCl (a principal decomposition product of
PVC-see Chapter 9), is insoluble and non-ionisable, so that the
electrical resistivity remains unimpaired as the stabiliser discharges its
function. In uPVC compositions lead stabilisers are used in many
formulations for extruded cladding and profiles: dibasic lead phosphite is of particular interest for opaque products for outdoor use, as it
imparts very good light stability. In Europe lead stabilisers are also
used in uPVC pipes, although in the USA tin stabilisers (see below)
are favoured for this area of application. The main limitations and
disadvantages of lead stabilisers as a group are toxicity (hazards in
processing, as distinct from potential risks in compounds, are reduced
91
92
W. V. Titow
93
The materials which may be grouped under this heading are the
already mentioned epoxy compounds and organic phosphites, most
commonly used as auxiliary, synergistic stabilisers with some metal
stabiliser systems. The epoxy compounds are very often epoxidised oils
(e.g. epoxidised soyabean oil), but epoxidised esters and some epoxy
resins can also be used (see also Chapter 9).
(c) Plasticisers
As has been mentioned, plasticisers convert the hard, inherently brittle
PVC resin into compositions of varying degrees of softness and
flexibility, processable into a variety of products with divers properties
and uses (determined to a large extent by the nature and amount of
plasticiser(s) present). Plasticisers and their effects in PVC are
discussed in several chapters of this book (in particular Chapters 5 to
7): because these chapters cover the subject thoroughly, and because
of its complexity and extent, only the most basic, general pointers are
given in the present section.
The proportion of plasticiser in a pPVC composition is always fairly
substantial, and may be very high in very soft materials. For this
reason cost considerations are particularly important in plasticiser
selection. In the absence of special processing and/or service
requirements which may dictate the choice (see below) the formulator
will normally consider first a relatively inexpensive, general-purpose
plasticiser. In most cases this will be a phthalate, very often dioctyl
94
W. V. Titow
95
(d) Lubricants
The functions of lubricants in PVC compositions are:
(i) to reduce the friction at, and adhesion to, working surfaces
when the composition is being processed (external lubrication);
and/or
(ii) to lower the inter-particle and inter-molecular friction in
processing (internal lubrication); this reduces the effective melt
viscosity and heat build-up.
Some lubricants discharge only, or mainly, one of these two
functions and are, accordingly, referred to as internal or external
lubricants; others act in both ways. The main factor determining the
type of lubricant action is the lubricant's compatibility with PVC: a
true external lubricant is poorly compatible, and a good internal
lubricant highly compatible with the resin. Chemical compounds used
as lubricants include paraffins, paraffin oils, polyethylene waxes, fatty
acids, fatty acid amides and esters, fatty alcohols, and metal soaps.
Lubricants must be used in uPVC compositions (for both internal and
external effects: two or even more lubricants are often combined, up to
a total content of about 3 phr) , and are beneficial in many plasticised
compositions (in amounts within the range O 2-1' 5 phr) mainly for
external lubrication, as much of the internal function is discharged by
the plasticiser. The nature and amount of lubricant(s) used in a
formulation depend critically and in a complex way on several factors,
viz. the other components (see below), the processing to be undergone
by the composition (the correct choice is particularly important in
many calendering compositions), and any subsequent treatments (e.g.
films to be printed must have no exuded external lubricant on the
surface). Possible interaction or co-action with other constituents of
the formulation, especially the stabiliser(s), is a most important
consideration in the choice of lubricant(s) and the amount(s) to be
used. For example, some stabilisers have a lubricant action, and/or
benefit from synergistic co-action with certain lubricants, whilst some
lubricants also exert a stabilising effect; more lubricant may be
necessary in compositions highly loaded with fine-particle fillers
(because of absorption effects), but relatively less if the filler is
surface-coated with a stearate (see Chapter 8); the degree of
Price economy
Characteristics required
Polymeric plasticisers;
for some purposes:
trimellitates,
high molecular weight
phthalates,
solid blending resins (e.g.
chlorinated PE, EVA
copolymers, nitrile rubber)
Examples of application
TABLE 4.1
Some General Features of Plasticiser Usage
o~
:::J
:<:::
BBP,DBP,
triaryl phosphates,
phthalates
Processing properties:
(a) Ease of solvation, fusion, and gelation
Packaging films
Clear compositions
Protective clothing
Tarpaulins, flexible tubing for use in
cold conditions
Foamed coatings
5'
;::s
i:>
I::
~
~
.5;,
(")
?-
is
W. V. Titow
98
99
in more detail in Chapter 11, Section 11.2). In most cases there is also
some processing-aid action, but this may be significant only at
processing temperatures higher than those at which regular processing
aids exert their effect. Some types of impact modifier (e.g. (iv), (v),
and certain kinds of (vii) below) are highly compatible with PVC and
may be incorporated in high proportions, to act as plasticisers (see
Chapter 11, Section 11.2). Commercially available impact modifiers
are polymers of the following types:
(i)
(ii)
(iii)
(iv)
(f) Fillers
The use of fillers in PVC is discussed in some detail in Chapter 8, and
referred to in other parts of the book in connection with various filled
compositions and products. Only the most basic points relevant to the
role and application of fillers in PVC formulations are briefly
100
W. V. Titow
TABLE 4.2
Filler
Precipitated
whiting
Hard clay
Carbon black
Omya BSH
Parts by weight
30
40
10
20
1700
1700
1700
1700
1420
1780
1900
1615
1350
1710
1920
1590
1200
1450
1550
1580
920
1200
1750
1370
50
60
750
890
510
1110
1250
1070
101
Filler
Composition a
content
and
properties
Resin
Di-2-ethyl hexyl phthalate
Tribasic lead sulphate
Paraffin wax
Filler: M 501 b
M501 (phr)
Nil
5
15
10
2500 2500 2500 2500
T~nsile strength
(lbfin- 2)
Modulus 100%
extension (lbf in -2) 1500 1700 1800 1900
Elongation at break
(%)
300 280 270 250
Tear strength (lb in-I) 1200 1300 1400 1400
32
38
32
30
BS softness No.
Volume resistivity,
conditioned x 1014
(23C, 65% RH)
11
03
13
15
Volume resistivity
(Qcm x 1014 ,
24 h immersion)
02
3
7
6
Volume resistivity at
60C x 1012
06
50
90 110
a Compounding
100
50
7
1
As stated
} Parts by
weight
20
2400
30
40
50
2500 2400 2500
2000
230
1400
29
13
12
100
90
70
60
102
W. V. Titow
103
104
W. V. Titow
105
Chapter 25, Section 25.3), and discoloration which may result through
interaction of some lead stabilisers with impurities in lubricants of the
glycerol ester type (cf. Chapter 11, Section 11.1.2(a)), or through the
interaction of sulphur-containing tin stabilisers with lead-containing
pigments (due to formation of coloured sulphides).
4.4.3 Side Effects of Formulation Components
(i)
(ii)
(iii)
(iv)
(v)
(vi)
(vii)
106
w.
V. Titow
(ii)
(iii)
(vi)
(vii)
107
plastics products (ct. Chapter 7, Section 7.12 and Chapter 12, Section
12.9), or-in cases of doubt-directly with such organisations.
4.5.2 Resistance to Weathering
This is of paramount importance in such PVC products as rainwater
goods, window frames, cladding, fencing, films for reservoir or
swimming-pool lining, tarpaulins and the like. Particular heat stabiliser
systems, normally incorporating synergistic co-stabilisers of the epoxy
type with chelators, are highly relevant here (see Section 4.4.1(b)
above; Chapter 9; and Chapter 12, Section 12.6), and-among lead
stabilisers-dibasic lead phosphite (see Chapter 9). Ultra violet
absorbers are also widely used in weathering-resistant formulations.
Polymeric modifiers in rigid products (e.g. rain guttering and
down-pipes, window frames) should be of the type which detracts least
from good weatherability, such as VClEVA copolymers or selected
acrylic modifiers (alternatively the PVC resin used may be a VClEVA
graft copolymer-see Chapters 1 and 2).
4.5.3 Electrical Insulation
The use of emulsion PVC polymer is precluded in this application (see
Section 4.4.3(b)(iii) above, and Chapters 1 and 2) because of the
deleterious effect of the trace impurities it contains upon electrical
resistivity (and hence insulation value). Lead stabilisers are the first
choice (for the stabilisation of all but transparent compositions)
because they are electrically non-conductive. For insulation and cable
covering resistant to high temperature selected plasticisers must be
used (ct. Chapter 7, Section 7.5.3 and Chapter 12, Section 12.3).
108
W. V. Titow
100
11-15 phr
12-20phr
02-05 phr
100
l'5-2'Ophr
02-03phr
10-12 phr
02-04phr
100
11-15 phr
05-08 phr
05-0'8 phr
109
08-20 phr
(iv) Calendered, clear pPVC with good stability to light: generalpurpose and horticultural applications:
PVC polymer (S or M, K value 69-72)
Stabiliser: BalCd liquid (e.g. Irgastab BC 26)
Co-stabilisers: epoxidised soyabean oil
an organic phosphite (chelator)
Plasticisers: DOP
triaryl phosphate
UVabsorber: (light stabiliser, e.g. Tinuvin P)
External lubricant: stearic acid
100
13-16 phr
5 phr
04-0'5 phr
55 phr
10 phr
02-03 phr
02-04 phr
100
0,9-1,8 phr
0'3-0'6phr
42phr
13phr
40phr
100
2'0-4'Ophr
CZ45M)
60-8Ophr
15 phr
10-2Ophr
110
w.
V. Titow
10-15 phr
100phr
160phr
100
2phr
12 phr
06phr
111
100
5phr
52phr
32phr
05-10phr
40phr
100
7phr
70phr
1phr
6phr
100
7phr
30phr
30phr
13 phr
70phr
W. V. Titow
112
4.6.5
Gramophone Records
100
1S-17phr
02-03 phr
10-1S phr
A copolymer resin is used for ease of processing, with low K value for
the best surface-detail reproduction (associated with ease of flow). The
carbon black should be of a sufficiently fine and readily dispersible
grade to meet this important requirement. An antistatic agent is
usually incorporated in the composition: this should be selected inter
alia for minimum effect on thermal stability.
4.6.6 Blow-moulded Bottles
(i) For mineral water:
100
0IS-020 phr
OOS-OlO phr
04-0S phr
30 phr
100 phr
OS-10 phr
100
14-16phr
10-12 phr
113
1-2 phr
10-15phr
100
l'0-2'Ophr
Irgastab 1'270)
Impact modifier: ABS type
Processing aid: acrylic type
Lubricants:
Internal/external: calcium stearate
fatty acid ester type
External: polyethylene wax
Pigment: titanium dioxide
Colourant: phthalocyanine type
8-lOphr
15-25 phr
08-10 phr
O5-10 phr
005-01 phr
3 phr
002-003 phr
Irgawax 360)
100
1,5-25 phr
5phr
03-05 phr
The lubricant used should be chosen, inter alia, for its suitability in a
clear formulation.
100
4phr
5phr
80phr
33phr
114
w.
V. Titow
100
6phr
1 phr
l'9-2'Ophr
0'4-0'8phr
6-10 phr
18-22phr
100
12-15 phr
04-05 phr
5 phr
47 phr
0'1-04 phr
100
2phr
65 phr
17phr
* Emulsion type.
100
20-30phr
115
40phr
35phr
5 phr
lOphr
100
15-30 phr
50 phr
85phr
20phr
100
15-25 phr
6'0-8'Ophr
45phr
30phr
25-45 phr
5phr
for the blowing agent in this foaming composition. The BBP (butyl
benzyl phthalate) is a highly solvating plasticiser, widely used in PVC
foam formulations for rapid, uniform fusion of the composition.
Top coat
PVC polymer (E, K value 70-72)
Stabiliser: liquid BalCd/Zn complex (e.g. Irgastab
BC206)
Co-stabiliser: epoxidised soyabean oil
Plasticiser: DDP
Pigment: titanium dioxide
Filler: whiting
Colourant: as required
100
15-25 phr
50 phr
52phr
0'0-3'Ophr
00-100 phr
The stabiliser is one suitable for clear PVC to enable the formulation
to be used for unpigmented, unfilled compositions.
CHAPTER 5
BUSZARD
118
D. L. Buszard
119
Plasticiser class
Phthalates
Phosphates
Aliphatic dibasic acid esters
Trimellitates
Polymerics
Epoxies
Chlorinated paraffins
Hydrocarbons
Others
% by weight
740
50
20
05
19
50
95
19
02
120
D. L. Buszard
this
also
not
no
121
+-
+Scr~~n typ~
Hing~ typ~
122
D. L. Buszard
very brief. For more detailed reviews of the theories the reader is
referred to several textbooks which cover the subject in much greater
depth,6,22,23 or to an extensive review of relevant literature, prepared
by Stafford for the RAPRA PVC-plasticiser Group.24,25
5.5
From the time a plasticiser first comes into contact with a PVC
polymer until the production of the final fused product-and possibly
even for some time after this-a complex series of interactions occurs.
Since the precise processing conditions and heat history of a PVC
plastisol are easier to control, the majority of the initial work
concentrated on the liquid-solid transition. Stich studies demonstrated
that increasing temperature led to an initial lowering of viscosity,
followed by a rapid rise. 26 ,27 Alter26 described the vertical region of the
viscosity/temperature curve as the gel region. Newton and Cronin27
refer to the attainment of 1000 P as the setting temperature.
McKenna28 devised a temperature gradient bar, and, by casting and
stripping of PVC films, determined gelation temperatures. Greenhoe 29
continued work on the temperature gradient bar and was able to define
six transition points between liquid plastisol and the fully fused
product. These were, with increasing temperature, the fluid point
(where the plastisol becomes dry and putty-like), dry point (where it
changes to a dry, crumbly solid), gel point (where physical strength
begins), haze point (where clarity increases), elastomeric point (where
tensile strength and elongation to break develop), and fusion point
(where optimum tensile strengh is attained).
Wheeler and Clifton30 used the concept of the temperature gradient
bar to develop the Geigy Gel Block, and Critchley et ai. 31 published
an extensive comparison of the gelation properties of different
plasticisers determined with this apparatus.
Although for practical reasons it is easier to follow PVC-plasticiser
interaction in plastisols, similar studies have been carried out on melt
blends, using a Brabender Plasti-Corder,32 and on dry blending. 33 ,34
Van Veersen and Dijkers34 compared published data from different
sources,35-39 and demonstrated that different methods involving
different processing techniques still show a comparable trend for the
solvation process of PVC when mixed with plasticisers (Table 5.2).
Diethyl phthalate
Dibutyl phthalate
Dihexyl phthalate
Dioctyl phthalate
Diisodecyl phthalate
Plasticiser
92
97
127
138
56
60
80
86
88
86
104
118
132
eC)
eC)
72
Solid/gel
transition
temperature3?
(0C)
Solvation
point 36
Dry point 35
65
75
75
80
85
Maximum
swelling
temperature 38
eC)
TABLE 5.2
58
62
84
84
94
Relative
melting
temperature39
(0C)
N
W
......
S"
;:.
1:;'
"l::l
~::to
"'"f;;
i:l
'"
"~
::to
<:;)
...'"
;;l
u,
124
D. L. Buszard
Sears, Darby and Touchette40 ,41 summarised the stages of plasticisation as follows:
(i) Irreversible uptake of plasticiser into the porous resin.
(ii) Absorption of the plasticiser, during which the total resinplasticiser volume may decrease although the resin particles
swell slowly on the outside.
(iii) Diffusion of the plasticiser within the particles with little or no
volume change, but involving high activation energies. At this
stage the plasticiser is probably present as clusters of molecules
between bundles of polymer segments or molecules.
(iv) The final stage of plasticisation when the plasticiser molecules
penetrate the bundles of polymer molecules so that they are no
longer rigidly held together but behave as a polymer in its
rubbery rather than glassy state.
In some processes these four steps may not be clearly defined and may
overlap. With the usual plasticisers for PVC, of moderate molecular
weight, plasticisation can only proceed through the first two steps at
room temperature. Steps (iii) and (iv) have high activation energies
thus requiring a threshold temperature to be reached.
5.6 REQUIREMENTS FOR PVC PLASTICISERS
It is obviously of great importance for the plastics industry to be able
125
/-LV2 =
P2 VIV~
V2 - - - -
Me
126
D. L. Buszard
+',5
+1
0+..........;........-.__
~ I
o~
~ I
-IO'C----,,:OO,;:_
200
500
Molcculor Wclqhl
127
TABLE 5.3
Plasticiser
Molecular
weight
Solubility
parameter
t> (call/2 mrl/2)
194
278
278
362
390
390
418
105
94
Dimethyl phthalate
Dibutyl phthalate
Diisobutyl phthalate
Dihexyl phthalate
Dioctyl phthalate
Diisooctyl phthalate
Dinonyl phthalate
Diisodecyl phthalate
Benzyl butyl phthalate
Tritolyl phosphate
Trixylyl phosphate
Dioctyl sebacate
Ceredor S52 (ICI)
92
90
885
885
85
85
446
312
326
410
426
99
98
975
84
93
97
Polyvinyl chloridea
a Solubility
by the plasticising effect of pure isomers of TXP, all of which have the
same calculated solubility parameter53 of 975 but widely differing
compatibility and plasticising effects (Table 5.4).
The solubility parameter of the chlorinated paraffin, Ceredor 552,
suggests that it should be much more compatible than is found in
practice.
TABLE 5.4
Xylenol isomer
Melting point of
TXpeC)
2:6
2:5
3:4
2:3
137
2:4
Liquid at room
temperature
3:5
78
71
58
40
Plasticising effect
Stiffest composition
Most incompatible
Not compatible
Borderline compatibility
Compatible
Compatible
D. L. Buszard
128
Tm
0'002226+0'3151(1- X)/V i )
(1)
129
TABLE 5.5
Clear point
temperature
(0C)
Dioctyl phthalate
Diisooctyl phthalate
Di-Linevol 79 phthalate
Diisodecyl phthalate
Ditridecyl phthalate
Benzyl butyl phthalate
Low temperature Dioctyl adipate
Diisodecyl adipate
plasticisers
Dioctyl azelate
Dioctyl sebacate
Tritolyl phosphate
Phosphates
Trixylyl phosphate
Re%s 50 (Ciba-Geigy)
Santiciser 148 (Monsanto)
Trioctyl phosphate
Trioctyl trimellitate
Trimellitates
Reomol LTM (Ciba-Geigy)
Morflex 525 (Pfizer)
Crestapol538 (Scott Bader)
Polymerics
Diolpate 150 (Briggs & Townsend)
Diolpate 171
Palamoll 644 (BASF)
Plastolein 9503 (Unilever-Emery)
Plastolein 9506
PLastoLein 9765
ReopLex 430 (Ciba-Geigy)
Reoplex GL
ReopLex 903
ULtramoll I (Bayer)
ULtramoll II
Phthalates
117
116
114
139
150
102
138
156
154
151
98
101
100
98
118
142
132
147
138
164
137
155
141
144
151
163
123
153
155
165
MW
The values of
lX
103
(2)
D. L. Buszard
130
TABLE 5.6
Flory-Huggins Interaction Parameters (X)
Plasticiser
Xb
053
062
052
048
032
Dioetyl sebaeate
Ceredor S52 (ICI)
Dioetyl adipate
Trioetyl trimellitate
Benzyl butyl phthalate
Mesamoll (Bayer)
Dioetyl phthalate
Dibutyl phthalate
Oetyl diphenyl phosphate
O 28
010
-003
-005
-035
017
007
005
004
-002
lYe
08
10
14
12
26
25
24
34
33
(2x8)+7 = 11.5
2
Similarly, the dioctyl phthalates have an AplPo ratio of 8 since aromatic
C atoms are ignored.
The AplPo ratio of a wide range of plasticisers correlates well with a
number of properties, including melting point, specific gravity,
modulus, water absorption, etc. (see also Section 5.7).
131
TABLE 5.7
Plasticiser
Dimethyl phthalate
Diethyl phthalate
Dibutyl phthalate
Dibutyl succinate
Dihexyl phthalate
Dibutyl adipate
Dioctyl adipate
Dibutyl sebacate
Trioctyl phosphate
Dihexyl azelate
Dioctyl adipate
Diisodecyl phthalate
Dioctyl azelate
Dioctyl sebacate
Ditridecyl phthalate
SGTT
eC)
93
88
86
96
104
98
1
2
121
127
8
95
10
118
117
137
139
142
150
151
4
5
6
8
8
10
115
12
13
The AplPo ratio also correlates well with the clear point temperature,
termed Solid-Gel Transition Temperature (SGTT) by Van Veersen
and Meulenberg37 (Table 5.7). In the same paper they also show clear
relationships with the data of Anagnostopoulos et al., 56 Darby and
Graham,36 Wiirstlin and Klein,62 Jasse,63 and Doty and Zable. 46
(f) Loop or Roll Compatibility Tests
These are extremely simple but very useful tests for assessing the
compatibilities of plasticisers or plasticiser mixtures in a given PVC
formulation. A number of test method variations exist, with differing
degrees of severity, but the general principle is as follows.
A test strip is moulded from the compound and rolled into a fairly
tight roll,37 or bent into a loop of fixed dimensions,64 and stored under
controlled conditions. Compatibility is judged on the amount of
plasticiser exuding out of the compound, when the tension is released,
from the inner surfaces of the PVC sample. The assessment is normally
visual, and although therefore subjective, a considerable degree of
accuracy can be achieved. It is well worthwhile carrying out such a
test-which takes at most 24 h-on any formulation in which
incompatibility can be a problem.
132
D. L. Buszard
133
TABLE 5.8
Effectivity Quantities for Common Plasticisers
Plasticiser
Tritolyl phosphate 40/42 ORD
(ORD = ordinary)
Tritolyl phosphate 40/42 LOC
(LOC = low ortho content)
Tritolyl phosphate 52/53 LOC
Tritolyl phosphate HOC
(HOC = high ortho content)
Tritolyl phosphate (tri ortho)
Tritolyl phosphate (tri meta)
Tritolyl phosphate (tri para)
Trixylenyl phosphate
Dibutyl phthalate
Diisobutyl phthalate
Diheptyl phthalate
Dioctyl phthalate
Diisooctyl phthalate
Dicapryl phthalate
Dinonyl phthalate
Dibutyl sebacate
Diisobutyl sebacate
Dioctyl sebacate
Dicyclohexyl sebacate
Paraplex G25 (Rohm & Haas)
Paraplex G50
D. L. Buszard
134
TABLE 5.9
Efficiency" of Common Plasticisers Relative to DOP
Plasticiser
Epoxidised soyabean oil
Tricresyl phosphate
Trixylyl phosphate
Dibutyl phthalate
Diisobutyl phthalate
Dioctyl phthalate
Diisooctyl phthalate
Di- Alphanol 79 phthalate
Dinonyl phthalate
Diisodecyl phthalate
Ditridecyl phthalate
Diisooctyl adipate
Diisooctyl azelate
Dibutyl sebacate
Relative efficiency
106
1-13
120
086
100
100
102
094
110
106
118
084
089
072
a The
135
D. L. Buszard
136
(a)
f------"'.
......
E1""'-
"
''9
(1 )
10
......0
""
I
.,
-10
10
OOA
OBP
EI OOS
"
OOP
x TTP
o ONP
E1'\
\
"\
(2)
".
X\
'{
0
10
20
30
40
50
60
70
Viscosily (c S)
Fig. 5.3 Variation of diffusion of plasticisers in PVC with their bulk viscosity.
(a) At 40C; (b) at 80C. Initial weight concentration ratios: plot 1, 30: 50 wt%;
plot 2, 10:30wt%.
137
(b)
I
-7
10
..
..........
e
...........
---
(11 .......
--
r---..
I!
..~ r--.-.
~ ~21
,
,
.11>
-. 0
10
10 I
3
Fig.5.3-contd.
9
ViscositJ (cS I
138
D. L. Buszard
139
'00
.,
'00
0
...
~
N
50
o~elYI epoxy
slearale
"'*
I~...........
.....0 p\
"l!
Ilo'Q
,~~
Oi n heptyl
phthalate
ille.r
'0..
- 1----
~~
<-.,.
.o~
~ ;.",
'\; ~~<"~~"
~
",o~ o\~\"",J ~oi"
,I---.
'"
....
'i).
.....
$"\~
10
~ ~
"" '"
~.. 0"
'\",
~..<. ~
,.~~ ~~
10
....
.00.
09
095
10
t.'"
.,,'
..
$"tJ
-- f -
e\
0",
085
"'P4/.
OBP
~.L
~-.y
""
"..
\..
:rp~
('i},
..."
B;=t~
'e.r
1>-
~'-t-
:OJ-I.,,,..... 1'00..
~. ~
...
ri oelyl phosphale
0
~1iiiD
~r~,~
DOS
".1
----
"nlnll
10
,f;
105
11
1-15
HO
140
D. L. Buszard
130- 60
400
300
..
>.
,..."
' tI
..
c:
~
f-
...c:
>.
u
>
200~
5u
Q.
11
lle- ~c: 40
I-
ij
'z
c:
(
'u
W
I'oto~-...------.----------,
6
..
10
11
12
'00
13
141
90
60
-6050
60
-50-
40
50
40
30~
oil
oil
-40-
U
I
0
0
0
lCl
1'1
....
oil
.!!
-30...
..
'-
Q.
.
...
.
~30
oil
20~
.c:
.2
l:
...
..."x
...'"
.~
.
~
~
'-
20
>-
'Q.
..-:
!!
...J
.2
l:
'e"n
o'"
:;::;
...
10 ;
>
1-,0-1
6
7
8
9
----l.~ A p Po ratio
Fig.
10
5.~ontd.
11
12
13
142
D. L. Buszard
5.9 ANTIPLASTICISATION
The addition of small quantities of plasticiser (up to 20%) to a PVC
compound leads to an increase in modulus and tensile strength and a
reduction in impact strength and elongation at break. This is the
opposite behaviour to that which might normally be expected of a
plasticiser and has been termed 'antiplasticisation'.85 The phenomenon
has been known for a long time. Brous and Semon86 reported the
anomalous behaviour of PVC containing up to 18% TCP as early as
1935, and since then it has been examined by many other workers. 87- 99
An illustration may be seen in Fig. 5.6 from the work of Ghersa,87
which shows the effect of low concentrations of DOP on tensile
strength, elongation at break, tangent modulus and impact strength.
As in plasticisation, the mechanism has not yet been fully elucidated,
although the major features have been well researched. Horsley88
demonstrated by X-ray diffraction that systems containing low
concentrations of plasticiser possessed increased order on a molecular
scale, and attributed it to increasing crystallinity caused by the
increased freedom of motion induced by the presence of the plasticiser.
However, more recent X-ray and IR data have suggested that only
minor changes in crystallinity accompany antiplasticisation. 9o ,91
Bohn,92 using viscoelastic measurements, related the onset of
brittleness to the suppression of the viscoelastic f3 relaxation process.
'"E
3'0
80
~f
'5
0'"
25 E ~
2.0
~ 60
'C z
g, <D
c:
400
o
c:
2002
-.;,
1Il
01
1Il
Q.
+----'T--"T"'""--,---+o
10
20
30
40
c:
.Q
143
REFERENCES
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
144
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
24.
25.
26.
27.
28.
29.
30.
31.
32.
33.
34.
35.
36.
37.
38.
39.
40.
41.
42.
43.
44.
45.
46.
47.
D. L. Buszard
145
146
D. L. Buszard
86. Brous, S. L. and Semon, W. L. (1935). Ind. Engng. Chem., 27, 667.
87. Ghersa, P. (1958). Mod. Plast., 36(2), 135.
88. Horsley, R. A. (1957). Progress in Plastics, (Ed. P. Morgan), Iliffe,
London, p. 77.
89. Shtarkman et al. (1972). Polym. Sci. USSR, 14, 1826.
90. Tabb, D. L. and Koenig, J. L. (1975). Macromolecules, 8, 929.
91. Jacobson, U. (1959). Brit. Plast., 32, 152.
92. Bohn, L. (1963). Kunststoffe, 53, 826.
93. Nakamura, K., Hashimoto, F., Nakanishi, M., Kinjo, N., Komatsu, T.
and Nakagawa, T., (1970). Proc. 5th Int. Congo Rheol., p. 409.
94. Kinjo, N. and Nakagawa, T. (1973). Polym. 1., 4(2), 143.
95. Pezzin, G., Ajroldi, G. and Garbuglio, D. M. (1967). J. Appl. Polym.
Sci., 11, 2553.
96. Pezzin, G., Ajroldi, G., Casiraghi, T., Carbuglio, C. and Vittadini, J.
(1972). J. Appl. Polym. Sci., 16,1839.
97. Robeson, L. M. (1969). Polym. Engng. Sci., 9, 277.
98. Robeson, L. M. and Faucher, J. A. (1969). J. Polym. Sci., B, 7, 59.
99. Mascia, L. (1978). Polymer, 19, 325.
CHAPTER 6
Commercial Plasticisers
D. L.
BUSZARD
6.1 INTRODUCTION
1-phthalate plasticisers
2-phosphate plasticisers
3--trimellitate plasticisers
4--low-temperature plasticisers
147
148
D. L. Buszard
Table 6.1 summarises the major characteristics, including the advantages and disadvantages, of the main types of plasticiser available
commercially. It is intended to provide a convenient means of selecting
the type or class of plasticiser which should be considered for a
particular application.
6.4 SYNONYMS AND ABBREVIATIONS
Polymeric plasticisers
Epoxy esters and
oils
Chlorinated paraffins
Azelates and
sebacates
ACJS acid esters
Adipates
DTDP
BBP
Triaryl phosphates
Alkyl diaryl
phosphates
Trialkyl phosphates
Trimellitates
C g phthalates
Linear phthalates
DNP, DlDP
C 4 phthalates
Plasticiser
type
Disadvantages
Expensive
TABLE 6.1
Characteristics of the Major Types of Plasticisers
150
D. L. Buszard
TABLE 6.2
Plasticiser Abbreviations and Synonyms
Preferred chemical
name
Q
Preferred
abbreviationsQ
6 Commercial Plasticisers
151
TABLE 6.2-contd.
Preferred chemical
name"
Dioctyl adipate
Dioctyl isophthalate
Dioctyl maleate
Dioctyl phthalate
Dioctyl terephthalate
Dioctyl azelate
Diphenyl cresyl phosphate
Dipropylene glycol
dibenzoate
Diphenyl octyl phosphate
Preferred
abbreviationsO
DOA
DOIP
DOM
DOP
DOTP
DOZ
DPCP
DPCF
DPDB
DPOP
DPOF
DUP
ELO
ESO
ODP
PPA
PPS
TBAC
TBEP
Diundecyl phthalate
Epoxidised linseed oil
ESBO
Epoxidised soyabean oil
Di-Alfold 810 phthalate
Octyl decyl phthalate
Poly(propylene adipate)
Poly(propylene sebacate)
Tributyl a-acetyl citrate
Tri(2-butoxyethyl) phosphate
Tributyl phosphate
TBP
Tri(2-chlorethyl) phosphate TCEP
Tricresyl phosphate
TCP, TCF, Tritolyl phosphate (particularly
TIP
in UK)
TDBP
Tri(2,3-dibromopropyl)
'Tris', T23P
phosphate
Tri(2,3-dichloropropyl)
TDCP
phosphate
Triethyl a-acetyl citrate
TEAC
Triisooctyl trimellitate
TIOTM
Trioctyl phosphate
TOF
Tri(2-ethylhexyl) phosphate
Tetraoctyl pyromellitate
TOPM
Tetra(2-ethylhexyl) pyromellitate
Trixylyl phosphate
TXP,
Trixylenyl phosphate
TXF
3,3,5-Trimethylpentane 1,4- TXIB
Texanol' isobutyrate
diol diisobutyrate
152
D. L. Buszard
(X~-O-R
C~R
II
o
As mentioned earlier, the phthalates are the largest single chemical
group of plasticisers used in PVC, the majority being general-purpose
Cs phthalates of which DOP is particularly important. There are,
however, a wide range of other phthalates which offer interesting
properties to the PVC formulator.
Phthalates can conveniently be divided into the following groups:
lower phthalates; general-purpose phthalates; linear phthalates;
higher phthalates; miscellaneous phthalates.
A comparison of the properties of PVC compounds plasticised with
54 phr (35%) of the more important phthalates is shown in Table 6.3.
The majority of alcohols used in the production of phthalates and
other alkyl diesters are manufactured by the 'OXO process' or
carbonylation reaction. The principal commercial alcohols produced by
this process, together with their raw materials and feedstocks, are
shown in Table 6.4. 1
6.5.1 Lower Phthalates
DBP and DIBP were widely used in PVC in the early 1950s. They
exhibit good efficiency but unfortunately their very high volatility and
poor aqueous extraction resistance lead to poor permanence properties. They have been replaced in the majority of plasticised PVC
applications by higher molecular weight phthalates, the exception
being certain areas where their rapid gelation properties are required
and their high volatility can be tolerated.
Certain plasticisers can seriously affect the growth of plants. 2 DBP
and DIBP have been shown to be very bad in this respect because of
6 Commercial Plasticisers
153
0983
0968
0975
48
55
31
DA79P
DCP
DNOP
DNP
Dinonyl
phthalate
0970
0981
53
DIOP
80
0980
56
86
77
79
80
77
78
74
1042
29
DIBP
DOP
72
1035
IRHD
16
Liquid properties
at 25C
Viscosity
Density
(cSt)
(g mr 1)
DBP
Abbreviation
Dioctyl
phthalate
Diisooctyl
phthalate
Di-Alphanol
79 phthalate
Dicapryl
phthalate
Di-n-octyl
phthalate
Dibutyl
phthalate
Diisobutyl
phthalate
Name
26
38
36
36
39
37
45
48
BS
softness
No.
-8
-25
-17
-18
-16
-19
-5
-19
eC)
Cold
flex
02
07
13
10
10
10
13
17
Volatile
loss
(%)
24
25
23
23
24
24
20
23
Petrol
17
19
16
18
17
19
12
18
18
23
15
17
17
18
12
19
20
21
25
11
18
20
20
24
14
15
Extraction resistance
(% mass loss)
MinDetereral
Olive
oil Soap gent
oil
TABLE 6.3
Properties of Phthalate Plasticisers in PVC Compounds at 54 phr
'"::>~
1;
r--
.".
.....
Vl
DINP
Benzyl butyl
phthalate
Di(2-methoxyethyl)
phthalate
32
DMEP
1167
1124
0950
243
45
0947
0964
37
54
0971
33
0962
0962
49
85
0985
0976
33
BBP
Diisodecyl
phthalate
DIDP
Diundecyl
phthalate
DUP
Diisotridecyl phthalate
DTDP
Di-Linevol
79 phthalate
Dlq9P
Di-Linevol
911 phthalate
D~l1P
Di-Alfol610
(DROP)
phthalate
Di-Alfol 810
ODP
phthalate
Diisononyl
phthalate
76
79
95
91
84
81
77
87
76
80
40
35
13
20
26
34
38
27
42
35
38
10
-12
02
01
02
07
01
08
03
-7
-16
-26
-16
-25
-27
-27
-26
-14
12
26
21
25
20
21
26
24
16
14
16
25
18
22
18
20
23
21
16
15
18
25
22
25
18
19
30
21
15
16
14
+1
03
12
17
06
17
+02
+02
01
08
18
+08
09
Ul
Ul
;;;
'"
00'
~~.
'"
a
'"....
3
3
<:>
0-
()
D. L. Buszard
156
TABLE 6.4
Principal Commercial OXO Alcohols
Raw material
Feedstock
Propylene
(Propylene)
Propylene + butenes
Propylene
Isobutane
Propylene
'Heptenes'
'Nonenes'
'Diisobutylene'
'Dodecenes'
Paraffin wax
Co C8 olefines
Alcohol
{n-Butanol
Isobutanol
2-Ethylhexanol
Isooctanol
Isodecanol
Nonanol
Tridecanol
{AIPhanol79
Linevol79
TABLE 6.5
Major Producers of Linear Plasticiser Alcohols
Producer
Conoco
Raw material
Ethylene
Monsanto Ethylene
{ p"affin wox'
Shell
Ethylene
Process
Ethylene growth
followed by oxidation
Ethylene growth
followed by carbonylation
emking fnllow,d by }
carbonylation
Ethylene growth
(SHOP) followed by
carbonylation
Alcohol
Alfo16IO,
AlfolBIO
Santicizer 711
(phthalate)
Linevol79
Linevol911
157
6 Commercial Plasticisers
7
Appa,.nl
plaslicis., loss
(%wIJ
6
OOP
OL 79P
OIOP
OL 911P
O+--_._---~----r_---_._---___r_
110
130
150
170
190
I.mp. S.tlin9 1 C)
158
D. L. Buszard
to
If
l3'
f ,.,//
e...
r,,//
(//
:s;c
..
;;:
.
l!
-20
Cl.
it
...
0
If
-10
.. '
-30
50:50
DOP/DOA
60:40
DOP/DOA
70:30
DOP
610P
_._810P
~--.~---.
1
DOP/DOA
2
3
Time [days]
6 Commercial Plasticisers
159
160
D. L. Buszard
TABLE 6.6
Comparative Performance of Triaryl Phosphates
Reofos
TXP
Reofos
TTP
Reofos
50
95
1-131
87
25
95
1134
87
24
60
1-161
85
27
60
1158
82
31
50
1170
83
30
+5
05
+8
03
+4
05
+6
06
+3
10
15
15
15
11
12
15
13
15
13
12
11
11
12
95
11
11
11
11
65
13
Formulation: PVC 100, plasticiser 54, white lead paste 4, calcium stearate 1.
6 Commercial Plasticisers
161
46f
36
~~
::1
28
26
24
10
20
30
40
50
60
70
80
90
100
IRHD
BS softness No.
Cold flex temperature
(BS 2782 method
104B) (0C)
Volatile loss at 82C (%)
Extraction resistance
weight loss (%)
Petrol
Mineral oil
Olive oil
Soap
Oxygen index (%)
15
13
13
12
34
17
16
18
12
27
-19
17
-50
17
3
10
76
41
78
38
83
30
22
21
21
19
29
(octyldiphenyl
phosphate)
141
Santicizer
TOF
(trioctyl
phosphate)
Reofos 50
(isopropylated
phenyl
phosphate)
20
17
16
17
29
-17
07
78
37
Santicizer
148
(isodecyl
diphenyl
phosphate)
20
17
18
12
29
-18
20
76
41
Phosphate
blend
(60% Reofos
50140% DOA)
TABLE 6.7
Performance of Different Phosphate Plasticiser Types in PVC Compounds at S4 phr
24
19
18
4
24
-19
11
78
37
DOP
(dioctyl
phthalate)
......
"'-
.,I:>
E;
tl:l
t""
Rl
6 Commercial Plasticisers
163
Products such as tri(2-chlorethyl)phosphate (TCEP) and the tri(monochloropropyl) phosphate for example, manufactured by Courtaulds, are effective flame retardants but exhibit poor compatibility
with PVC. They are of more interest as flame retardants in other
polymers (e.g. polyurethanes) but may occasionally be used as
additional flame-retardant additives in PVC.
6.7 GROUP 3 PLASTICISERS-TRIMELLITATES
C-o-R
~
R-o-C~C-o-R
II
II
o
Tri-Alphanol 79
trimellitate
Tri-Linevol 79
trimellitate
Triisooctyl
trimellitate
Tri(2-ethylhexyl)
trimellitate
Tri-Alfol810
trimellitate
Plasticisers
0995
0993
0988
0985
0971
107
250
205
925
Density
25C
(gml- I )
181
Viscosity
25C
(cSt)
24
17
93
20
91
88
30
30
BS
softness
No.
83
84
lRHD
01
01
02
02
01
-15
-7
-10
-20
(%)
Volatile
loss
-10
Clash
and
Berg
("C)
26
22
22
21
21
26
12
19
14
14
22
14
14
15
14
+1
+04
+04
+02
+01
+08
+08
+07
+03
+03
TABLE 6.8
Properties of Trimellitate Plasticisers in PVC Compounds at 54 phr
N
l:l
1:;
~
I:l:l
165
6 Commercial Plasticisers
RIf-O-C-RI-C4R-O-C-RI-e-1RIf alcohol-terminated
II
II
II
II
Diisodecyl
succinate
Isooctyl ester
of AGS acids
Isodecyl ester
of AGS acids
Dioctyl
adipate
Diisooctyl
adipate
Diisodecyl
adipate
Benzyl octyl
adipate
Diisooctyl
azelate
Dibutyl
sebacate
Dioctyl
sebacate
Diisooctyl
sebacate
Plasticisers
79
86
74
81
85
74
78
72
0928
0917
0924
0926
0912
0916
0913
0933
0911
0911
135
233
123
135
22
142
18
87
195
224
80
80
85
IRHD
0919
Density
at 25C
(g ml- 1 )
224
Viscosity
at 25C
(cSt)
05
04
-51
-46
34
48
37
35
04
-39
17
-48
-52
24
-45
06
10
-38
-47
75
-47
32
18
Volatile
loss
(%)
-38
Clash
and
Berg
(0e)
-36
45
27
33
46
25
37
26
BS
softness
No.
26
24
26
24
23
27
25
26
23
26
25
Petrol
27
24
26
22
23
26
21
22
23
23
24
26
25
27
25
23
25
21
26
24
24
24
04
18
14
17
13
75
35
15
45
Extractions (%)
Mineral Olive
oil
oil Soap
TABLE 6.9
Properties of Linear Diester Plasticisers in PVC Compounds at 54 phr
10
75
Og
45
19
Detergent
.....
s::.
!;;
t:x:l
t'"'
167
6 Commercial Plasticisers
Molecular weight
Viscosity at 25C (P)
Hydroxyl value (mg KOH g-l)
Compound properties
BS softness No.
Cold flex temperature eC)
Volatile loss (%)
Tensile strength (MN m- 2)
Extraction loss (%)
Hexane
Mineral oil
Soap solution (1 %)
2000
150
55
3000
250
45
4000
350
30
9000
850
25
27
-17
32
178
24
-15
27
198
23
+2
24
199
20
+58
23
208
04
10
90
03
04
68
01
01
47
01
0
38
168
D. L. Buszard
1,3-Butylene
glycol
Alcohol
3400
34
-75
211
37
8 X lO"
39
H
03
54
Moderate
1,2-Propylene
glycol
Alcohol
2300
32
-6
205
41
1 x 1012
42
39
02
61
Moderate
Diol
Chain stopper
Viscosity at 25C (cP)
BS softness No.
Cold flex eq
Tensile strength
(kgfcm- 2 )
Volatile loss (%)
Volume resistance
(0 em-I)
Extraction loss (%)
Hexane
Mineral oil
Water
Soap solution (1%)
Humidity (compatibility)
Adipic
Adipic
Acid
27
18
01
47
Moderate
6 X 10 13
10 12
37
Poor
z.l
07
01
210
29
1,3-Butylene
glycol
None
22000
25
-05
Neopentyl
glycol
Alcohol
5500
30
0
198
39
Adipic
Adipic
10 12
07
07
23
48
Poor
202
32
1,2-Propylene
glycol
None
24000
24
-15
Adipic
1013
57
55
06
93
Very
good
210
40
1,2-Propylene
glycol
Alcohol
800
36
-5
Adipic!
phthalic
anhydride
1013
28
34
06
69
Moderate
223
29
1,2-Propylene
glycol
Alcohol
32000
29
2
Adipic!
phthalic
anhydride
10 12
101
60
12
116
Excellent
191
67
Diethylene
glycol
Alcohol
700
33
-2
Phthalic
anhydride
1013
151
43
03
114
Very
good
210
120
1,2-Propylene
glycol
Alcohol
900
34
15
Phthalic
anhydride
TABLE 6.11
The Effect of Composition on the Properties of Commercially Available Polymeric Plasticisers
1013
350
160
0
130
Excellent
147
224
45
-20
72
~OP
10
0-
\0
....
'"
;;:
:::.
f
'"0;'
"tl
'"
3
3
0-
170
D. L. Buszard
6 Commercial Plasticisers
171
172
D. L. Buszard
Ceredor 545
Ceredor 552
43-45
CI5
1-16
0154l25
50-52
CI5
125
1-2
28
14
006-01
007--012
Very low
Very low
The use of chlorinated paraffin secondary plasticisers is straightforward and, provided that compatibility limits are not exceeded, no
exudation occurs. The compatibility limit is of the order of 25-30 phr in
compounds of BS softness 40 (Shore A 75) based on octyl phthalates.
It is recommended, however, to refer always to the chlorinated
paraffin manufacturer's literature when reformulating. Normally PVC
compounds are reformulated to the same hardness. The lower
plasticising efficiency of the chlorinated paraffins and their higher
density mean, however, that phthalates are not replaced part for part.
Typically, 15 phr of Ceredor have to be included for each part of
replaced octyl phthalate. Table 6.13 shows that the physical properties
are relatively unaffected in compounds reformulated to contain either
Ceredor 545 or 552.
In addition to ICI, chlorinated products are also available from,
amongst others, the following manufacturers: Hoechst, Huls, Dynamit
Nobel, and Caffaro in Europe; Diamond Shamrock, Keil, and Dover
6 Commercial Plasticisers
173
TABLE 6.13
Properties of Compounds" containing 'Cereclor'
Plasticiser
OlOP
OlDP
Re%s 95
Ceredor 845
Ceredor 852
54
BS softness No.
Shore A
Tensile strength
(MNm- Z)
% elongation at
break
Cold flex (0C)
% ageing loss (24 h
at 100C)
Volume resistivity
(0 cm x 1013)
40
75
40
75
40
75
40
75
40
75
173
17-8
172
156
17-6
38
35
62
25
51
315
-20
66
30
35
40
75
40
75
40
75
162
201
193
15
30
300
-16
48
320
-16
20
315
-16
325
-18
330
-16
245
-6
290
-10
075
095
085
036
074
052
015
06
06
05
06
Formulated for constant BS softness by varying the plasticisers (amounts given in phr)
in otherwise the same formulation.
in the United States; and Toya Soda, Asahi Denka, and Ajinomoto in
Japan.
6.10.3 Monoesters
This group comprises a wide number of different plasticisers, the
majority of which are only of interest in certain specialist formulations.
Examples of these are butyl oleate, phenoxyethyl oleate and
tetrahydrofurfuryl oleate. They are claimed to be good lowtemperature secondary plasticisers with advantages in some plastisol
applications.
An exception which may be included in this class is Mesamoll, an
alkyl sulphonic acid ester, manufactured by Bayer and popular in
Germany. It is a good primary plasticiser with properties similar to the
general-purpose phthalates.
6.10.4 Glycol Esters
These also are of low interest and not very wide application. They
include aromatic glycol esters such as diethylene glycol dibenzoate and
174
D. L. Buszard
Hydrocarbon Extenders
Dutrex (Shell);
Enerflex (BP);
Electrofine (D'Electro-Chemie);
Lipinol (Huls);
Mobisol (Mobil);
Ravolen (Manchester Oil);
Kenplast (Kenrich Petrochemicals, USA).
These oils are used as cheap extenders in certain PVC compounds
and plastisols. They are true extenders and have very limited
compatibility with PVC.
6.10.6 Other Miscellaneous Plasticisers
175
6 Commercial Plasticisers
Butyl rubber
Ethylene propylene rubber
Chlorosulphonated polyethylene
Natural rubber
Nitrile rubber
Polyamide
Polychloroprene
Polyethylene
Polypropylene
Polytetrafluoroethylene
Polyurethane
Silicone
Viton
Ratinlf
1
2
4
4
3
1
4
2
2
1
3
2
2
a Rating:
D. L. Buszard
176
10000
l'\.
r\ \ \
'f\.
5 OOO++-+-~~~-+l~-'--+-+--+--+--+--+--+--+--+---l
3000
\
\
2000
~\
\ \
I\.
\.
'\..
'\.
\.
1500t--t-l~......-\'~:-+--->ot--lI'Tt-+--+--+--+--+--+--+---+---i
1000
\\
-10
~\
10
\.1\ I\.
'\.
'\
'\..
20 30 40 50 60 70 80 90 100110120130140
Ttlmptlraturtl, C
6 Commercial Plasticisers
177
TABLE 6.15
European and US Plasticiser Manufacturers
Classes
manufactured
Company
United Kingdom
Albright & Wilson
B.P. Chemicals
Briggs & Townsend
Ciba-Geigy
1,2,4
1,3,4,6E
5
1,2,3,4,5,6A,6F
Trade names
Q
Pliabrac
Bisoflex, Enerflex
Diolpate
Reofos, Reomol,
Reoplast. Reoplex
Courtaulds
Diamond Shamrock
(Europe)
ICI
Robinson Bros
Scott Bader
Shell Chemicals
1,3,4,6A
1,4,6B
5
1,3,5
1,6E
Tenneco
Victor Wolf
2
5,6C
Lankroflex
Ceredor, Hexaplas
Arbeflex
Crestapol
Linevol, Dobane,
Dutrex
Wolflex
Austria
Chemie Linz
Mollan
Belgium
Argus Chemicals
Essochem Europe
Monsanto Europe
UCB-FTAL
6A
1
1,2,4,5,6F
1,3,4,6F
Drapex
Jayflex
Santicizer
1,3,4
Scandinol
1
6E
1,3,4
6D,6F
Gedeflex
1
1,2,4,5,6B
Plastifiant K
Garbeflex, Garbefos,
Alaiflex
1,4,5,6F
Palatinol, Plastomoll,
Palamoll
Denmark
Scandiflex
France
CdF Chemie
D'Electrofine-Chemie
ICI Europa
Nyco S.A.
Products Chemie Ugine
Kuhlman
Rhone Poulenic Polymeres
Hexaplas
Nycoflex
Germany
BASF
178
D. L. Buszard
TABLE 6.15-<:ontd.
Classes
manufactureda
Company
Bayer
1,2,4,5, 6E, 6F
Trade names
Adimoll, Disftamoll.
Mesamoll, Ultramoll, Unimoll
Vestinol, Lipinol
Reproxal
Witamol, Witaclor
Edenol
Wacker
Holland
Akzo Chemie
Unilever-Emery
6A
4,5, 6A, 6C, 6F
Uraplast
1,4,5
Estabex
Emery, Plastolein,
Unem
Uraplast (formerly
Scadoplast)
Italy
Akzo Italia
Distillerie Italiane
4,5,6C,6F
1,4,5, 6A, 6F
Montedison
Sisas
Sprea
1,4
1
5
Estaftex
Diplast, Diepox,
Staftex
Sicol
Spreaftex
Sweden
Berol Kemi
1,4
Switzerland
Reichhold Chemie
Ricatyl, Contrastat
4,6C,6F
5
1,3
1
6B
6B
Kesscoftex
USA
Armak
Ashland Chemicals
BASF Wyandotte
Continental Oil
Diamond Shamrock
Dover Chemical
Eastman Chemical
International
Emery Industries
Exxon
FMC
C. P. Hall
1,3,4,5,6F
4,5, 6A, 6C, 6F
1,3
2,6A,6C
4,5,6F
Plastomoll, Palatinol
Chlorowax
Chlorez
Kodaftex, Texanol
Emery, Plastolein
Jayftex
Kronitex
179
6 Commercial Plasticisers
TABLE 6. 15-contd.
Company
Classes
manufacturedO
Harwick
Hercules
1,4,6F
1,5, 6B, 6F
ICI Americas
Keil
Monsanto
6B,6F
6B,60
1,2,3,4,5,
6A, 60, 6E, 6F
3,4,5,6F
4, 60, 6F
1,3,4,5, 6A, 6C, 6F
4,5, 6A, 6C, 6F
5,6A
2
6A
1,2,3,4,5
2, 6A, 60
1,3,4,5,6C
1,3,4, 6A, 6C
60
Pfizer
pva
Reichold
Rohm & Haas
Sherex
Stauffer
Swift
Tenneco
Union Carbide
Union Camp
USS
Velsicol
Trade names
Polycizer
Clorafin, Hercoflex,
Hercolyn
Cereclor, Hexplas
Aroclor, Santicizer
Citroflex, Morflex
Peroxidol, Staflex
Monoplex, Paraplex
Admex
Phosflex
Epoxol
Nuoplaz
Flexol
Uniflex
PX
Benzoflex
180
D. L. Buszard
REFERENCES
1. Murfitt, H. C. (1970). E.C.N. Polymer Intermediates, Oct. 30th.
2. Inden, T. and Tachibana, S. (1975). Mie Diagaku Nogakubu Gakujutsu
Hokoku, 1-10.
3. 'Plasticised PVC in Horticulture'. BASF Technical Bulletin.
4. Murfitt, H. C. (1979). PRI Symposium, Loughborough University, April.
5. Sherwood, M. (1982). Chern. Ind., 24,994.
6. Shell Chemical Int. Report on 'Vapour Losses During Processing of
Plasticised PVC', Fig. 2.
7. Condea Petrochemie, Information bulletin No. 3151, Fig. 6.
8. Buszard, D. L. (1978). Chern. Ind., 16,610.
9. Moseley, J. and Dawkins, P. (1978). Chern. Ind., 16,620.
10. Buszard, D. L. (1983). PVC Processing II Proceedings, PRI, 22.7.
11. British Patent No. 1455196.
12. British Patent No. 1455390.
CHAPTER 7
BUSZARD
7.1 INTRODUCTION
182
D. L. Buszard
7 Properties of Plasticised
pvc
183
184
D. L. Buszard
7 Properties of Plasticised
pvc
185
D. L. Buszard
186
90
t-
80
'0
.e>
70
~'"~
%..
t-
...
E
....."
i"
<;,
~
'.j
.Q
::J
III
?..
-0
0
60
50
30
20
10
---,L-__...L.:-_ _----:-&:--_ _
_ _....L._ _
O~
50
IlO
70
80
Shore A durometer hardness
90
100
7 Properties of Plasticised
pvc
187
100
80
'-
Ci
.a
60
III
III
Ci
.5
'5III
40
Vl
1Il
20
20
40
60
Plasticis~r I~V<lI,
phr
80
100
100
80
...
CI
.a
E 60
:J
C
III
III
Ci
...,c
'5III
8
40
Vl
1Il
20
20
40
60
Plasticis~r l~v~l,
80
phr
100
D. L. Buszard
188
100
90
<l:
80
L-
.c
VI
70
60
50
2
0
20
40
60
80
100
90
<l:
80
L-
.c
VI
70
60
9
5
50
0
20
40
60
80
100
7 Properties of Plasticised
pvc
189
/10
100
~ 90l
:I
..
eoi
70l
60~
ID
I
!
so:
4d
I
I
30~
1
20
10
2O=------:30~---:40'::-----:S-::0:-------:'60'=""'"----:7:'::0:----='eo
Temperature.
The efficiency factor can be very useful in calculating the ratios and
concentrations of plasticisers necessary to replace one with another.
For example, if it is desirable to improve the low-temperature
properties of a compound containing 50 phr of TIP by replacing 20 phr
of it with DOA and yet retain the same modulus, then the 20 phr of
TIP should be replaced by (see Table. 7.1):
094
20 x 1.25
190
D. L. Buszard
25
20
15
....Ol
~
c:
til 10
~
iii
c:
~
20
40
60
80
100
40
60
80
Plasticisftr IftVftl, phr
100
25
20
~15
....Ol
.t:
c:
....~
Ul
.5!
iii
c:
~
10
20
7 Properties of Plasticised
pvc
191
500
4
1
1ii
c
o
~200
til
iii
100
20
40
60
80
100
500
~~
8
20
40
60
80
100
D. L. Buszard
192
TABLE 7.1
Comparison of Plasticisers at Equal Concentration and Equal Efficiency
Plasticiser
Efficiency
concentrationa
Efficiency
factol'
Properties at
60phr
Cold
Tensile
strength
flex
(MNm- 2 ) ("C)
Dibutyl phthalate
Dioctyl phthalate
Diisooctyl phthalate
Di-Alphanol 79 phthalate
Dinonyl phthalate
Tritolyl phosphate
Trixylyl phosphate
Dibutyl sebacate
Dioctyl sebacate
Dioctyl adipate
a
b
540
635
655
612
742
793
83-1
495
588
599
085
10
1-03
097
117
125
131
078
093
094
170
17-4
184
165
194
23-1
235
147
161
166
-25
-23
-22
-25
-125
-15
+l
-56
-47
-49
Properties at
efficiency concentration
Tensile
strength
(MNm- 2 )
179
159
17-1
159
160
176
172
169
163
165
Cold
flex
("C)
-21
-275
-30
-28
-245
-13
-]25
-39
-46
-49
7 Properties of Plasticised
pvc
193
~ 3
-'
:>
:f
>-
....
~
2
a:
<:>
-'
"- .....
-50
-~o
-30
-20
-10
10
20
"-
30
.....
~o
50
TEMPERATURE (OC)
194
D. L. Buszard
20
.
u
10
(:I
;l -10
nl
E-20
...
(:I
(:I
>< -30
....
(:I
1J
(5
U
-40
-50
10
-60+----r----r----r---~~____,
20
40
60
100
Plasticisar laval,
20
10
.u
~ -10
...
:J
nl
~ -20
a.
.3 -30
><
(:I
~-40
1J
(5
U_ 50
-60+---"'T'"'"--"---"'T'"'"--"---"
100
o
20
40
60
80
Plasticisar laval, phr
7 Properties of Plasticised
pvc
195
TABLE 7.2
2-EH-adipatel
2-EH-phthalate
(Ph,)
(BS 2782: 1970 M 104 B)("C) -44 -36 -31 -21 -23 -34 -30 -22 -35 -32 -24 -14
Cold flex temperature
after 7 days at 100C
(BS2782:1970MI04B)("C) -16 -15 -16 -13 -23 -30 -29 -22 +13
+9
-8
-5
a Extract
from technical literature of Shell Chemicals International Ltd, reproduced with their
permission.
D. L. Buszard
196
DOP
BBP
TXP
05
45
-20
17-8
335
225
06
43
-12
115
195
163
09 5
41
41
+2 -12
203 165
280 365
69 90
35
158
235
01
128
140
124
154
05
196
155 186
67 107
9-6 145
+03 01
212 41
130
28
-3
187
320
29
12
+05
31
1-6
7-2
9
42
-6
180
315
3-6
7-6
73
98
04
82
35
41
-7
17-4
330
H
29
z.t
58
03
27
41
44
-4
169
350
3-3
24
19
38
01
29
7 Properties of Plasticised
pvc
197
appropriate compounding/processing equipment for a particular product will achieve full gelation, then it is preferable either to use a lower
molecular weight endstopped polymeric or to include a proportion of
rapid-gelling plasticiser, such as triaryl phosphate, in the formulation.
It can be seen that the replacement of an alkyl by an aryl group in a
dialkyl phthalate reduces the nonpolar extraction resistance of the
plasticiser. Triaryl phosphates and epoxidised soyabean oil exhibit
intermediate extraction resistance between the dialkyl phthalates and
the polymeric plasticisers.
As mentioned in Section 6.9 of Chapter 6, solid polymeric resins
have replaced high viscosity polymeric plasticisers in certain applications. Typical physical and extraction properties of a polyurethanebased solid elastomer are shown in Table 7.4. It will be noticed that
whilst such products impart excellent extraction resistance to a PVC
compound, they are far less efficient than conventional polymeric
plasticisers.
The thickness of a sample can also have an effect on its extraction
resistance. This is shown schematically in Fig. 7.9. With very thin
TABLE 7.4
Physical Properties of a PVC Compound
Containing a Solid Polyurethane Elastomer-'Durelast loo,a
BS softness No.
Cold flex temperature eq
100% modulus (MN m- 2)
Tensile strength (MN m- 2)
Elongation at break (%)
Tear strength (kN m- 1)
Volatile loss (%)
Extraction loss (%)
Hexane
Mineral oil
Olive oil
Water
Soap (1%)
Formulation:
a Trade
PVC
Durelast 100
ESO
Cd stearate
45
-225
56
15
530
59
02
+03
+01
-01
+07
+04
100
100
10
6
D. L. Buszard
198
J.. --::l
.Q
,
._,. ,.
~
~ ,.'
1-
,.'
'
"
".
I
I
--- ---
1:C7l
.~
--_. '0
.,!!
~
~
.Q
---11
1:
samples the concentration gradient throughout the sample on extraction is very low (region A), whereas thicker samples exhibit a marked
concentration gradient with a reservoir of plasticiser in the centre of
the sample, thus resulting in the extraction being diffusion-controlled
(region B). Extraction resistance is normally quoted as % weight loss of
the sample (as in Table 7.3, etc.) or, less commonly, as % loss of
plasticiser. However, in certain cases, it has become accepted to quote
the results as actual weight loss per unit area of the sample tested. This
is so in a number of national and international directives relating to the
loss of additives from food-packaging materials into the contained
foodstuffs. For example, the EEC draft directiveS on overall migration
of plastics additives puts an upper limit of 10 mg per square decimetre
of packaging material when tested by a particular method using a range
of food simulants (distilled water, citric acid solution, aqueous alcohol
and olive oil). Expression of the results in this manner obviously means
that, as shown in Fig. 7.9, a particular compound may meet the
requirements when tested at one thickness, but may fail when tested in
a thicker section. In order to meet the olive oil extraction requirements
of the above directives, it has been necessary to reformulate the thin
PVC cling film to include a proportion of polymeric plasticiser as
shown in Table 7.5.
7 Properties of Plasticised
pvc
199
TABLE 7.5
Reformulation of Stretch Wrap PVC Food Packaging Films
to Include a Polymeric Plasticiser
Old
New
formulation formulation
pO
100
25
3
1
100
10
20
5
3
1
32
D. L. Buszard
200
TABLE 7.6
Migration Resistance of Plasticisersa
Cellulose Natural Polyethylene
nitrate
rubber
PPS
PPA
PPS/acid endstopped
PPAlacid endstopped
PPA/alcohol endstopped
Epoxidised oil
27
22
91
107
64
91
141
DOP
a Method
29
10
25
07
13
110
01
034
03
07
01
025
22
7
14
0302
0623
0785
0956
0019
0027
0027
0037
0062
0114
0132
0157
0058
0127
0146
0173
a Modified
b
DIN 53 405-1981.
Trade name of Victor Wolf.
7 Properties of Plasticised
pvc
201
30
HUG
Hcxaplal PPA
200
400
600
Houri at 100 0
800
1000
202
D. L. Buszard
7 Properties of Plasticised
pvc
203
TABLE 7.8
Fogging Test Results on Typical PVC Formulations for
Automotive Use o
CRASH PADS
b
Breon S125/12
Blendexc 101
Chemigum d NB B1 A2
1rgastabe CH55
Titanium dioxide
Antimony trioxide
Reomof LTM
1rgastab 17M
Fogging at 90C
50
50
10
05
5
3
25
15
95%
CALENDERED SHEETING
Breon S125/12
Reomol LTM
Palatino! 911
Reofose95
Titanium dioxide
Calcium carbonate
Antimony trioxide
1rgastab 17M
Irgawax e 372
Fogging at 60C
Fogging at 75C
LEATHERCLOTH
Vinno[8 P70
Solvich 374 NB
ReomolLTM
Palatinol 911
Reofos 95
Titanium dioxide
Antimony trioxide
Irgastab 17M
Fogging at 60C
Fogging at 75C
100
50
2
5
5
1
03
98%
95%
100
30
20
2
5
1
03
97%
98%
33
66
70
33
66
33
66
70
2
5
1
99%
93%
2
5
1
96%
90%
45
25
2
1
98%
91%
204
D. L. Buszard
Obviously the most stringent fogging test is that carried out at 90C,
which is for crashpad and window visor components. To meet the 90%
reflectance requirement, it is necessary to formulate with plasticisers
such as trimellitates, high molecular weight phthalates or other high
molecular weight plasticisers, as well as a carefully chosen polymer and
stabiliser system. Normal polymeric plasticisers are generally unsuitable since the low molecular weight 'tails' can fog severely.
Trimellitates are technically preferable to high molecular weight
phthalates, since it is far easier to strip Cg alcohols from the finished
product than C lO-C14 alcohols.
7 Properties of Plasticised
pvc
205
20
o
o
0>(
ClI
"0
.!:
c
ClI
~
>(
025
,/
"0
-40
Fig.7.11
75
0/0 Reofos 95
50
/oL79P
25
206
D. L. Buszard
in conjunction with the data in Figs 7.2 and 7.8 enables the properties
of other blends to be estimated.
The use of chlorinated paraffins particularly in conjunction with
phosphate plasticisers allows compositions with good flame retardancy
to be formulated economically, providing that a high degree of light
stability is not required. Alkyl diaryl phosphates can give formulations
with reduced smoke evolution. The partial replacement of triaryl
phosphates by chlorinated paraffins,6 particularly in the presence of
certain fillers, such as magnesium oxide and hydroxide. is also claimed
to give a reduction in smoke evolution;? see also Chapter 11, Section
11.5.
7.7 ELECTRICAL PROPERTIES
7 Properties of Plasticised
pvc
207
Eu
c:
13
> 10
>-
>
>-
.r>
.r>
10'2
....
:J
o
>
1010L..J~_ _~:----~:----~:---
40
50
60
70
Fig. 7.12 Effect of plasticiser type and level on volume resistivity at 23C. 8
208
D. L. Buszard
7 Properties of Plasticised
pvc
209
TABLE 7.9
Fungal Resistance of Plasticisers13 ,a
Plasticise,P
TXP
D79P
DIOP
Polyester B
Polyester C
Polyester A
DIOA
DIOS
ESO
% plasticiser
% sample
shrinkage
o
o
o
loss
419
524
621
1458
1828
5313
5643
6383
32
22
27
85
107
150
D. L. Buszard
210
'.n
'.n.t
7 Properties of Plasticised
pvc
211
TABLE 7.10
Plasticisers Approved Q for PVC in Contact with Foodstuffs
DBP DOP DIOP DIDP DMEP DBS DOS DOA DIDA ESO Reop/ex Reop/ex
FG
430
Council of Europe
Federal Republic
of Germany
Franceb
HoUand b
Italt
UK
USA
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
Limitations not indicated in the table may apply to, for example, maximum permissible concentration, type of food to be packaged, form of finished product, etc.
b Subject to an overaU migration limit.
212
D. L. Buszard
TABLE 7.11
Vapour Pressure of Dialkyl Phthalates
Plasticiser Molecular
weight
DBP
DOP
DIDP
278
390
447
Vapour
pressure
(rnrnHg)
Concentration in
saturated air
at 160"C (g rn- 3 )
12
0121
0029
12
175
048
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
7 Properties of Plasticised
pvc
213
15. Wolkober, Z., Gyarmati, I. and Farkas, P. (1978). Int. Polym. Sci.
Technol., 5(4), no.
16. Bultman, J. D., Southwell, C. R. and Beal, R. H. (1972). Naval Res. Lab
Report No. 7417, Washington DC.
17. Anon. (1965). Mod. Plast., 42(5), 168.
18. Pinner, S. H. and Massey, B. H. (1963). Brit. Plast., 36(10), 564.
19. USA Food and Drugs Administration (FDA) Code of Federal Practice.
20. 'Plastics for Food Contact Applications-A Code of Practice for Safety in
Use', The British Plastics Federation.
21. 'Kunststoffe in Lebensmittelverkehr', Kunststoff-Kommission des Bundesgesundheitsamtes, Berlin, Federal Republic of Germany.
22. NTP Technical Report series 217. 'Carcinogenesis Bioassay of Di(2ethylhexyl)phthalate (CAS No. 117-81-7) in F 344 Rats and B6C 3F1 Mice
(Feed Study), NIH Publication No. 82-1773.
23. NTP Technical Report series 212. Carcinogenesis Bioassay of Di(2ethylhexyl)adipate (CAS No. 103-23-1); F 344 Rats and B6C 3F1 Mice
(Feed Study), NIH Publication No. 81-1768.
24. CEFIC. (1982). 'Di-(2-ethylhexyl)phthalate (DEHP), CEFIC Plasticiser
Toxicological Working Group Report on Developments in DEHP
Toxicology, Avenue Louise 250, Bte 71, B-1050 Brussels.
25. Poppe, A. C. (1980). Kunststoffe, 70(1), 38-40.
26. 'Threshold Limit Values for Chemical Substances in Workroom Air for
1978', American Conf. of Govt. Ind. Hygienists, Cincinnati, Ohio.
27. 'Threshold Limit Values 1980', Health and Safety Executive, Guidance
Note EH 15/80.
CHAPTER 8
Fillers in PVC
I. D. HOUNSHAM and W. V. TlTow
8.1 INTRODUCTION
For the purpose of this chapter fillers may be broadly defined as solid
particulate or fibrous materials, substantially inert chemically, incorporated in plastics compositions (including PVC) to modify the properties
or to reduce material cost. Cost reduction is often the primary reason
for the use of a filler, and because of this the term is occasionally
treated (incorrectly) as if it was synonymous with 'cheapening
extender'. In fact all fillers-when present in significant quantitiesaffect in some measure the material and/or processing properties of the
plastic, and some-which may be termed 'functional fillers'-are
indeed used, often at increased cost, expressly as property modifiers,
e.g. glass fibres as reinforcing filler in uPVC compositions, antimony
trioxide or alumina trihydrate as flame retardants in pPVc. It may be
noted that the functional aspect is emphasised in the standard
definitions of a filler (ct., for example, ISO 472-1979; BS 1755: Part 1:
1967; ASTM D 883-83).
In the ideal case the incorporation of a filler might confer the
combined benefits of cost reduction with increased output (involving
no processing difficulties and no rise in the process/production costs)
and some technical advantages in the properties and service performance of the plastic. In practice, usually only one, or some, of these
features can be secured, often at the expense of the others, and the
selection of a filler (or filler system) will thus be a compromise,
dictated by the balance of the technical requirements and cost
considerations. For example, whilst such low-cost fillers as ground
215
216
limestone and coarse ground whitings offer the highest material cost
savings in many flexible PVC compositions, they can also adversely
affect the processing, and some physical properties of the end product;
incorporation of glass-fibre reinforcement in uPVC upgrades mechanical
properties but increases the cost and affects the processing behaviour
of the material.
A wide variety of materials has been evaluated as fillers for PVC
compositions: in this chapter attention is centred on those which are of
current technical interest. Among these, certain kinds of calcium
carbonate and chrysotile (white) asbestos have attained particular
commercial importance.
8 Fillers in PVC
217
218
.
z
...'"
...
&>
E
:>
5 50
Ul
Ul
ID
40
30
200~---"I""'O---2""'0--~30'--"l---"40'-----"50->o.---<60
0/0
by Weight of Filler
219
8 Fillers in PVC
400
300
c 200
C;arbon black'
II
'"o
C
iii
100
10
20
30
40
50
60
70
Among the sulphates of the alkaline-earth metals (Be, Mg, Ca, Sr, Ba
and Ra) only barium sulphate (BaS04) is of some (albeit relatively
limited) practical interest as a filler for PVC. The two grades of barium
sulphate in use as fillers are both produced from the mineral barytes,
220
TABLE 8.1
Some Effects of Varying Filler Content in a PVC Componnd
Filler (% by weight)
Tensile
strength
(lbfin- z)
Water absorction
(increase % y wt,
48h at 500C)
1700
-21
06
20
30
40
50
-20
60
1300
1210
920
750
500
15
15
15
12
12
20
30
40
50
60
1700
1400
1210
890
1090
20
30
40
50
-17
60
1450
1150
780
820
1100
1920
1710
1760
-145
-11
-7
No filler
Precipitated
calcium
carbonate
Calcium silicate
(wollastonite)
-19
-18
-18
-15
-9
-165
-16
28
37
49
51
65
113
83
68
65
71
12
09
09
the naturally occurring form of BaS04' They are: the natural material,
ground and purified; and precipitated BaS04' known as 'blanc fixe'.
Except where a high-density compound may be required for some
special reason, the high density of barium sulphate (about 4,5) is a
disadvantage because it makes the filler expensive on a volume-cost
basis. The advantageous features include high dry brightness (up to
995% reflectance) and low oil absorption (see Table 8.2). Flexible
PVC compositions incorporating this filler find use in specialised
applications where high acid resistance or opacity to X-rays is required.
Note: Calcium sulphate, found in nature as the minerals, gypsum
(CaS04.2HzO) and anhydrite (CaS04), can also be prepared
8 Fillers in PVC
221
whiting;
ground limestone, marble, and calcite;
ground dolomite;
precipitated calcium carbonate.
6
14
12
155
165
165
150
159
163
159
140
255
447
440
270
271
2.68
290
233
Calcite (Hydrocarb C )
Precipitated
Calcium silicate:
Wollastonite
Precipitated
26
360
15-65
18
34
40
158
240
Alumina trihydrate
(TrihydeC )
Asbestos (chrysotile)
Barium Sulphate:
Barytes
Blanc fixe
Calcium carbonate:
Dry-ground whiting
(stearate-coatedBritomya BSHC )
Oil
absorption b
(weight %)
Refractive
index
Filler materiaL
Specific
gravity
50
50
30
30
30
30
30
25-40
25
Moh
hardness
TABLE 8.2
Some Properties of Filler Materialsa
Crystalline
Crystalline
Crystalline
Crystalline
Crystalline
Granular
Granular
Granular or
crystalline
Fibre
Particle
shape
Particle size-mean
20 pm; top cut 15 Ilm
Particle size-mean
15Ilm; top cut 7 Ilm
Various particle
size grades
Remarks
152
151-152
150
159
160
145
154
1-40
155
155
159
250
249
021
275
260
220
200
265
265
265
280
Spheres, hollow
(thin-walledQ-cel 300c)
150
55-180
120
32
20-30
27-40
47
20
35 d
30
15
36
25
60
70
55
10-15
30
60
65
65
65
25
25
Spherical
Amorphous
Diatom
Crystalline
Amorphous
Platy
Platelet
Crystalline
Sphere
Sphere
Amorphous
Platelet
Platelet
Various particle
size grades
IV
IV
W
Mica (muscovite)
Nepheline syenite
Silica:
Colloidal (pyrogenic)
Precipitated gel
Diatomaceous earth
Ground quartz (sand)
Novaculite
Talc (Garotalc C )
156
162
260
263
Clay (kaolin):
Ground
Calcined ground
Glass:
Ground
Spheres, solid
(Ballotin{)
224
8 Fillers in PVC
225
226
8 Fillers in PVC
227
Sales Co. Ltd), Omya BLR/3 and Omyalite 95T (Pliiss-Staufer AG, or
Croxton and Garry, UK and Europe), and Gama-Sperse CS 11
(Georgia Marble Co., USA). Some CaC0 3 fillers are marketed as
'double-coated' grades, e.g. Britomya BSH 30 (Croxton and Garry
Ltd, UK); in comparison with the corresponding uncoated material
(Britomya M) the coating reduces oil absorption by about 25% and
DOP absorption by about 35%.11
(b) Organotitanate Treatments
Alkoxy organotitanates, introduced comparatively recently (1974/75)
in the USA as coupling agents for fillers in thermoplastics (as well as
some thermoset systems )4,12 have entered the commercial field, inter
alia, as surface treatments for calcium carbonate fillers and alumina
trihydrate flame retardants used in PVC. On the former filler certain
organotitanates (Ken-React TTOP-12 and TTOPP-38-Kenrich Petrochemicals Inc., USA) have been claimed 12 to improve substantially
the extrusion characteristics and impact resistance of 40%-filled rigid
PVC pipe compounds 4 ,13 and enable significant reduction in the
amount of lubricant used. In flexible PVC compositions the use of
TIOP-12 has been said to improve performance beyond that
achievable with stearate-coated CaC03 12 It has also been suggested
that the presence of an organotitanate coating on the CaC0 3 filler can
have some flame retardant effect in a compound. 13 Among commercial
calcium carbonate fillers for PVC surface-treated with organotitanates
are some of the grades supplied (in the USA) by the Sylacauga
Calcium Products Co., and the So/emite calcium carbonates from
Solem Industries Inc.
(c) Proprietary and Miscellaneous Treatments
The nature of proprietary surface treatments on some commercial
(ilC0 3 fillers (e.g. Super-Pflex 200-Pfizer Inc., Minerals, Pigments
and Metals Division, USA) is not generally disclosed, although some
are believed to be of the stearate type. Others include the so-called
'calcium resinate' treatment (as, for example, on Gama-Sperse
CR-12-George Marble Co., USA) and those involving the proprietary surface-active agents of Byk-Mallinckrodt (West Germany and
USA), as applied, for example, to some CaC03 filler grades of the
Calcium Carbonate Co. (USA). The opacifying surface treatment
(used, for example, on Omya BLR 2 and BLR 3-Croxton and Garry
Ltd., UK) may also be mentioned, although its function is not to
228
8 Fillers in PVC
229
230
Note: If the filler has not been sufficiently 'wetted-out' by the PVC
composition 'stress whitening' ('crease whitening') can occur
when the material is locally stressed. This is due to the
formation of minute voids as the solid phase of the filler
separates from the polymer.
As the refractive index of the filler increases from 153 the optical
transparency decreases.
50
5
50
15
50
25
125
375
625
075
225
375
495
485
475
8 Fillers in PVC
231
232
233
8 Fillers in PVC
200
180
160
?:
'>II
tO>
120
100L.-_ _----1
o
100
----1
200
--J~_
300
CaC0 3 phr
Ground whiting, s
Ground calcite
Precipitated, s
General
Dry blends
(a) Flexible:
2. Extrusion compounds
10
10
<4-
<1
10
200
30
10-20
3-5
Nominal
maximum
60-75
Mean
Typical particle
size (,mt)
Relevant filler
13-15
Ground calcite
Type"
Spread-coated flooring
(base coals)
1. Plastiso/s
Fabric coatings; foams
Application
Good dispersion, low equipment abrasion, good flow, relatively low plasticiser demand
Good physical properties are not normally critical in this application, hence
relatively coarse filler can be used for
high loading and fast spreading rates
TABLE 8.4
Applications of CaC03 Fillers in PVC
Day/Cal;c
Hakuenka b
Britomya BSHb
Millicarbb
Millicarb;b
Omya D2 b
Omya D40b
Millicarb;b
Omya BLH b
Calibrite b
Examples
of
commercial
products
:-:::
:::J
s:>
~
s:>
;:,
l:l..
~
I':
i:l;:>0-
V>
tv
General
(b) Rigid:
Pipe fittings
Shoe-sole compounds
General
(a) Flexible:
10 } These fine-particle grades give good
balance of physical properties, ease of
10
dispersion and processability
Good physical properties and fast output promoted by filler fineness (fastest
production with coated grades). Special 'electrical' grades available
Generally similar to those for rigid extrusion compounds, but fine particle size (especially
low maximum size) even more important (because of need to ensure good physical
properties of compounds based on polymer of lower K value)
Finest particle grades required for good wear properties, resistance to flex cracking, cut growth and other effects of damage in
service
Ground whiting, s
Ground calcite
Ground whiting (s)
Precipitated, s
Ground calcite
10
Ground whiting, s
3. Injection-moulding
compounds
About 7
5
<5
10
1-2
Up to 2
7-10
Precipitated, s
Ground whiting, s
1-3
Pipe, cladding,
profiles
(b) Rigid:
Ground calcite
Britomya BSHb
Hydrocarb b
Omyalite b
Millicarb b
Britomya BSH b
Super-Pflex 200d
Omyalite 95Tb
Britomya M or
BSH b
Millicarb;b
Hydrocarb b
N
W
VI
So
<:::
::!1
00
2-3
1-2
Ground whiting, s
Thick sheeting
5-10
10-100
Fine grades (coated for good dispersion) required, to give good physical
properties. Finest particle size for high
impact strength sheeting
= Stearate or other suitable surface treatment (desirable but optional if shown in brackets).
Croxton and Garry Ltd, UK.
C Harrison Enterprises, USA.
d Pfizer Inc., USA.
as
3
<5
2
Thin sheeting
10
10
10
Millicarb b
:--
Britomya BSH;b
Omyalite 95Tb
Morden R;b
Britomya V/L b
Britomya BSH b
Pfinyl402 d
Britomya BSH b
;;;
15
:::'l
s::.
~
s::.
;:s
;:>-
'"~
Nominal
maximum
Examples
of
commercial
products
Mean
Typical particle
size (JJ11I)
(a) Flexible:
Type"
Relevant filler
0\
4. Calendering compounds
Application
TABLE 8.4-<:ontd.
237
8 Fillers in PVC
3
104
ll.
~
.~
9
8
'CIl
300
6
5
<:3"
10L.
500
1031......-~=-=-
300
~::--
-='="=--__--=-=~
400
500
Calibrite loading, phr
600
Fig. 8.4 Plastisol viscosity as a function of filler loading and shear rate.
system, viscosity decreased with increasing shear rate at all loading
levels; it also increased with loading levels for each individual shear
rate up to about 420 phr filler, but then dropped (with increasing
sharpness) at higher loadings and shear rates. The results suggest that
it should be possible to increase substantially the loading level without
a corresponding rise in viscosity if the shear rate (in practice the
spreading speed) is suitably increased. In actual manufacturing
operations the optimum loadings for maximum output should be
established in production trials.
(b) Plasticised Compounds
Fine ground whitings and calcites are the most suitable CaC03 fillers
for extrusion compounds. Filler loadings in the range 20-100 phr are
normal. Some typical effects of increasing filler loading are shown in
Table 8.5. As can be seen the effect of a fine whiting (in loadings up to
40 phr) on some physical characteristics of the compound is not very
great. Table 8.6 shows the effects of increasing loading level of a
coated whiting (Omya BSH). The coated whitings have good
dispersion characteristics and improve the processability of the
compound. They suffer little agglomeration and, being hydrophobic,
resist moisture pick-up in storage. The coating also improves the
free-flowing characteristics of the filler, making it particularly suitable
PVC resin
Plasticiser
Stabiliser: BalCd
Lubricant: stearic acid
Filler
100 phr
55 phr
2phr
05 phr
0-40 phr
-50
1234
2585
325
79
20
2500
325
81
1312
-35
-40
10
2605
335
80
1271
30
315
82
1350
-30
2465
305
83
1384
-30
40
2410
QPVC resin
Plasticiser: DOP
Stabiliser: dibasic lead phthalate
Lubricant: dibasic lead stearate
Filler
Filler (phr)
Tensile strength (lbf in-2)
Modulus at 100%
elongation (lbf in-2)
Elongation at break (%)
Tear. resistance (lb in-I)
Brittle temperature caq
1985
210
81
-19
2225
200
81
-20
100 phr
50phr
3phr
1 phr
0-150phr
10
2500
0
2700
1970
215
80
-19
12
2475
1965
210
78
-18
15
2425
1925
210
76
-18
20
2425
1850
200
75
-17
35
2225
1775
185
67
-14
50
2035
TABLE 8.6
Some Effects of Increased Loadings of a Coated Whiting ('Omya BSH') on a Plasticised Compound
Filler (phr)
Tensile strength (lbf in -2)
Elongation at break (%)
Hardness (Shore A)
Relative density
Brittle temperature (0C)
TABLE 8.5
Some Effects of Filler (3 Jim Whiting) Loading on Plasticised Compound
1950
125
47
-5
150
1925
'"
C>
:0::::
:'":l
'";:s"'-
~
;,-
l::
00
239
8 Fillers in PVC
TABLE 8.7
100
190
200
-17
17xl014
Relative density
45
3
1
15
o
133
100
433
3
o
o
15
195
210
-18
133
240
None
Precipitated CaC03
Ultrafine ground,
coated whiting
Ground, coated whiting
Nature
TABLE 8.8
Filler
140
100
80
37
650
-
01
10
25
435
Elongation at
break (%)
Tensile strength
(kgfcm- Z)
(pm)
Properties of compound
11
12
7
12
Impact strength
(kgf cm cm- Z)
~
.....
(j
-.:::
'"tl
::J
00
242
8 Fillers in PVC
243
Dawsonite
Fybex
Chrysotile
15-20
04-06
244
153
15-17
4-7
01-016
320
235
7-10
1000-40000
001-10
255
150-155
3-4
Typical dimensions of potassium titanate fibres from Otsuka Chemical Co. (the
only current source since supply of Fybex was discontinued in 1974) are: 16 length
20-30,um, average diameter 02,um. These fibres are claimed to have a higher heat
resistance than Fybex.
The dimensions of PMF (slag) fibre (cf. Section 8.4.1) are quoted!3 as: diameter
4-5 ,urn, aspect ratio 40-60.
b Surface area measurement by the BET N2 method.
21-0 (1120'3)
5647 (389)
041 (2826)
11760 (81'0)
075 (5170)
ASTMD790
Flexural modulus
339 (180'8)
64
153 (68)
ft Ibf in-I (J m- 1)
Ibfin- 2 (MN m- 2)
1()6lbfin- 2 (MNm- 2 )
Ibfin- 2 (MN m- 2)
(J m- I)
10- 5 x C- 1
ASTM D 696
in- 1
OF
ASTMD648
COq
ASTM D 256(E)
ASTMD638
ASTMD638
ASTM D 790
47
ft Ibf
gper 10 min
Units
ASTM D 256(A)
ASTM D 1238-73F
Method
of
determination
Property
1-13 (7791)
181 (9656)
5900 (40'6)
054 (3723)
12420 (85 6)
300 (1600)
38
155 (69)
35
75
154 (10620)
165 (880 2)
6100 (42-1)
1-43 (9859)
12900 (88,9)
2-62 (1398)
3-l
160 (71)
32
15
TABLE 8.10
Some Effects of 'Dawsonite' in Rigid PVC 4
233 (16060)
104 (554,8)
6200 (42'7)
160 (11030)
13160 (907)
236 (1259)
21
163 (73)
27
30
i;
:::l
:0:::
I'>..
.,;:.,;:~
~
;::
:--
ASTM D 648
638
638
790
256
ASTM
ASTM
ASTM
ASTM
Tensile strength
Tensile modulus
Flexural modulus
lin (H75mm) bar
Heat distortion at
264lbf in- 2 (1,82 MN m- 2 )
D
D
D
D
ASTM D 792
Method
of
determination
Specific gravity
Mould shrinkage
Property
'C
in in- 1
or
mmmm- 1
lbf in -2 (MN m -2)
Ibfin- 2 (MNm- 2)
Ibf in- 2 (MN m- 2)
ft Ibfin- ' (J m- 1)
Units
867
0001
14000 (96'5)
1200 000 (8273)
950 000 (6 550)
35 (186'71)
0002
9000 (620)
650000 (4481)
600 000 (4 136)
6 (320'08)
0'003-0'004
6400 (441)
420000 (2 896)
375 000 (2 585)
15 (80020)
817
153
145
140 002
706
20% glass
161
30% glass
878
0001
16000 (110'3)
1 300 000 (8963)
1100 000 (7584)
2 (10669)
Reinforced
(Ethyl 7042 compound)"
10% glass
Unreinforced
(Ethyl 7042
compound)"
TABLE 8.11
Effect of Glassfibre Reinforcement on Some Properties of Rigid PVC 4
(j
""
"1:l
:::l
00
246
compounds reinforced with glass fibre have been available commercially for some time,! recently in special grades (e.g. from B F Goodrich)
with the reinforcement coupled to the matrix.
(d) Carbon Fibres
If the magnitude of the reinforcing effect was the only consideration,
carbon fibres would offer advantages over glass-fibre reinforcement in
uPVc. However, their use in this polymer has never been an
economically sensible proposition. In round figures, the cost of carbon
fibre (chopped strand) is about 60 times that of PVC polymer (cf. cost
factor of about 17 times for glass fibre). Thus the cost of base polymer
in a compound containing, say, 25% carbon fibre is relatively
insignificant. For applications calling for the highest performance
(which would be the reason for considering carbon-fibre reinforcement
in the first place) a base polymer can be afforded with inherent stability
and 'engineering' properties better than those of PVC (e.g. nylon, or
polycarbonate).
(e) Glass Spheres
Neither hollow nor solid glass spheres are used to any significant extent
in PVC compositions. The former kind cannot, in any case, be
regarded as a reinforcing filler in the proper sense. Purely from the
technical standpoint, the main effects of incorporating solid glass
spheres as a filler in uPVC would be broadly similar to those in other
thermoplastics, viz. increased compressive strength, modulus, hardness
and abrasion resistance, reduced creep and shrinkage: the reinforcing
effects would be isotropic, as with the spherical filler orientation
cannot be a factor. In processing, the effect upon the viscosity of a
molten thermoplastic is normally less with glass spheres than with
comparable volumes of glass fibres or even inorganic fillers of irregular
particle shape.
247
8 Fillers in PVC
250
IV
ll.
~~20
....r:.g'
200
i"
1ii 15
~
'iii
c:
~ 10
20
40
AI (OH)3
60
80
content, phr
Fig. 8.5 Tensile strength (1) and elongation at break (2) as functions of
alumina trihydrate content in a pPVC composition (50 phr plasticiser). Based
on data from Ref. 7.
248
100
.u...
90
'a.5 80
Ol
'c
...'0
~
en
Fig. 8.6 Vicat softening point (1) and hardness (2) as functions of alumina
trihydrate content in a pPVC composition (50 phr plasticiser). Based on data
from Ref. 7.
indeed the case with other particulate fillers (ct. for example, Figs
8.1-8.3). Apart from its flame-retardant and smoke-suppressant
action, which can be very effective at suitable loadings (say, broadly,
between 30 and 100 phr), alumina trihydrate can be especially useful in
certain compositions in that it does not impair the electrical properties
(tracking resistance in particular can actually be improved) and its
opacifying effect is comparatively slight (especially with ultra-fine
particle grades). As has been mentioned in the preceding section, the
fibrous mineral filler Dawsonite has some frame-retardant and
smoke-suppressant action in PVC compositions in which it also acts as
reinforcement.
8.4.3 Miscellaneous Functional Fillers
Fillers in PVC
249
250
(d) Starch
A technically significant early use of starch in PVC compositions has
been as an extractable filler (removed by hydrolysis and dissolution
with dilute acid) in the production of porous rigid PVC sheet used in
the manufacture of battery separators and in some filtration applications (see Chapter 25). More recently, starch-filling of plasticised and
8 Fillers in PVC
251
252
TABLE 8.12
Some Commercial Sources and Trade Names of Fillers
Supplier
Limestone
Trade name
Bennite
Calmote
Superlon
Snowcal
Britomya
Polycarb
Microcarb
Omya
Calibrite
Millicarb
Omyalite
Fordacal
Whiting
Clays
Alumina Trihydrate
Alcoa of Great Britain Ltd
B. A. Chemicals Ltd
Croxton and Garry Ltd
Barytes
Richard Baker Harrison Ltd
Vine Chemicals Ltd
Zach Cartwright Ltd
Tilcon Gregory Ltd
Synthetic Silicas
Joseph Crosfield and Sons Ltd
Degussa (UK) Ltd
W. R. Grace UK Ltd
Microdol
Hakuenka
Winnofil
Calofort
Calofil
Sturcal
Calopake
Burgess
MlOO, M501
Hydral
BacoFRF
Trihyde
Gasil
Aerosil
Syloid
8 Fillers in PVC
253
TABLE 8.12-contd.
Supplier
Antimony Trioxide
Anzon
Asbestos
A. A. Brazier & Company (Asbestos) Ltd
Cape Asbestos Fibres Ltd
Central Asbestos Company Ltd
Johns Manville (GB) Ltd
Marley Tile Company Ltd
Turners Asbestos Fibres Ltd
Cyprus Asbestos Mine Ltd
Henry Kiver & Partners Ltd
Trade name
Timonox
REFERENCES
1. Titow, W. V. and Lanham, B. J. (1975). Reinforced Thermoplastics,
Applied Science Publishers, London.
2. Fletcher, W. J. and Tully, P. R. (1967). 23rd ANTEC SPE Proceedings, p.
537.
3. Moreland, J. E. (Oct. 1971). In Modern Plastics Encyclopedia, Vol. 48,
No. lOA, McGraw-Hill, New York, p. 247.
4. Titow, W. V. (1977). In Developments in PVC Production and Processing-l, (Eds A. Whelan and J. L. Craft), Applied Science Publishers,
London, Chapter 4.
5. Private communication from TBA Industrial Products, Reinforced Plastics
Division, Rochdale, Lancashire, England.
6. Blumberg, J. G., Falcone, J. S., Smiley, L. H. and Netting, D. I. (1980).
In Kirk-Othmer Encyclopedia of Chemical Technology, 3rd Edn, Vol. 10,
John Wiley, New York, pp. 198-215.
7. Plastichem Ltd, Technical Bulletins and data sheets.
8. Rogan, J. (1979). Plast. Techno!., 25(8), 100.
254
CHAPTER 9
V.
TITOW
9.1 INTRODUCTION
PVC polymers and copolymers are susceptible to degradation by heat
(the thermal degradation is sometimes referred to as 'thermolysis') and
by light (photolysis, also called photodegradation, and-in some
contexts-photochemical degradation): in both cases degradation is
rapid and more severe in the presence of oxygen. In the practical
context photochemical effects are of special concern in outdoor
exposure of PVC materials, where they may be accompanied by those
of other factors instrumental in weathering (see Chapter 12, Section
12.6) so that the overall deterioriation can be faster and more drastic
than that caused by exposure to light alone.
Heat stabilisers are incorporated in all PVC compositions to protect
the polymer against thermal degradation at the high temperatures of
processing (higher for uPVC, and generally ranging-depending on
composition and process-from about 170C to about 220C) and also
subsequently in service. UV-absorbing and antioxidant additives are
included where appropriate as stabilisers against photochemical
degradation. Many heat stabilisers have some antioxidant action. An
antioxidant is also often incorporated as a component in composite
commercial heat stabiliser systems.
Formulation components other than the base polymer may also
suffer degradation: e.g. chlorinated polyethylene (by dehydrochlorination and oxidation on excessive heating!), rubbery impact
modifiers (by disruption and oxidation-e.g. on weathering-of the
double bonds their molecules contain), and chlorinated paraffin
255
W. V. Titow
256
257
~C-c=c-e-e-e-e-e-e-e~
I @) (j)~1 I I I I I I
<DCI H Cl H CI H CI
lenergy
HHHHHHHHHH
~C-C=C-;:~::;-CI-CI-el-e-C~
'Cl-H+'
I
HI
~.
~CI H
CI HI Cl
(1)
1energy
HHHHHHHHHH
~~-W-W-W-t-t-t~
I
I I I
~-----_.-:
H
HCl
L~l~_!t: CI H CI
and so on.
The development of colour is attributed to the conjugated double
bond systems formed in this process* (d. reaction scheme (1)), and
also, by some investigators,7 to the formation of strongly coloured
carbonium salt complexes (possible with an ionic mechanism of
dehydrochlorination) .
HH{H HfH H
I I I I
-C=C C=C
"c+iI
H ~ry H11
Cl-
(2)
~+-lL--i* Colour appears with as few as seven conjugated double bonds in a polyene,
whilst it is known 7 that sequences of up to about 30 can arise in the course of
dehydrochlorination of PVc.
258
w.
V. Titow
259
t = to exp (E/RT)
(3)
"
260
W. V. Titow
particular contammg traces of surface-active agents used as emulsifiers), the amount of unsaturation in the chains and the kind of
end-groups (both the latter factors also differ in polymers from
different sources). As has been mentioned, higher molecular weight
makes for greater resistance to degradation. Homopolymers are,
generally speaking, more resistant than copolymers. 17 In compounds
the stability of the PVC resin can also be adversely influenced by other
constituents (e.g. phosphate plasticisers; antistatic agents; some
colourants-see Chapter 11). The ease of stabilisation and response to
particular stabilisers in particular conditions also vary with the above
features. Considered in conjunction with the requirements of processing
and service in any given case the variety and possible interactions of
these factors provide strong support for the often expressed view that
every PVC composition should be treated as in individual stabilisation
problem.
9.2.2 Photochemical Degradation
All the main external manifestations associated with thermal degradation of PVC appear also as a result of photolysis (i.e. dehydrochlorination, development of colour, and deterioration of properties).
In plasticised compositions, exudation of plasticisers (resulting in sticky
surface layers), embrittlement and cracking can also occur in varying
degrees. However, in comparison with typical thermal degradation,
there is greater variability in the occurrence of these effects (for
example, more often than not colour development is slight or absent
altogether) as well as in their onset, progress and respective intensities.
The situation can be further complicated where-as is often the case in
service~xposure to light is associated with weathering: this introduces a number of further destructive factors (see Chapter 12, Section
12.6).
The dissociation energy of a carbon-ehlorine bond is about
77 kcal mol- 1 : this corresponds to the energy of light of wavelength
375 nm. 8 In theory, therefore, light of this wavelength (in the near-UV
part of the spectrum) should be able to cause photodegradation of
PVc. In practice the process requires higher photo energies (UV light
of shorter wavelengths): it is known (cf. Chapter 12, Section 12.6) that
the UV band between about 290 and 315 nm is mainly responsible for
the photochemical degradation of plastics, including PVc. However,
the mechanisms of this process in PVC, alone or as part of weathering,
261
are less well understood than those of thermal degradation: the main
features indicated by available evidence may be briefly summarised as
follows.
The first phase of photolysis of PVC in air appears to be
photooxidation,7 proceeding through a free-radical mechanism8,18,19and at a general rate proportional to the intensity of radiation (in the
appropriate UV region)-with the formation of hydroperoxide, keto,
and aldehyde groupS?,9,18 which undergo further light-induced reactions and breakdown:? the presence of these hydrophilic groups is
thought to playa part in the disruptive effects of atmospheric water in
weathering of PVC materials. 18 Dehydrochlorination also occurs at an
early stage7 ,8,20 (starting immediately, at a relatively fast rate, in an
inert atmosphere8), but usually proceeds more slowly than in typical
thermal degradation (although the rate, both in air and in nitrogen, is a
function of the intensity of irradiation and the temperature8):
conjugated double bond sequences are formed 7 ,8,18,19 (whose presence
may be expected to increase UV absorption l9) but these are liable to
be disrupted early in the process by reaction with oxygen 8,9,20
(probably resulting in the formation of carbonyl groups, themselves
light-absorbent and thus capable of accelerating the photolysis8), which
would counteract the formation of colour. Chain scission and
cross-linking also take place. 9,19,20 Exudation of plasticisers on
weathering of pPVC has been attributed 20 to their reduced affinity for
the cross-linked structures. Prior degradation by heat (even if not very
far advanced), e.g. such as may be allowed to arise by lack of strict
attention to conditions in heat processing (or through inadequate
stabilisation), can enhance and accelerate photodegradation: this
should be borne in mind in the formulation and processing of PVC
compositions for outdoor use. Impurities, and other adventitious
'additives' (e.g. residual solvents in films 8,21) can also have an effect in
this direction.
262
W. V. Titow
looked for in an ideal stabiliser: rapid binding of free HCl, high ability
to replace labile Cl atoms with stable groups, saturation of double
bonds, antioxidant action, disruption of chromophoric groups, absorption of free radicals, neutralisation of impurities and degradation
products, effective screening of UV radiation.
It is self-evident that the stabiliser itself, and any reaction products
resulting from the exercise by it of the above functions, should ideally
be innocuous, non-migratory, non-toxic, odourless, and should not
impair the colour, clarity or any other properties of the PVC
compound.
In addition, from the standpoint of processing and use, the ideal
stabiliser should also:
(i)
263
264
W. V. Titow
lead compounds;
organotin compounds;
compounds of other metals;
organic stabilisers.
265
266
W. V. Titow
267
TABLE 9.1
Some Characteristics of Lead Stabilisers
Stabiliser
White lead
Tribasic lead
sulphate
Dibasic lead
phosphite
Specific
gravity
PbO
(totaf)
'Safe'
PbO
64-68
86
288
70
86
65
67
895
60
Lead silicate
267
89
665
Lead stearate
Dibasic lead
stearate
124
19
315
55
315
365
Tribasic lead
maleate
60
89
665
Quantity to use
(on 100 phr)
Extrusion
Rapid extrusion
Calendering
Spreading
Extrusion,
plasticised
Extrusion,
unplasticised
Calendering
Spreading
Extrusion,
plasticised
Extrusion,
unplasticised
Calendering
Moulding
Extrusion
Calendering
Used alone
Used in
combination
3-5
8-10
3-5
2-5
3-5
5-10
3-5
2-5
3-5
5-10
3-5
3-8
5-7
4-6
15-25
2-4
05-1
2-4
268
w.
V. Titow
269
270
W. V. Titow
271
I
Alkyltin compounds
(R = an alkyl group)
Methyltin
compounds
(R=-CH3)
Butyltin
compounds
(R=-C4~)
1_- - _ _,
1
Octyltin
Lauryltin
compounds
(R = -CsHd
Estertin compounds
(R = an ester group:
R'.OOC.CH2 CH2- )
compounds
(R = -C12H 2S)
272
W. V. Titow
273
274
w.
V. Titow
can be made of synergistic effects that can arise between the thiotins
and some lubricants, notably internal lubricants of the partial glyceride
type. Conversely, these lubricants (both liquid and solid) can impair
the heat stability of compositions stabilised with tin carboxylates
(which give very good results when used in conjunction with lubricants
of the fatty alcohol ester type).
Lubricant capability can be built into methyl, butyl, and octyl tin
compounds by suitable choice of the ligand (substituent group A).
Thus some alkyltin mercaptides with a long aliphatic chain in the
ligand have lubricating properties (e.g. dibutyltin-bis(lauryl mercaptide), used in some rigid compositions in Europe), as have members of
the new group of 'reverse-ester' alkyltin mercaptides developed in the
USA for rigid pipe compositions, in which the A substituents are esters
of a mercaptan (such as thioethanol).
In lauryltin compounds the presence of the lauryl group is
conducive to lubricant action but the overall effect is governed also by
the nature of the A substituent.
The potential scope for imparting lubricant properties to the
estertins through chemical structure modification is considerable,
in that significant effects can be obtained by the appropriate choice
of the R' substituent in the ester groups25 (see classification scheme
above).
In the USA, where lead compounds are not permitted in PVC water
pipes, alkyltin stabilisers are used in this large-scale application. Their
relatively high cost, and the vigorous competition among their
manufacturers, prompted the development of new alkyltin stabiliser
systems effective in rigid PVC pipe compositions at very low
incorporation levels (down to about 03 phr). Among the main trends
in such systems have been the increased use of monoalkyl tins,
exploitation of synergists (e.g. some organotin sulphides), and
introduction of the lubricating tin stabilisers.
Note: The effect of the monoalkyl compounds in tin stabiliser
systems has been likened 25 to that of zinc in Ba/Cd/Zn
stabilisers (cf. Section 9.4.3 below), i.e. promotion of good
initial colour and long-term stability improvement. In some
blown-bottle and rigid-film formulations, an increased proportion of monoalkyl compound in the alkyltin stabiliser systems,
coupled with suitable lubricant choice, can reduce the
stabiliser requirement to below 1 phr.
275
276
w.
V. Titow
do not contain them (cf. (b) and Section 9.4.4 below, and Chapters 4
and 10).
ANTIMONY MERCAPTIDES
277
"'/
~"ti-'/
20
L.
.c
.~-\
~/
Co
0"0./
/
<1./
L.
ell
.a
11l
1ii
c
i= 10
25
1~
~O
278
W. V. Titow
Zinc compounds are never used as sole stabilisers in PVC compositions. This is because PVC polymers are sensitive to zinc, in the sense
of increased susceptibility to degradation in its presence (amounting in
effect to a catalytic de-stabilisation by the metal). The degree of
sensitivity varies widely with the type and grade of PVC polymer, and
also in different compositions (e.g. plasticised, filled compositions of
vinyl chloride/acetate copolymers are among the least sensitive). The
variations in response of emulsion polymers used in PVC pastes to zinc
compounds and individual commercial zinc-containing composite
stabilisers are well known as a general fact (although the actual effects
in particular cases normally have to be ascertained by tests). Thus,
whilst individual zinc compounds (e.g. zinc octoate, zinc stearate) are
available within the regular ranges of many stabiliser suppliers, they
are always used in conjunction with other metal compounds (e.g. those
of cadmium, calcium, magnesium or barium), incorporated either
singly or in pre-combination (e.g. as barium/cadmium or calcium/
magnesium stabilisers). In such made-up combinations the zinc
compound improves initial colour, long-term stability, and resistance
to cross-staining with sulphur compounds (which can occur, for
example, with cadmium stabilisers). Liquid zinc compounds do not
279
280
W. V. Tilow
Barium compounds (such as, for example, the stearate and laurate
which are available from commercial stabiliser sources) can impart
good long-term stability to PVC compositions, but the initial colour is
poor and progressive yellowing usually takes place. The compounds
are thus unsuitable for use as sole stabilisers, but-as would be
expected from a consideration of the respective effects-they complement well the action of cadmium compounds. Moreover, when
compounds of the two types are used together synergistic effects also
arise, making the resulting stabilisation even more effective than would
be expected from a mere addition or superposition of their individual
contributions. These are the reasons underlying the wide use of
composite stabilisers based on the barium/cadmium combination, often
including also a zinc compound as the third component (see (b)
below). Barium/zinc systems, without cadmium, are also employed, as
are some barium/lead compositions in which the barium compound
improves long-term stability (see, for example, Durham Chemicals'
Durostabe S70 and S65, respectively, in Table 10.4, Chapter 10).
Barium compounds are not as toxic as those of cadmium, but they
are not suitable for use where non-toxicity is required.
LITHIUM COMPOUNDS
281
and even in combinations with other metal stabilisers its use is not
widespread. Like other stearates it has lubricant properties, and may
be regarded as a non-toxic substitute for other metal soaps in some
formulations (but its admissibility in particular cases should be checked
with the supplier or the appropriate organisations).
MAGNESIUM COMPOUNDS
282
W. V. Titaw
In terms of the amounts used this is the most important group among
PVC stabilisers, although none of its members can equal the organotin
systems in stabilising power and versatility (in the sense of equal
suitability for use with all grades and types of PVC polymers).
However, systems of this type can impart high degrees of thermal
stability, good light stability, and be compatible with good clarity in
transparent compounds. Their effects are improved (and especially the
light stability increased) by the addition of epoxy co-stabilisers and
organic phosphite 'chelators' (see Section 9.4.4 below), and these
synergists are normally included either by the formulator or ab initio as
constituents of the composite proprietary system. Weathering properties are further improved by addition of UV absorbers (see Section
9.5 below). Liquid BalCd and BalCd/Zn systems are particularly
widely used in flexible PVC materials, typically at levels of 1-2 phr
(with about O5-10 phr of a chelator and up to about 5 phr of an epoxy
co-stabiliser where appropriate).
Solid (powder or flake) systems are combinations of the metal soaps,
with or without the further additives just mentioned. Whilst they can
be used in both rigid and flexible compositions they are of special
interest for uPVC as they have some lubricant action, and affect the
softening temperature less than do liquid stabilisers. In most cases they
are suitable for translucent (as well as opaque) compositions, but only
some are suitable for highly transparent ones. Typical incorporation
283
Members of this system are the most widely used non-toxic stabilisers
for PVC (although not all its commercial variants have approval, or the
same wide approval, in various countries). Stearates and octoates of
the two metals, and many of their proprietary combinations, are widely
permitted in most countries for use in rigid and plasticised compositions for the production of food-packaging materials and containers,
medical goods and toys.
Ca/Zn combinations are not very powerful stabilisers. Wherever
possible (and this is permitted in many 'non-toxic' applications) they
are used in conjunction with an epoxy co-stabiliser (which is a
component of many proprietary systems) to improve the stabilising
effects both against heat and light, and an organic phosphite synergist
(which improves initial colour and transparency, inter alia). Other
organic synergists available for use (in conjunction with organic
phosphites if desired) to improve the stabilising action and efficiency of
Ca/Zn systems include stearoylbenzoylmethane (Rhodiastab 50Rhone-Poulenc, France) and some proprietary polyol compounds (e.g.
those supplied by Perstorp AB, Sweden): stability improvements by
factors up to x2 can be obtained in some compositions through the
addition of these compounds (02-05% with solid CalZn systems).
The CalZn stabilisers are available in both solid and liquid forms. In
* Generally unsuitable for alkali-prestabilised emulsion grades.
284
W. V. Titow
285
(i)
286
w.
V. Titow
OrganiclMiscellaneons Stabilisers
287
II
H 3 C-C=C-C-oR
288
W. V. Titow
II
I II I
diphenyl urea (C6 H s)-N-C-N-(C6H s);
H S H
I II I
diphenyl thiourea(C6 H s)-N-C-N-(C6 H s).
These compounds may be used as heat stabilisers (with little
light-stabilising effect) for compositions based on alkali-prestabilised
emulsion polymers, and especially in plasticised compositions of this
kind (yellow discoloration may occur in semi-rigid and rigid PVC).
Typical incorporation levels are relatively low, around 03-05 phr,
because of the low compatibility of these stabilisers' with plasticised
PVC. Long-term stability can be substantially improved by the
presence of an epoxy co-stabiliser (up to about 3 phr). At temperatures
above 150C some commercial urea stabilisers may start decomposing
with evolution of ammonia: this point should be checked with the
supplier in individual cases (and preferably also by tests) with
reference to the processing method and equipment used, as such
gassing can give rise to porosity in products.
The main effect of stabilisers of this type is thought to be
neutralisation of any hydrogen chloride evolved as a result of thermal
dehydrochlorination: this mode of action would be in keeping with the
basic nature of these compounds. They are also thought to have some
antioxidant action.
(c) Epoxy Compounds
Epoxy compounds used as plasticisers for PVC are discussed in Section
6.10.1 of Chapter 6. These, as well as others (e.g. epoxy resins
marketed as components for thermoset systems), also have a stabilising
effect in PVC compositions. Whilst this effect is relatively mild in the
absence of other stabilising additives, epoxy compounds (and in
particular some of the epoxy plasticisers, e.g. epoxidised soyabean oil,
epoxy esters) are very important, and widely used, as strongly
synergistic co-stabilisers for metal-based stabiliser systems, as well as
289
....c
&80
Cl
'c
Ol
....ru
u
;;:
70
l:.- - - - - . . . . 1-----......L- - - - - - - o 1
ESBO
cont<2nt, phr
Fig. 9.2 Vicat softening point (DIN 53460) of a rigid PVC composition
stabilised with 2 phr of a liquid dibutyltin mercaptide as a function of the
amount of epoxidised soyabean oil co-stabiliser present.
290
W. V. TilOW
compounds in PVC compositions are their susceptibility to microbiological attack (see Section 12.7.1, Chapter 12). and the possibility of
exudation, with formation of tacky surface deposits, in some cases
where-in discharging its stabilising function-the compound loses its
epoxy groups through the chemical reactions involved, so that its
compatibility with PVC is reduced. This effect can be a potential
problem, especially in weathering or ageing situations. The compositional factors which promote it are the use of the epoxy compound as
the sole stabiliser and/or its presence in a relatively high proportion as
a component of the plasticiser system. Thus, to prevent this kind of
problem, an epoxy compound should not be used as the only stabiliser,
and its level of incorporation as a plasticiser should preferably not be
higher than about 25% of the total plasticiser system in PVC compositions likely to experience any but mild ageing or weathering conditions.
Note: Interaction of epoxy compounds with unsaturated additives in
a PVC composition (e.g. ricinoleates or oleates which might
be present in stabilisers or plasticisers) can also lead to
permanent chemical modification (loss) of epoxy groups, with
consequences similar to those just described. This was the
cause of development of surface tackiness in, for example,
calendered sheeting when, in the early days, the barium
component of Ba/Cd stabiliser systems then coming into use
was frequently barium ricinoleate, and addition of epoxidised
oils (and phosphate chelators) was beginning to be practised
as an effective way of improving heat and light stability. 34
Changing to the metal soaps (e.g. Ba and Cd laurates) and,
later, liquid complexes (e.g. Ba and Cd phenates) eliminated
the problem. However, inferior clarity and plate-out could
still be troublesome with the soap systems (especially in
high-speed, high-temperature processing), and yellowish colour and susceptibility to sulphur staining with both the soaps
and the complexes: incorporation of zinc compounds subsequently became a meanS of alleviating these disadvantages
(see Section 9.4.3(a) above).
(d) Organic Phosphites
291
w. V. Titow
292
293
* Octadecyi 3-(3,5-di-tert-butyi-4-hydroxyphenyi)propionate.
t 2,4,6-Tris(2,5-di-tert-butyi-4-hydroxybenzyi)-1,3 ,5-trimethyibenzene.
294
w.
V. Titow
9.5.2 UV Absorbers
The cardinal role of UV radiation of wavelengths 290-315 nm in the
photodegradation of PVC polymer has been mentioned in Section
9.2.2 (310 nm is often quoted as the wavelength most damaging to PVC,
and 290-400 nm as the band instrumental in the photodegradation of
plastics generally). Light in the 'damaging' wavelength range excites
the PVC polymer molecules, in the sense of imparting excess energy
sufficient to break bonds in the molecular chains: the free radicals
formed as a result initiate, and participate in, the degradation process,
which is accelerated by the presence of oxygen (cf. Section 9.2.2).
Whilst many heat-stabilisers and antioxidants provide a measure of
protection against photolytic and photooxidative degradation of PVC,
they operate essentially after the process has started (in the case of
antioxidants mainly by disposing of the free radicals formed).
Moreover, they are used up as they exercise their protective functions,
so that the protection is of finite duration. The UV-protective additives
which are frequently included in PVC materials for outdoor use afford
additional and complementary protection, in that they absorb and
dissipate the incident UV radiation essentially before it can initiate
degradation, without themselves undergoing de-activating chemical
changes (see below).
The types of organic compound in widest commercial use as UV
absorbers for PVC compositions are modified benzophenones (especially certain alkoxy derivatives of 2-hydroxy or 2,2-dihydroxy
benzophenone), and benzotriazole derivatives. Proprietary additives of
the first type are exemplified by Cyasorb UV 9, UV 24, and UV 531
(American Cyanamid Co., Polymers and Chemicals Dept and
Cyanamid of Great Britain Ltd); Uvinul D408 (BASF Wyandotte
Corp.); UV-Chek AM 541A (Ferro Corp., Chemical Div.); Carstab
700 (Carstab Corporation). Benzotriazole compounds figure promin* Pentaerythrityl tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate].
295
(i)
296
W. V. Titaw
fairly sharply with distance into the material: interaction of the radiation with the PVC material itself would also be a factor progressively
reducing the amount of radiation with distance of penetration. *
Note: The validity of this explanation is not affected (and is in fact
indirectly supported) by the frequently cited observation42-44
that the protective effects of two other kinds of additive with
light-stabilising action-viz., phenolic antioxidants, and the
nickel complexes used mainly in polyolefins-are independent
of material thickness. Neither of these two types of stabiliser
interacts with UV radiation. As has been mentioned, phenolic
antioxidants are essentially scavengers of free radicals. The
nickel complexes are known as 'quenchers' because they
de-activate, evidently by resonant energy transfer, some
groups in the polymer chain (e.g. carbonyl groups formed in
polyolefins in the course of photochemical degradation) which
have become 'excited', i.e. raised to a higher energy level by
absorption of UV radiation (and thereby primed to promote
chain scission).42,43 Thus both types of stabiliser act on
chemical species formed as a result of absorption of UV
energy by the polymer (i.e. only after this has already taken
place), so that, as would be expected, the only locational
factors influencing their operation are the distribution and
concentration of those species in the polymer, in relation to
their own distribution and concentration.
297
298
w.
V. Titow
Titanium dioxide also has some UV absorption but its screening action
is principally due to reflection and scattering of radiation (IR, visible,
and UV). This mechanism is less efficient than that of carbon black,
and higher loadings are needed (typically 5-15 phr) for appreciable
effect. It is self-evident that the use of both these pigments as light
stabilisers is ipso facto restricted to opaque compositions (and only
black ones in the case of carbon black).
Zinc oxide is another particulate, inorganic screening agent which
may be considered for those PVC compositions that are not too
zinc-sensitive (cf. Section 9.4.3 above): it is thought to benefit
synergistically from the presence of certain antioxidants, to the point
where suitable combinations of this kind can be more effective than
normal amounts of organic UV stabilisers.
As has been mentioned, UV absorbers incorporated in PVC
compositions are less effective in the outermost surface layers than in
the body of the products; yet it is the surface which needs the most
protection, as it is the most directly and extensively subjected to
photochemical attack on exposure. The problem is particularly
relevant in transparent compositions for outdoor service, in which UV
absorbers are widely used: surface application, rather than internal
incorporation of the stabiliser, can be a useful solution in some cases.
PVC sheeting, for example, may be surface-coated with a lacquer
containing a relatively high concentration (say 1-3%) of the stabiliser:
such lacquers, based on vinyl copolymer resins (cf. Chapter 24), acrylic
resins, or other binders, are available from commercial sources. This
approach can offer cost and protection efficiency advantages in suitable
circumstances. 49 Surface absorption (from solution) of a UV stabiliser
(MPB*) has also been claimed to give good results. 49
Such physical factors as the degree and uniformity of dispersion,
ease of migration through the composition, extractability, and
volatility, influence the performance of any additive in PVC: a useful
discussion of their effects on the performance of stabilisers, including
UV stabilisers, has been published by Allara. 23
Antioxidants, UV absorbers and screening agents are available
individually, as composite light-stabiliser systems, and as components
of polyfunctional 'single-pack' additive combinations. The individual
stabilisers or stabiliser systems are also supplied as ready-made or
* 2-(2'-Hydroxy-5' -methylphenyl)benzotriazole.
299
Lead Stabilisers
300
W. V. Titow
(4)
where A is a mercapto or carboxylic acid substituent (see Section
9.4.2(a. Like lead chloride, the dialkyltin chlorides do not impair the
stability of PVC polymer.
Work with model compounds (employed as PVC polymer
analogues)7,51 has shown that organotin stabilisers can replace labile
(allylic) chlorine atoms with their own ligand (A) groups, whereby
the stability of the thus substituted compound is significantly increased.52-54 The substitution could be either direct,l1 or possibly on
the carbon originally in the 4 position to the chlorine: 7
(5)
or
301
~C=C~
+ HA -
H H
~C-C~
H A
(6)
I
H~
HC
Hn-COOR
H6 + HC-COOR II
Hi
CH
HC/'
'cH-COOR
H~
tH-COOR
. . . . . . C H/
(7)
The fact that dibutyltin maJeate is a better heat stabiliser than the
corresponding succinate (which would not undergo a Diels-Alder
reaction) has been cited7 in support of this possibility.
302
w.
V. Titow
303
~C~
I
CI
~C~
~]
/OOCR
+Cd
--+
'-.....OOCR
/OOCR
+Cd
--+
~l
~C~
60CR
+ Cd
/OOCR
(8)
'-.....0
(9)
304
W. V. Titow
Cd
. . . . . . 'OOCR
. . . . . . CI
. . . . . . .O OCR
+ Ba
. . . . . . OOCR
OOCR
Cd"""""'"
+
'cl
Cd
. . . . . . .Cl
............
CI
OOCR
Bi
--+
"cl
. . . . . . .O OCR
+ Ba
............
. . . . . . .O OCR
. . . . . . .O OCR
Cd
+Ba
(10)
. . . . . . O OCR
'cl
. . . . . . .O OCR
. . . . . . .Cl
Cd
+B,
.........OOCR
CI
. . . . . . .O OCR
------.OOCR
--+ elf
OOCR
. . . . . . .Cl
+ Ba
............
(11)
(12)
CI
The ways in which these additives are believed to operate have been
indicated in Sections 9.4.4 and 9.5. The following additional points
may be mentioned here.
Epoxy compounds are widely thought to bind HCI through their
oxirane groups: 7 ,9,11,62
-CH-CHI
I
OH CI
(13)
These groups are also believed to participate in the role the epoxy
co-stabilisers may play in the transfer of HCI to the main stabiliser,62
and the exchange of the PVC polymer's labile chlorine atoms for
stabiliser groups. 11
The antioxidant action attributed to organic phosphite co-stabilisers
(cf. Section 9.4.4) may operate through the following kind of reaction
305
~CH-CH2~
CI*
+ P(OR)3
----+ ~TH-eH2"""""
(14)
O=P(ORh + RCl
However, the function with which these additives are most widely
credited, and after which they are known as 'chelators', is the
formation of complexes with the metal chlorides arising as by-products
of stabilising reactions (see above). This 'complexing out' reduces the
deleterious effect of the chlorides on the PVC polymer, and also
improves the clarity of transparent PVC compositions (ct. Section
9.4.4). The mechanism of operation of po/yo/ co-stabilisers used, like
the phosphites, with mixed-metal stabilisers (cf. Section 9.4.3), is
believed to be similar.
9.7 SOME GENERAL EFFECTS AND COMMON FAULTS
IN STABILISED COMPOSITIONS
Some general effects of stabiliser-associated factors upon the properties of PVC compositions are summarised in Table 9.2.
The most common general faults to which certain stabilisers may
give rise in PVC compositions are plate-out and sulphide staining.
Both have been mentioned in passing: their principal features may be
summarised as follows.
9.7.1 Plate-out
Processing and
service
Service
Service
Heat welding
Processing
Lubrication
Electrical properties
Non-toxicity
Clarity
Weldability
Paste viscosity
Service
Significant
in:
Softening point
(uPVC)
Property
Remarks
TABLE 9.2
Some General Effects of Stabilisers on Properties of PVC Compositions
:-::::
;:E:
...,
307
308
W. V. Titow
Colourant for test mix: Sico Red WRC* (0,1 weight % on the total
mix). Run the test mix for 7 min at 165C (without friction); sheet and
remove from the mixer. Run the scavenging mix for 3 min: remove and
judge the degree of red staining (related to the amount of plate-out) by
comparison with an unused portion of this mix. For increased accuracy
of assessment, the comparison specimens may be moulded into sheets
of identical size. Constant, uniform conditions are essential; in
particular the mixer should be in thermal equilibrium (achieved by
running for some hours prior to the test): the tests should be run by
one and the same operator as a continuous series, and each series
completed on the same day. The recommendations include the
following formulation for the scavenging composition.
100
PVC polymer: So/vic 239 (Solvay et Cie. SA, Belgium)
Stabiliser: Irgastab OM 18 (Ciba-Geigy) (dibutyltin maleate) 05 phr
Epoxy co-stabiliser: Reop/ast 39 (Ciba-Geigy)
50 phr
Plasticiser: DOP
300 phr
Lubricants: Irgawax 330 (Ciba-Geigy) (stearic acid)
08 phr
Irgawax 331
08 phr
White pigment: Kronos A (Titangesellschaft mbH,
West Germany) (Ti0 2-anatase)
15 phr
9.7.2 Sulphide Staining
PVC composItions contammg stabilisers (or other additives, e.g.
pigments) based on cadmium or lead can develop colour on contact
with sulphur compounds. This phenomenon is known as sulphide
staining. In cadmium-containing compositions the colour is yellow,
caused by the formation of yellow cadmium sulphide (CdS). Compositions incorporating lead compounds may tum black-in patches or
overall-due to the formation of black lead sulphide (PbS), or
sometimes dark brown ranging to black: this is probably attributable to
the presence of the reddish-brown lead sulphochloride, Cl.Pb.S.Pb.Cl.
Organic
sulphur - free
Organic
sulphur- ctg
Ca/Zn
Ba/Cd/{Zn)
Tin carboxylate
Thiotin
Lead
Organic
sulphur - free
Ca/Zn
Sulphide formation,
with visible effects
as indicated
No effect
Tin
carboxylate
Ba/Cd/{Zn)
Lead
TABLE 9.3
Visible Manifestations of Interaction of the Main Types of Stabiliser in PVC Compositions
'"'0;"'
'"~
a
<:>-
'0
310
w. v.
Titow
311
312
W. V. Titow
r-----------------Maximum
acc~ptabl~ l~v~1
of
d~gradation
x
~
S
I
I
2ro
I
I
I
~
~
Tim~
Fig. 9.3
313
314
X
eI .... - - -
"
W. V. Titow
.S
c:
:;:;
C1I
~
L.
Cl
eI
Timq--_.
Fig. 9.4 Effect of stabilisation (or severity of treatment) on the stability time
(t) of a PVC composition: schematic representation. A, No stabiliser (or most
drastic conditions); B, moderately effective stabilisation (or medium-severe
heating); C, highly effective stabilisation (or mildest treatment).
100
1
2
3
....
10
23
22
21
1/& , K- 1 x 103
20
Fig.9.5 Arrhenius plot (ct. Section 9.2.1) of log stability time (ts> minutes) as
a function of the reciprocal of absolute temperature (1/8) for three PVC
compositions of increasing stability (1) 2> 3): schematic representation (but
values roughly representative of some uPVC compositions, with HCl emission
as the degradation index).
.g
.S
Maximum
accczptablcz
"
~
01
(#
:
I
j--- -- -- -
I
I
315
---
I
I
tA
tT
Timcz
Fig. 9.6 Residual heat life (stability time), tA - tT, tB - tT , tc - tT, of PVC of
the same composition, processed under conditions of increasing severity
(A> B > C) after an initial heat treatment (T): schematic representation.
Apart from their role in development and research work, heat stability
tests on PVC compositions and products are important in the practical
contexts of processing and service. Evaluation of the suitability and
effectivity of stabilisers, and stabiliser/lubricant systems, in protecting
PVC against degradation both under processing conditions and in use,
is one of their main applications. Others include direct assessment or
prediction of the stability of PVC compositions in various circumstances of treatment and/or exposure, with reference-where relevantto the effects of formulation components and/or heat history in this
regard. Investigation of PVC material failures, and 'trouble shooting'
generally, are related areas in which stability tests can be helpful.
A stability test normally comprises a suitable treatment of the PVC
material to induce degradation under controlled conditions, followed
by detection, or quantitative determination, of a significant level of the
316
W. V. Titow
317
thick.
pPVC: Process for 5 min at a temperature between 165 and
170C (depending on nature and amount of plasticiser) into a sheet about 05 mm thick.
The heating equipment may, typically, be an air-circulation oven,
containers for the specimens immersed in a heating bath, or-in some
cases-a press with suitable arrangements for heating and cooling the
platens. Stability is determined in terms of heating time to reach a
certain level of the degradation index used in the test (Le. stability
time in those terms): this may be the first appearance, or attainment of
a certain degree, of discoloration in the composition (ct. the example
below). Colour change of an indicator in continuous contact with
volatiles evolved by a specimen, or the other effects mentioned in
Tables 9.4 and 9.5, may also be used.
Note: A test method which can give rapid results, and in which the
Static
Colour change
Colour change
Evolution of HCI
Evolution of HCI
Static
Method, and/or
stability criteria
Test treatment
for which
determination
method
is suitable
Visual
General means
Development of
colour in PVC
material
Manifestation
of degradation
detected or
measured
TABLE 9.4
Heat Stability Tests Relevant to Practical Assessment of the Effects of Stabilisers in PVC
'"
::j
:00::::
00
Titration
Conductivity
determination
Torque-time
plot
Evolution of
HCI
Evolution of
HCI
Static
Static
Static
Ref. 66
ASTMD793
a Volatile alkyltin chlorides are formed on heating of PVC compositions containing alkyltin stabilisers (cf. Section 9.6).
These can dissociate in aqueous solution, and may thus interfere with HCI determination by conductivity and pH
methods.
pH determination
Evolution of HCI
\(:)
'-0
"<:;'"
{;
:J;.
'";::
'"
il
~
c:J
'"
(;;,
::::0
<:J-
is
v,
320
W. V. Titow
Basis of
test
Standard
specijications
Test equipment
and reagents
Test specimens
Temperature
DeterminaISO 305-1976
Glass tubes for Discs of about
As agreed
individual
tion of col14mm dia(consistent
our developspecimens
meter, about 1 with signi(with closely
ment in
mm thick
ficant colour
fitting alumiPVC comdevelopment
position on
nium plug inwithin the test
heating
serts); oil bath
period)
ASTMD2115- Forced-draft
Squares of sheet 177 1C un67 (reapproved oven with aluabout 082 mm less otherwise
1974)
minium foil
thick; side at
agreed
supports for
least 254mm
PVC specimens
(on oven racks)
DIN 53 381,
Part 2-1975
Detection or
determination ofHCl
evolved by
PVC material on
heating
As in ISO 305
Essentially as
As in ISO 305
ISO 305, but
disc diameter 1
mm less than
that of the aluminium blocks
321
specification
Test treatment
Time
Procedure: main
points
Assessment and/
or expression of
results
Visual assessment of
Test duration Specimens heated in
tubes immersed in oil colour developed, in
limits 60bath; one withdrawn
120 min
comparison with unfor inspection every
treated specimen
5 min (enough should
be used for completion ottest)
Specimens heated in
Relative heat stability
Up to 120
oven and removed
assessed visually, in
min
for inspection at suit- comparison with
able intervals, e.g. af- standard sample or
ter 30, 45,60,90 and control, in terms of
120 min
time for particular
degree of discoloration
As in ISO 305
As in ISO 305
Limits as in
ISO 305,
but test time
so selected
that the last
specimen to
be removed
is black
Specification
based on an earlier (1963) version of ISO 305
TABLE 9.5Basis of
test
Standard
specifications
Test equipment
and reagents
Test specimens
Temperature
As in ISO/R
BS 2782, Part 1, As in ISO/R 182 Powder, graMethod l30A:
nules, frag182
ments of sheet
1976c (Congo
Red Method)
(5-6mm
square), or
other formsamount as in
ISO/R 182
DIN 53 381 Part Substantially as the ISO and BS Congo Red Methods
1-1971
ISO/R 182-1970 Glass tubes for
10 g of commi- As in Proceindividual
Procedure B
nuted test
dure A
specimens with material
(pH Method)
provision for
passage of a
gas; heating
bath; supply of
gas (air or nitrogen); pH
measuring cells
(one for each
test tube); pH
meter
BS 2782, Part 1, As in ISO/R 182 As in BS
As in ISO/R
Method BOA
182
Method l30B:
1976d (pH
Method)
DIN 53 381 Part
Substantially as the ISO and BS pH Methods
3-1971
Specimen flasks 10 g of test
ASTM D 79349 (reapproved (250 ml Erlenmaterial cut
into pieces with
meyer) with
1976)
provision for
one dimension
passage of nitno larger than
rogen (pre1/16 in; spread
heated to test
evenly on bottemp.); HCl
tom of flask
absorption tube
with NaOH
soln; oil bath
C
contd.
specification
Remarks
Test treatment
Time
Procedure: main
points
Assessment and/
or expression of
results
As in ISO/R 182
30 min
Volatiles generated by
specimen heated in flask
swept into absorption
tube by nitrogen bubbling through at 2-4
bubbles S-I. After 30
min Cl pptd. with
AgN0 3 and determined
by titration with KSCN
324
W. V. Titow
An oven used for static heating tests must be reliable, with good
control, and even distribution, of temperature. ASTM D 2115 gives a
useful summary of requirements in this regard. In the interests of the
greatest uniformity of exposure, specimen carriers rotatable during the
test treatment should be provided inside the oven in preference to
ordinary shelves. These may take the form of self-levelling shelves
carried in a horizontally mounted cylindical frame after the manner of
a 'big dipper', or a turntable 67 (with the specimens placed around the
periphery). An oven test, employing discoloration of the specimens as
the degradation index, is illustrated by the following example. 71 Both
the test and its results are fairly representative of good early practice,
325
reasonably in line with current standard tests of this kind (d. ASTM D
2115; ISO 305; DIN 53381/2 in Table 9.5).
A sequence of colour change was established by preparing a series of
strips of PVC sheet degraded to the colours listed below. The strips
served as standards for a quantitative expression of colour changes
produced by the test treatment in specimens of the composition tested.
O.
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
clear,
barely detectable change,
very slight change,
slight yellow tinge,
pale yellow,
yellow,
faint tinge of red,
pale red,
red,
deep red,
very deep red/black,
black.
A
B
C
PVC
resin
DOP
100
100
100
100
50
50
50
50
Barium
stearate
Zinc
stearate
Epoxidised oil
(Pliabrac A)
25
25
05
05
50
Dibutyltin
dilaurate
20
The compositions were made into sheets 006 in thick, and I-in squares
of the sheets were used as test specimens. The squares were placed on
aluminium mesh trays in an air-circulation oven at 180C. * One
specimen of each composition was taken out at IS-min intervals and its
colour number determined by reference to the standards. Figure 9.7 is
* Temperatures of 175-180C are most commonly used in static stability tests,
although higher ones are also sometimes recommended-e.g. 200C by the
French Centre Scientifique et Technique du Batiment. 72 For the same PVC
composition and test method, stability times at different temperatures should
normally conform to the Arrhenius relationship given in Section 9.2.1 (see also
Fig. 9.5).
326
W. V. Titaw
11
10
9
8
01
.S 7
-g6
u
L
54
10
20
30
40
50
60
70
80
90
100
110
327
-!
o
ts
TimlZ., minutlZs
chamber (head cavity) with the rotors running. The amount of material
is selected in relation to the cavity volume: if it is desired to ensure
good exposure of the composition to air during mixing, the cavity
should not be filled completely. If colour development is used as the
degradation index, samples of the composition are withdrawn for
examination at suitably frequent intevals (say every two minutes).
Otherwise the time is determined from the start of mixing to the rise of
torque indicating the decomposition point. The roller speed and the
temperature are the principal variables; their values should be selected
in the light of the purpose of the test. The following may be mentioned
by way of example of combinations which have been used in
investigations of stability of PVC compositions in relation to their
behaviour in industrial processing: roller speeds of 35, 45, 55 and
65 r min -1 at temperatures of 165C, 180C and I85C;65 or 50 and
100 r min- 1 at 140C and I80C. 66
Note: An interesting study by Collins et ai. 65 provided evidence for
good correlation between Brabender thermal stability values
and those obtained with a capillary rheometer. Data obtained
with the latter instrument also demonstrated, inter alia, a
w.
328
V. Titow
correspondence between the 'time to black' of PVC compositions and a pronounced increase in melt viscosity (reflected by
the commencement of an upward sweep in a plot of the
extrusion load versus time).
A feature of properly designed dynamic stability tests employing the
Brabender torque rheometer or a suitable extruder, is that they can
bring out the important role of lubrication in the heat stability of PVC
in processing. The reduction of frictional heating by proper internal
and external lubrication can substantially increase the stability of a
generally adequately stabilised PVC composition (by reducing the heat
history and hence extending the heat life), in comparison with an
unlubricated, or poorly lubricated, but otherwise identical composition. This factor is not brought out by static tests, in which the stability
time depends essentially on the stabiliser system and is not significantly
influenced by the lubricants66 (unless these are of the stabiliserlubricant type--cf. Chapter 11, Section 11.1.2).
9.8.3 Light Stability Testing
The general format of tests for stability to light is the same as that of
heat stability tests-i.e. a test treatment producing degradation,
followed (or accompanied) by a determination of its extent. All the
test treatments in common use are static ones. In the practical context,
the ultimate significance of light stability tests is as sources of guidance
to resistance of the material tested to photodegradation in service
(although good correlations with actual service performance may be
difficult to establish-see Chapter 12, Section 12.6): this is implicit, at
least to some extent, even in the use of such tests for direct comparison
of the stability of similar materials, as criteria of specification
requirements, and in quality control. The usual test treatments consist
of exposure of suitable specimens to 'natural' light (with or without
accessibility to general weathering), or to artificial light sources in the
laboratory. The laboratory tests may also include exposure to heat and
water (liquid and/or vapour) to simulate the effects of these factors in
outdoor weathering. The popular tests in both these categories
(including international and national standard tests), their effects,
applications, significance, and limitations are discussed in Section 12.6
of Chapter 12, in connection with weathering resistance of PVc. As
mentioned in that section, laboratory tests which involve exposure to
329
330
W. V. Titow
REFERENCES
1. Abu-Isa, I. A. (1975). Polyrn. Engng. Sci., 15(4), 299-307.
2. Sosa, J. M. (1975). J. Polyrn. Sci., Polyrn. Chern. Ed., 13(10),2397-405.
3. Voigt, J. (1966). Die Stabilisierung der Kunststoffe gegen Licht und
Wiirrne, Springer Verlag, Berlin.
4. Silberman, E. N. (1968). Preparation and Properties of Polyvinyl Chloride
(in Russian), Izd. Khimia, Moscow.
5. Thinius, K. (1969). Stabilisierung und Alterung von Plastwerkstoffen,
Verlag Chemie, Weinheim.
331
332
W. V. Titow
333
CHAPTER 10
COFFIN
10.1 INTRODUCTION
336
P. S. Coffin
Emery Inc.
Ferro Chemical
Hammond Lead Products Inc.
Interstab Chemicals Inc.
M and T Chemicals Inc.
Stauffer Chemical Co.
Synthetic Products Co.
Tenneco Chemicals Inc.
Vanderbilt Co.
Sakai Chemicals
Saukyo Chemicals
Seido Chemicals
Shinagawa
Shin ChwQ Kagaku
Tannan Kagaku Kogyo
Toyko Chemicals
10
337
338
P. S. Coffin
339
340
P. S. Coffin
341
grade from Associated Lead). Most lead stabiliser and mixed metal
soaps can be supplied as pastes dispersed in a suitable plasticiser.
Agglomerated forms such as granules and flakes are widely used
because of their reduced dusting tendencies. More recently, this type
of product has been taken a stage further with the introduction of
'strands' (see Section 10.6) and 'pearls'3 with considerably reduced
dusting tendencies and free-flowing characteristics. Finally, the stabiliser can be supplied packaged within a sealed polyethylene bag for
addition direct and whole into a high-speed mixer. The mixer shreds
the bag and the polyethylene then constitutes part of the lubricant
system.
10.5 HYGIENE AND ENVIRONMENTAL
CONSIDERATIONS
342
P. S. Coffin
approved for potable water pipe in all countries except the USA and
France. Extensive testing of the water extraction from lead-stabilised
pipe6 ,7 has shown that only a trace of lead is leached out during the
first pass through the pipe. Thereafter, the inner core is rendered
passive to the extraction of lead. Cadmium compounds give overall the
most problems of the various stabilisers, and at present considerable
restrictions on the use of cadmium in PVC are being considered in
Sweden. However, there are strong arguments for using barium/
cadmium stabilisers for certain applications, 8 and the restrictions are
under review.
For the applications where more stringent environmental restrictions
are necessary, such as medical or food-contact articles, the calcium/zinc
systems are generally acknowledged as non-toxic. The octyltin class of
stabilisers have wide approval for food-contact applications from such
bodies as the FDA (USA), BGA (West Germany) and BIBRA (UK).
The recently introduced estertin stabilisers are also claimed to be
non-toxic, but there is to date insufficient evidence for approval to be
given to this type of product.
10.6 UK STABILISER MANUFACTURERS-PRODUCT
RANGES AND APPLICATIONS
343
Performance
characteristics
SQ, BQ or XQ
Basic lead
sulphate
SQ, BQorXQ
Basic lead
sulphate
SQ,BQorXQ
3103
Basic lead
sulphate
SQ orBQ
3104
Basic lead
phthalate
SQ orBQ
3105
Basic lead
phosphite
SQ orBQ
White lead
3101
3102
3106
High stabiliser action with balanced lubricant effect for applications with high thermal stability specifications
Good stabiliser action with efficient lubricant system; good general-purpose performance
High lubricant action for applications where
high shear and/or high linear speeds are
experienced
Designed for high electrical quality cable
and for cables used under high ambient
temperature conditions
Good weathering protection for cables subject to outdoor exposure during service
life
High-cost efficiency where low melt temperatures are maintained, particularly when
chlorparaffin extenders are used
TABLE 1O.2-eontd.
Stabiliser products for rigid PVC pipe extrusion
Performance
characteristics
Trade
name
The selection of the correct stabiliser for pipe extrusion depends on the type of
extruder, the overall formulation and the specifications to be met. Associated
Lead offer the series of products below with varying but balanced lubricant
action, while retaining similar stabiliser effect:
XQ, SQ or BQ 3201
XQ, SQ or BQ 3202
XQ, SQ or BQ 3203
XQ, SQ or BQ 3204
XQ, SQ or BQ 3205
The performance of each product can be further altered by varying the dosage
rate. For example, a stabiliser used at between 20 phr and 24 phr without
filler would be recommended at a higher dosage, 26 phr to 30 phr in the
presence of high filler loadings. Different balances between internal and
external lubricant action are also available within the Associated Lead's range.
Stabiliser products for convoluted drainage pipe
SQ or BQ3221
SQ or BQ3251
SQ or BQ 3252
SQ or BQ3261
Good early gelation performance for applications where physical properties are
critical
Basic lead phosphite based for mouldings
subject to outdoor exposure
345
TABLE 1O.2-eontd.
Product
type
LF037
BalCd
liquid
BalCd
liquid
CalZn
liquid
Ba/Zn
paste
Pb liquid
LF114
LH 1671
PN 1678
LLOO5
Main
application
Flexible PVC moulding, e.g. footwear
Flexible PVC extrusion, e.g. tubing
Flexible PVC extrusion and calendering
Sulphur-staining resistant cable covering
Alternative to powdered lead stabilisers for
flexible PVC applications
Pipe extrusion
Pressure
pipe
100
PVC (Suspension K65)
CaC0 3 filler: (e.g. Omyalite
95T-Croxton and Garry Ltd)
1
XQ3204
22
XQ3203
XQ3221
Processing aid:
Paraloid K120N
(Charles Lenning Chemicals)
Pigment
Soil
pipe
100
Convoluted
drainage
pipe
100
10
28
40
1
As required
346
P. S. Coffin
Pipe
fittings
100
3
Exterior
mouldings
100
3
45
50
2
As required
Interior
profile
(twin-screw)
50
50
5
35
Interior
profile
(single-screw)
50
50
5
45
If required
As required
System A
100
40
System B
100
39
10
4
10
5
05
As required
TABLE 10.3
The Basic Stabiliser Range of Ciba-Geigy Ltd
Heat stabiliser products
Trade
name
Product
type
Main
application
General
comments
Irgastab DIM
Methyltin
mercaptide
Irgastab T4
Butyltin
carboxylate
Irgastab 1'9
Butyltin
carboxylate
Irgastab 17M
sheet
Good light stability
Butyltin
Rigid PVC
mercaptide
Irgastab 17MOK
Octyltin
mercaptide
sheet
food-contact applications
Irgastab T649}
Irgastab T
Estertins
Assessment of non-toxic
characteristics in
Irgastab BC445
BalCd/Zn
Irgastab BCZ06
BalCd/Zn
liquid
sheet
BalCd
progress
liquid
Irgastab BCZ8
PVC film
solid
Good weathering
properties
reduced form
Irgastab CZ11 }
Irgastab CZ113
CalZn
pastes
Irgastab A70}
Irgastab A80
Irgastab G1
Aminocrotonates
Irgastab S110
Antimony
PVC records
Product type
Function
Reoplast 39
Reoplast 38
Co-stabiliser
Irgastab CH55
Irgastab CH300
Irgastab CH310
Co-stabiliser
Tinuvin P }
Tinuvin 320
Substituted benzotriazoles
UV absorbers
Irganox 1076}
Irganox 1010
High-molecular-weight
hindered phenols
Antioxidants
348
P. S. Coffin
only other class of commercial tin stabiliser, the lauryltins, are mainly
used in Japan. A range of mixed metal stabilisers, both of soap and
complex-type, are also manufactured. The products mentioned in
Table 10.3 illustrate the range of such products available. In addition,
aminocrotonate products are available as metal-free stabilisers for
non-toxic applications and Irgastab SlIO is an antimony stabiliser
specifically for PVC records. Ciba-Geigy's range of auxilliary stabilisers
is extensive, with epoxy oils and organophosphites as co-stabilisers, as
well as UV absorbers and antioxidants.
10.6.3
TABLE 10.4
Calcium laurate
Calcium stearate
Nonnal lead stearate
Dibasic lead stearate
Lithium stearate
Magnesium stearate
Potassium stearate
Strontium strearate
Zinc stearate
Trade
name
Main
application
General
comments
Durostabe S59
Durostabe S64
Good general-purpose
performance
Durostabe 2048
BalCd
paste
Good general-purpose
performance
Durostabe 2176
BalCd
flake
Injection moulding,
e.g. footwear
Durostabe 2230
BalCd
paste
Durostabe 2240
BalCd
flake
Durostabe 2201
BalCd/Zn
flake
Durostabe S70
BalZn
powder
Durostabe 2188
BalCd/Pb
flake
Durostabe S65
BalPb
flake
Durostabe 2090
CalZn
powder
Non-toxic, FDA
approved ingredients
Durostabe 2147
CalZn
powder
Non-toxic, FDA
approved ingredients
Durostabe 2236
CalZn
powder
Durostabe S67
Zn/organic
Cable extrusion
Effective with
powder
asbestos loadings
Durostabe 2239
Pb
Durostabe 2248
3BLS'
Injection moulding
Durostabe 2270
3BLS'
Pipe extrusion
chlorinated extenders
flake
P. S. Coffin
350
TABLE lO.4-contd.
Mixed metal liquid complexes
Trade
name
Main
application
Product
type
General
comments
Nuostabe 979
BalCdlZn
liquid
flexible PVC
General-purpose
stabiliser
Nuostabe 1317
BalCdlZn
liquid
Effective with
chlorinated extenders
Nuostabe 1500
BalCdlZn
liquid
Nuostabe 1515
BalCdlZn
liquid
Nuostabe 1842
BalCdlZn
liquid
Nuostabe 3060
BalCdlZn
liquid
General-purpose
stabiliser
Nuostabe 1471
BalZn
liquid
flexible PVC
Nuostabe 1829E
BalZn
liquid
Nuostabes 1223,
1627, 3029, 3044
CdlZn
liquid
Nuostabe 983
CalZn
liquid
Nuostabe 1420
CalZn
liquid
Nuostabe 1602
CalZn
liquid
Plastisols
Nuostabe 1830
CalZn
liquid
Nuostabe 1839
CalZn
liquid
Plastisols
Nuostabe 1844
CalZn
liquid
Nuostabe 1858
CalZn
liquid
Nuostabe 1465
Pb
liquid
Alternative to powdered
Pb stabilisers
Nuostabe 1251
Chelator
liquid
Auxiliary stabiliser
Composed of FDA
approved ingredients
Effective at high
temperatures
footwear
351
3
3
2
05-10
3
352
P. S. Coffin
TABLE 10.5
The Basic Stabiliser Range of Diamond Shamrock Ltd
Flexible PVC calendering
General category
(1) Stabilisers with low
lubricant effect, good
clarity and light stability
(2) Lubricating stabilisers,
good plate-out performance
(3) Stabilisers for semi-rigid
PVC
(4) 'Do-it-yourself system
using all three components
as required
(5) Non-cadmium stabilisers
Trade name
Product type
Lankromark
Lankromark
Lankromark
Lankromark
LC 266
LC 145
LC 68
LC 442
Ba/CdlZn
Ba/CdlZn
BalCd
Ba/Cd/Zn
Lankromark
Lankromark
Lankromark
Lankromark
Lankromark
Lankromark
Lankromark
Lankromark
Lankromark
Lankromark
Lankromark
Lankromark
Lankromark
Lankromark
LP 15
LP 48
LP 125
LC 288
LZ 22
LE 98
LZ 253
LZ 242
LZ 341
LZ 330
LN 138
LP 103
LP 147
LP 301
Ba/Cd
BalCd
BalCd
BalCd
Zn
Chelator
BalZn
Ba/Zn
Ca/Zn
Ca/Zn
Ca/Zn
Ba/Cd
BalZn
Organic
Trade name
Lankromark
Lankromark
Lankromark
Lankromark
Lankromark
LC 431
A 3021
A 3131
LP 114
LP 356
Product type
BalCd
Ba/Cd
Ba/Cd
Trade name
Product type
10
353
TABLE 1O.5-contd.
(2) Stabilisers for footwear
(3) Non-cadmium stabiliser for
footwear
Lankromark LP 378
Lankromark LP 257
Lankromark LP 422
Ba/Cd
Ba/Cd
Plastisols
General category
(1) Stabiliser/activators
-kickers for foamed PVC
(2) Clear wear layers
(good light stability)
(3) Vinyl wallpaper
(4) Rotational moulding
(good mould release)
(5) Coal Board belting
(6) General-purpose paste
stabiliser
(7) General-purpose leathercloth stabiliser
(8) Non-toxic stabiliser
Trade name
Product type
Lankromark LZ 440
Lankromark LC 101
Lankromark LC 90
Lankromark LZ 187
Lankromark LZ 473
Lankromark LZ 352
Lankromark LZ 528
Lankromark LT 41
Lankromark LT 19
Lankromark LZ 528
Lankromark LZ 110
Lankromet LA 105
Lankromet LA 175
Lankromark LA 247
Lankromark LA 105
Lankromark LP 301
Lankromark LC 310
Zn-fast action
Cd/Zn-fast
Cd/Zn-fast
Ba/Zn-slow
Ba/Zn
Ba/Cd/Zn
BalZn
Tin maleate
Tin
BalZn
CalZn
Ca/Al/Zn
Ca/Al/Zn
Ca/Zn
Ca/Al/Zn
Organic
Ba/Cd/Zn
Lankromark LZ 121
Ba/Cd/Zn
Trade name
Product type
Lankromark LP 125
Ba/Cd solid
Lankromark LT 96
Butyltin maleate
Lankromark LT 118
Butyltin
mercaptide
354
P. S. Coffin
TABLE 1O.5-contd.
Rigid injection moulding
General category
Trade name
Product type
Lankromark LT 162}
.
.
Lankromark LT 63 Butyltm mercaptide
Lankromark LP 103 BalCd solid
Trade name
Lankromark
Lankromark
Lankromark
Lankromark
Lankromark
Lankromark
LT74}
LT 85
LN 303}
LN 402
LE 87 }
LE 109
Product type
Octyltin
mercaptide
Ca/Zn
Chelators
The above stabilisers (i.e. for blow moulding) would also be recommended for
rigid PVC calendering, but the lubricant system would be different.
100
3
2
05
05
10
10
40
40
355
100
25
14
08
07
07
As required
100
05
08
12
015
2
15
Tin
Ca/Zn
stabilised stabilised
100
15
10
12
10
100
12
05
35
08
12
13
Tin
Ca/Zn
stabilised stabilised
100
15
03
10
10
05
100
12
08
40
01
05
10
05
P. S. Coffin
356
Product
type
Vinco 348
Baled
liquid
Vinco 249C BalCdlZn
liquid
BalCdlZn
Vinco 265
liquid
Vinco 332 BalCdlZn
liquid
Vinco 374B BalCdlZn
liquid
Vinco 2810
Vinco 268
Vinco NlO
BalCdlZn
liquid
CalZn
liquid
CalZn
liquid
Vinco 654
CalZn
paste
Vinco 681
Phosphite
chelator
Main
application
General
comments
Extrusion
Good general-purpose
performance
Good resistance to
pigment plate-out
Good general-purpose
performance
Good sulphur-staining
resistance
Low toxicity, good
sulphur-staining resistance
Low toxicity, good
sulphur-staining resistance
Rigid and flexible PVC, e.g. For non-toxic applications,
flexible dairy and
moderate lubricant action
beverage tubing
Rigid and flexible PVC
For non-toxic applications,
for co-use with Vinco 654
type, but also included are Vinca 654 and Vinca 681 which constitute a
mixed metal soap system for such applications as flexible dairy and
beverage tubing.
REFERENCES
1. Press, J. B. (1978). Paper presented at the PRI International Conference on
357
CHAPTER 11
11.1 LUBRICANTS
11.1.1 Functions, Nature and Effects
Lubricants are essentially processing additives-their primary role is to
influence some aspects of behaviour of PVC compositions under the
heat and shear experienced in the processing machinery, so that the
processing is made easier, whilst certain factors promoting thermal
degradation of the polymer are counteracted (see below). For
example, in the extrusion of a rigid PVC composition effective
lubrication can increase output for a given heat and power consumption, or reduce the heating and mechanical power required for a given
output rate. As constituents of a PVC composition, lubricants can also
influence some material properties. for example the thermal stability
359
360
w.
V. Titow
processthermal
for, and
stock.
11
361
If the compatibility of such an additive is limited in the circumstances just mentioned, then it will have an external lubricant effect
(which may be combined with a degree of internal lubrication),
providing that its relevant chemical and physical properties make it an
effective 'slip agent' at the hot metal/PVC interface.
In broad terms, the compatibility of the common additives capable
of lubricant action, and their usual level of addition in PVC
compositions, decrease in the sequence:
primary plasticisers > secondary plasticisers and extenders >
impact modifiers* and processing aidst > stabilisers and
lubricants:j:
Thus the main operative features of additives incorporated specifically
as lubricants are:
(i) generally low compatibility with PVC (lowest for external
lubricants) ;
(ii) chemical nature enabling the lubricant effects to be exerted in
significant measure at the low level of addition (between O 2 and
about 30 phr for the total lubricant system, usually comprising
more than one lubricant).
Since the mode of a lubricant's action (internal or external) is closely
associated with its compatibility with PVC, several studies have been
made of the degree of compatibility of lubricants, measured in terms of
some relevant property of the lubricated PVC composition, with a view
to classifying the lubricants and/or predicting their suitability in
practical applications. 2 The properties measured included the amount
of haze introduced by the additive into a clear PVC compound3 (haze
being a manifestation of incomplete compatibility), and the reduction
of the glass transition temperature (Tg ) caused by its incorporation 4
(lowest Tg with the most highly compatible lubricant). The effect of
lubricants on the fusion behaviour of a PVC composition in a
*Some impact modifiers (e.g. extensively chlorinated polyethylene; nitrile
rubber; VC/EVA graft polymers) are highly compatible with PVC polymersee Section 11.2.
t Some processing aids are occasionally used in high proportions to increase
the resistance of PVC to deformation at elevated temperatures-see Section
11.2.
Lubricants with internal lubricant action are more compatible with PVC
polymer than typically external lubricants.
362
W. V. Titow
11
363
TABLE 11.1
Compounds Used as Lubricants2,4,9
General type
Class of compound
Examples
Hydrocarbons
Natural hydrocarbons
Synthetic hydrocarbons
Hydrocarbon
derivatives
Fatty acids
Fatty alcohols
Stearic acid
Cetyl, stearyl, octadecyl
Derivatives
of organic
acids
Amides
Esters and partial
esters
Stearamide
Butyl stearate, glycerol
monostearate, glycerol
monoricinoleate;
Stearyl esters, montan acid
esters
Wax esters
364
w.
V. Titow
Direct stabilising action: Most lubricants of the metal soap type (see
Table 11.1) have some stabilising effect, and some can act as stabilisers
in their own right, albeit their action in this role is not as strong as that
of the more powerful 'primary' stabilisers. Thus certain metal soap
lubricants (e.g. calcium stearate) can be used in either capacity in PVC
formulations (but when employed as the sole stabiliser, a relatively
large amount will be needed to provide a reasonable measure of
long-term stability, and the overall stabilisation will not be as good as
that conferred by a smaller proportion of a strong primary stabiliser).
Lead stearate and dibasic lead stearate are widely used as lubricating
components of lead stabiliser systems.
Synergistic action with stabilisers: Some lubricants can enhance the
effectivity of some stabilisers by a synergistic effect. The synergistic
lubricants are of the internal kind (i.e. comparatively highly compatible with PVC) and usually contain reactive functional groups (in
particular hydroxyl) in the molecule. Typical examples are partial
esters of glycerol with relatively long-chain saturated or unsaturated
aliphatic acids. In those compositions where it occurs, the synergistic
effect depends, in a complex way, on several factors, including the
PVC resin (type and grade), the nature and amount(s) of stabiliser(s)
in the stabiliser system, and the amount of the synergistic lubricant
present. The stabiliser systems which benefit from the effects of
lubricant synergists are those based on sulphur-containing tin compounds (thiotin or tin mercaptide stabilisers) or on lead compounds. In
rigid compositions incorporating calcium stearate as the sole heat
stabiliser (e.g. in some pipe compounds for potable water in Europe)
most lubricants, whether synergistic or 'neutral' in their effects with
other stabiliser systems, can produce some stability improvement. 12
Calcium stearate used as a lubricant synergistically improves heat
stabilisation by antimony mercaptide stabilisers. 13 With BalCd,
Ba/Cd/Zn, CalZn and Ca/Mg/Zn stabiliser systems synergistic effects
are important, but they are provided by epoxy-compound co-
11
365
366
W. V. Titow
The internal lubricating action of primary plasticisers has been mentioned (see Section 11.1.1 above): this makes the addition of internal
lubricants to plasticised compositions unnecessary in most cases.
However, if the external lubricant used is highly compatible with the
plasticiser(s), its lubricating action in the composition will normally be
reduced, necessitating an increase in the level of addition.
SECONDARY PLASTICISERS AND EXTENDERS
11
367
Most ABS and MBS modifiers have no lubricant action. With those
highly compatible modifiers which may be incorporated in large
proportions to act as permanent plasticisers (nitrile rubber, chlorinated
polyethylene of high chlorine content, VClEVA graft copolymers)
lubricant effects may arise. The presence of some impact modifiers
increases the compatibility of external lubricants with the composition,
so that the external lubricant has to be carefully selected (and a
relatively high amount may have to be used) for optimum results.
(d) Effects of Fillers and Pigments
Fillers and pigments (especially fine-particle grades) can bind lubricants by absorption (ct. plasticiser demand-Chapters 4 and 8) so that
their presence in a PVC (especially uPVC) composition can increase
the lubricant requirement. However, this effect may be reversed-at
least with regard to external lubrication-if the filler carries a stearate
coating (see Chapter 8) as this can not only block absorption of
lubricants at the particle surface, but also actually provide additional
lubrication.
11.1.3 Assessment of Lubricant Effects
W. V. Titow
368
employed. The torque rheometer is widely used for this purpose (as
indeed, in general, for practically oriented studies of melt-processing
characteristics of PVC compositions): very popular and well-known
commercial equipment of this kind is the Brabender Plasti-Corder. * In
essence this consists of a thermostatically heated mixing chamber
housing two rotors mounted in a measuring head and driven by a
variable speed motor. The equipment is instrumented for continuous
measurement of the torque on the rotors (which is a function of the
resistance of the PVC composition to the mixing action) and the mix
temperature. A plot of torque against mixing time typically shows a
rise of the torque as the mix is fluxed, and something of a drop when
the fusion point is reached (see Fig. 11.1): the 'fusion time' taken to
reach this point is increased by external lubrication; the torque value
can also reflect lubricant effects. A standard method for carrying out
CJl~
:J
L.
f-
~ ~ - ~-
- - - -
- ----=-=_::"':_=-=_:":_==--=-=-=-=-=_:-
A
Time
369
370
W. V. Titow
Underlubrication:
Product
371
Many suppliers of heat stabilisers for PVC (ct. Chapter 10, especially
Table 10.1) also supply lubricants. Listings of lubricant suppliers (as
well as those of most other additives) in the Western World will be
found in the publications mentioned in Section 8.5 of Chapter 8. Many
British suppliers are also listed in the Buyers' Guide for Plastics
Additives published by the British Plastics Federation. The following
may be mentioned by way of a few examples.
372
W. V. Titow
(b)
(c)
(d)
(e)
373
styrene/methacrylate copolymers;
acrylonitrile/butadiene/styrene (ABS) polymers;
styrene/acrylonitrile (SAN) copolymers;
poly-a-methylstyrene (PAMS).
Effects (i) and (v) can be sensitive to the nature and amounts of the
lubricants present in the composition (especially where the processing
aid is PAMS23).
Note: In view of effects (iv) and (v) the practice-occasionally
encountered-of calling processing aids for PVC 'flow promoters' is questionable. It would be preferable to restrict the
latter term entirely to its original use as a name for the group
of additives sometimes incorporated in thermosetting resin
systems to reduce the rate of interaction of reactive groups by
a dilution effect. 25
374
W. V. Titow
Effect (ii) is a contributory factor in the improvement in thermoformability conferred on PVC sheeting by processing aids (especially of
the acrylic type).
The mechanism whereby processing aids produce their effects is not
yet fully understood. In certain respects their action is similar to that of
internal lubricants, but there are also important differences (e.g. the
opposite effect on melt viscosity in most cases): attempts to treat the
action of both these types of additive as a simple case of plasticisation
at high temperature,25 fall short of a complete explanation.
In addition to their role in the processing of uPVC, which is the
primary reason for their use, processing aids present at the normal
levels of addition can also affect some properties of the material.
Typically (e.g. with acrylic processing aids) such effects may include
improved surface finish (freedom from defects; improved gloss), better
colour stability of coloured materials, and improved transparency of
clear compositions.
Incorporation in uPVC compositions of high proportions (up to about
50 phr) of some polymers with processing-aid action (e.g. certain
styrene/acrylonitrile (SAN) copolymers) can improve the heat distortion temperature, increase the Vicat softening point and reduce the
linear thermal expansion. However, impact strength is also usually
reduced, and suitable impact modifiers should be included in the
formulation to counteract this effect. Such compositions may be used
in a number of applications calling for a higher than average degree of
resistance to heat distortion (e.g. some pipes and injection moulded
pipe fittings, some extruded profiles): transparent versions in which the
polymeric modifiers (as well as the other components of the
formulation) are approved for food contact are of interest for the
manufacture of containers (jars, bottles) for food products which are
still hot at the filling stage (e.g. jam, marmalade, some liquids). The
following formulation has been cited (by Sahajpat26 ) as a good general
basis for a transparent composition of this kind, with low haze and
yellowness index, a Vicat softening point (DIN 53 460, 5 kgf load) of
85C and impact strength (ASTM D 256) of 324 kgf cm cm- 2.
Suspension PVC polymer, K value 58
Stabiliser: Irgastab 17 MOK (Ciba-Geigy)
Polymeric modifiers: SAN
MBS
Lubricants: Sapchim Lubricant 4150
Sapchim Lubricant 6164
100
12 phr
20phr
10phr
07phr
05 phr
11
375
376
W. V. Titow
The other difference lies in the respective test speeds (and hence
rates of deformation): those obtainable with ordinary strength-testing
equipment are much lower than the ones occurring in impact tests,
where the testing speeds are comparable with the speeds which can be
experienced by freely dropped objects (about 2-7 m S-I). These
differences do not mean that impact tests are fundamentally different
from strength tests. Although not measured directly in the latter, the
total energy to break can be computed from the area under the
stress/strain curve. Whilst the value so obtained will correspond to the
rate of deformation in the strength test concerned, and will thus
normally be numerically different from one furnished by a relevant
impact test (in which the deformation rate will be different), it has
been shown27 that both values can lie on the same smooth curve in a
plot of energy to break versus rate of deformation, if the mode of
failure (see below) is the same in the two tests.
Note: With special apparatus and instrumentation, tensile-strength
11
377
directly endowed. In both the material and its derivative products the
impact resistance is influenced-in a complex way-by many factors,
which may be grouped under the following headings:
'Internal' material factors: composition; morphology; fine structure (including crystallinity and molecular orientation); presence of impurities, nibs or gels.
(ii) Effects of processing conditions: modification of the material
properties (e.g. crystallinity, orientation, impurities, etc.) in
processing; heat degradation;* incomplete fusion;* incomplete
interdispersion of formulation components* (and especially
impact modifiers and particulate additives in the polymer); such
process-induced product features as 'skin-and-core' effects in
mouldings, presence of internal stresses (cooling and packing
stresses in mouldings); surface imperfections or faults; and
weak sites (e.g. weak weld lines in injection mouldings, or nip
closures in blow-moulded containers).
(iii) Design factors: In products:t abrupt changes in section
(especially sharp corners); moulded-in metal inserts; machined
holes and screw threads. In standard test specimens: 'geometry';
presence and characteristics of notches. In both: material flow
(direction and pattern) in the course of formation in relation to
the 'geometry' of the object (position and type of gates in
injection mouldings).
(iv) 'External' factors:+ energy and speed of impact (and hence the
rate of deformation); shape and hardness of impacting object;
point of impact; temperature; nature of environment (possible
presence of stress-cracking agents).
(i)
(some .crack-initiating).
:t:Operative in service conditions and/or tests.
378
W. V. Titow
DIN 55448-1977
ASTM D 1822-79
Plastics compositionsa
Plastics compositionsa
(specimens as in
ASTM D 1822)
Energy to break in J
or ft lbf
Energy to break per
unit cross-sectional
area, in J m- 2 or
ftlbfin- 2
(NB Test also gives
tensile strength, in
Pa or lbfin- )
Energy to break, in
mJ mm- 2 or kJ m- 2
Tensile impact
Energy to break, in
J; kgf cm; or ft lbf
Mean tup weight for
failure, in kg or lb
Energy to break, in J
BS 2782:1970: Methods
306B and C
ASTM D 3029-78
Falling weight
impact
Expression of results
See Table 11.3
Applicable to:
Rigid plastics compositions;a
rigid plastics sheet
Relevant standards
Flexural impact
(Izod and Charpy
type)
Test type
TABLE 11.2
Types of Standard Impact Test in General Use
V.l
a6'
S"
l':
~
~
"tI
t:;
;:
~c
1:;
;:
t:;.
'"a::
~
::l
''-
380
W. V. Titow
381
V
V
V
Specimen type A
Specimen type B
Specimen type C
V
V
Notch type A b
Notch type B
Izod
Shape
(crosssection)
Specimen
or notch
designation
Standard specification
Test type
45
45
45
45
45
45
Included
angle
025
0.25}
100
Tip radius
(mm)
Notch characteristics
Remarks
tv
Impact
resistance
unitsa
TABLE 11.3
Notch Characteristics and Impact Resistance Units in Standard Flexural Impact Tests
ClO
DIN 53 435-1977
DIN 53453-1975
BS 2782:Part 3: Method
351A:1977
Small standard
bar
Notch width:
2mm
Notch width:
08mm
45
Notch width:'
2mm orO8mm
45
45
Notch width: d
2mm or 08mm
45
45
U
U
V
V
Notch type B
Notch type C
Standard bar
V
V
Notch type Bb
Notch type C
Notch type A
Notch type A
Corner radii:
:/-01
Jm- 2
kJm- 2
kJm- 2
kJ m- 2 or
mJmm- 2
*o.J
*01 }
Com"
"d;;'}
:/-02
025
Com",.iiii,
02
10
l-(lO
Com,,,.dii,
025
00
Dynstat
Charpy
w.
384
V. Titow
TABLE 11.4
Conversion Factors for Common Units of Flexural Impact Resistance
Other units
SI unit
kJ m- 2
kgfcm cm- 2
ft [bf in- 2
ft [bf
(per inch of specimen
(notch) width O)
1
0981
210
524
102
1
214
536
0476
0467
1
250
0,191
0187
0401
1
with notch-tip radius of 025 mm and thickness of material under the notch of
1 mm (cf. ASTM D 256), on the assumption that-in general-the energy to
break is proportional to this thickness. 3
385
o
Fig. 11.2 Load (L)/deformation (D) curves for the three general types of
failure mode. Schematic representation. A, Brittle failure; B, ductile failure;
C, intermediate failure.
386
W. V. Titow
of the curve after the yield point depends on the actual mechanism of
plastic deformation of the material in the particular case (e.g. necking,
cold drawing, etc.). With the mode of failure intermediate between
brittle and ductile there is some yielding in the region of failure before
or during the propagation of a crack (cf. the curve of Fig. 11.2(C)).
Although the diagrams of Fig. 11.2 are schematic, they do illustrate the
typical shape of the load/deformation curves for the different modes of
failure, and the fact that-other factors being equal-the energy to
break (as represented by the area under the curve) increases with the
mode of failure in the sequence brittle ~ intermediate ~ ductile.
Among the 'external' factors influencing impact resistance, the
temperature and the speed of impact (rate of deformation) have a
special significance, in that changes in their values which can occur
within the general range of possible service conditions can alter the
mode of failure of many thermoplastics from ductile to brittle (or vice
versa) and thus sharply reduce (or increase) the energy to failure. The
'internal' and processing factors most strongly affecting this transition
under service conditions (or in tests) are the basic composition (e.g.
presence or absence of impact modifiers in uPVC) , local stress
concentrations, and structural anisotropy. Lowering the temperature of
a thermoplastic which initially breaks in the ductile mode will normally
eventually result in a change to brittle fracture. Where the change is
sufficiently sharp, * the temperature at which it occurs is the
ductile/brittle transition temperature (Tb ), sometimes also referred to
as 'brittleness temperature', 'brittle temperature' or 'brittle point'. Its
value in any given circumstances is influenced by the various factors
affecting impact resistance (see above), and in particular by the
presence and magnitude of stress concentrators (surface faults or
damage in service, presence and tip radius of notches in tests): even
when all the main factors are kept constant the value assigned to the Tb
can be affected by the choice of criterion for identifying the change of
failure mode (e.g. whether sudden drop in impact strength, appearance
of fracture surface, load/deformation curve, etc.), and even by the
sensitivity of assessment under the same criterion (e.g. examination of
fracture surface with the naked eye, under the microscope, or by
electron scan). 29 However, these considerations do not invalidate
* With some plastics materials the drop in impact resistance with temperature
(and the associated evidence of transition from ductile to brittle deformation
on the fracture surface) may be very gradual, so that no definite Tb can be
established. 29
387
----------., - - - - - --
pc------- ---------.
I
I
20~
I
PPO
....cen-
c
~ 10
ti
...
..
u
a.
~~~;;~;;;;:===::::=~:==::::::-
= _.....L
OL-_
_200
-150
PSPMMA
-:'::-_ _----:::-:---_~
50
100
150
Fig. 11.3 Impact resistance (in a Charpy-type test on notched specimens with
025 mm notch radius) as a function of temperature for five polymers. PC,
bisphenol-A polycarbonate; PPO, poly(2,6-dimethyl paraphenylene oxide);
uPVC, unplasticised polyvinyl chloride; PMMA, poly(methyl methacrylate);
PS, polystyrene. (Reproduced from Ref. 34 with permission of the copyright
holder, ICI, and the publisher, John Wiley and Sons Ltd).
* In order of increasing impact resistance: brittle, blunt-notch-brittle, sharpnotch-brittle, tough but crack-propagating, very tough, crack-arresting.
388
w.
V. Titow
are in the glassy state, and below their brittle temperatures (which
roughly coincide with the glass-transition temperatures), throughout
the entire temperature range covered, and hence break in brittle
fashion, with low energy to break.
Note: In contrast with the impact resistance, the tensile strength of
thermoplastics increases with decreasing temperature. * The
brittle point may be defined in terms of this property as the
temperature at which the yield strength is just equal to the
brittle strength (and below which the latter becomes
higher).34
Ziebland 38 increased from 77 x 103 1bf in- 2 at 20C to 197 x 103 1bf in- 2 at
389
60
~~
20
20C
40
:::.
.:L
111
CI
'E
....,
'-
.0
.:L
E
~10
20
'CI
C
002
(05)
004
Notch radius, in
(10)
(mm, approx)
006
008
(1-5)
(20)
390
W. V. Titow
relatively narrow range of common service temperatures, is attributable to the onset of brittle fracture brought about by the relatively
severe 025 mm notches at the speed of impact employed in the test.
As has been mentioned, the effects of both these factors are
reasonably representative of those of stress-concentrating faults and
impact speeds which may occur in service.
Note: Notches, or 'natural' faults, in a polymeric material can raise
the Tb and thus promote brittle failure not only by causing
stress concentration, but also by limiting the amount of plastic
deformation which can take place locally before fracture
occurs, through a modification of the stress field at the
incipient crack tip (transition from plane-stress to plane-strain
conditions29 ). Contributory factors which can arise in practice
include incomplete fusion (gelation) of the PVC composition
(in consequence of inadequate heat processing), or degradation of the polymer (excessive heat processing).
11
391
392
W. V. Titow
SW = 100 [1 - (Is/I)]
where: SW is the stress whitening (%), Is is the % light
transmission after stressing, and I is the % light transmission
before stressing.
In processing, many impact modifiers act as processing aids,
11
393
Extrusion compounds of this kind are used, for example, for profiles,
and sheets for thermoforming (with particular suitability for deep draw
forming) into such products as panels, casings (e.g. computer
housings), and battery covers; injection moulding compounds are used,
inter alia, for electronic equipment covers and housings, television
cabinets and the like. Good surface finish and low SG are among the
useful features of these materials.
In semi-rigid sheeting ABS modifiers can also substantially improve
thermoformability and reduce post-forming shrinkage.
Very high proportions of suitable ABS polymers can be incorporated
in flexible PVC compositions (e.g. 65/35 ABS/PVC in some cases) if
10
15
10
15
10
15
10
15
10
15
Amount
(phr)
58
62
54
61
45
48
48
49
36
34
13-8
325
220
370
101
152
64
82
51
72
at -36C at 23C
Notched impact
resistanceb
(kgf cm cm- 2 )
CaC03 filler
Chlorinated
polyethylene
EVA/VC
Modifier
43
44
37 d
42
41
30-35
20-25 d
30-35
30-35
Brabender
rheometer,
30 rpm
30-35
oven
Heat stability at
2000C (min)
CC)
88
91
83
82
83
82
82
85
82
81
1 kg load
72
73
70
70
70
68
70
69
69
68
5 kg load
TABLE 11.5
Effects of Different Impact Modifiers on some Properties of a Rigid PVC Composition
(Summary of selected data from Ref. 26)
<:;
:::;j
:<:::
'R
...,
11
395
the plasticisers are chosen for compatability with the ABS component.
In such compositions it is the PVC which may be regarded as the
modifier for ABS, improving the latter's tear and abrasion resistance,
hardness and tensile strength, and reducing flammability.21
MBS MODIFIERS
Whilst modifiers of this class can be used in opaque formulations, they
are of particular interest for clear compositions (e.g. bottle, film and
sheeting compounds), as many have refractive indices in the right
range to promote good clarity: with several MBS modifiers this may be
combined with good colour and surface gloss as well as resistance to
stress whitening, good heat stability and low degree of odour and taste
transfer in containers. Increases in the room-temperature impact
strength of rigid compositions obtainable with some MBS modifiers can
be as high as 25-fold (e. g. from about 1 ft lbf in -1 to about 25 ft lbf in- 1
with Blendex 436 (Borg-Warner Chemicals) in a notched Izod-type
test).
EVA MODIFIERS
This group comprises EVA copolymers, and graft copolymers of vinyl
chloride with EVA. In general, the impact-modifying effect of EVA
copolymers in PVC increases with increasing vinyl acetate content.
Room-temperature impact strengths of about 20 ft lbf in-1 (notched
Izod, ASTM D 256) can be attained in some compositions at 10-15 phr
loadings.
The vinyl chloride component in EVAlVC polymers promotes
compatibility with PVC. Some graft copolymers of this kind (e.g. Du
Pont's Elvaloy resins 741 and 742) can be used as solid plasticisers of
exceptionally high permanence, in amounts as high as 80 phr. 13 ,43
Like some all-acrylic modifiers (e.g. Aeryloid KM 323B-Rohm and
Haas) EVA modifiers (e.g. Levapren 245O-Bayer; Hostalit HHoechst; Elvaloy 836 and 837-Du Pont) do not appreciably impair
the retention of physical properties (and, in many cases, colour) on
weathering of uPVC compositions which contain them: they are
therefore applicable in such products as window frames, cladding and
fencing profiles for external use, and rainwater goods.
Note: As has been mentioned in Chapter 1, a suitable EVAIVC
graft copolymer can be used on its own (instead of a PVC
resin/modifier combination) in uPVC products of this kind.
396
W. V. Titow
* The trade name Paraloid is used by Charles Lenning Chemicals and affiliates
in the UK and certain other countries: the product coding is universal.
11
397
398
W. V. Titow
properties of the blend (and any composition in which the blend is the
base polymer) will reflect this mutual effect. The ratio of the components is the most important single factor governing the extent of
modification in a given case, but other factors also play a significant
part, e.g. the acrylonitrile content and Mooney viscosity of the rubber,
and the molecular weight of the PVC polymer,5! as well as the nature
and content of any other constituents of the composition (e.g. plasticisers, fillers). As a broad generalisation it may be said that in the blend
the PVC polymer contributes ozone, oil and fuel resistance, strength
(tensile and tear), and stiffness, as well as weatherability (with proper
stabilisation), abrasion resistance, flame resistance (which may be
enhanced by the presence of phosphate plasticisers and/or chlorinated
plasticiser-extenders in the composition) and higher electrical resistivity. Thus these properties of a nitrile rubber will be upgraded by
modification with PVC.
Note: The increase in strength (and especially tear strength) can be
maximised in vulcanised PVC-modified nitrile rubber compounds if the vulcanisation system is based on the total
polymer blend (not the rubber component alone).
11
399
40
(A)
(B)
10 20 30 40 50 60 70
'0 PVC
10
20
30
0'. PVC
40
50
Fig. 11.5 Some effects of PVC content in blends of PVC homopolymer with
nitrile rubber. (A) Tensile strength (TS) and modulus (M) of nitrile gum stock.
(B) Oil resistance of medium-acrylonitrile rubber.
regard to the toughening effect of nitrile rubber in PVC, the point has
been made39 that, whilst a rubbery additive capable of being dispersed
in PVC polymer on a molecular level could increase the impact
resistance by reducing the yield strength (promoting ductile failure) in
the same way as a plasticiser, a two-phase system is more effective in
producing a high degree of toughening.
In the production of blends of PVC polymer with nitrile rubber,
melt-compounding is necessary for maximum uniformity and completeness of inter-dispersion. However, availability of the rubber in powder
form enables it to be included in PVC compounding processes at the
pre-mix (dry blend) stage. Ready-made blends (in slab, chip, or powder
form) are also available from commercial sources: e.g. the Breon
'Polyblend' 500 series (BP Chemical International Ltd-blends of
butadiene/acrylonitrile copolymers of medium-to-high acrylonitrile
content with PVC homopolymer). The blends may be compounded
with additional nitrile rubber or PVC polymer (to adjust the ratio of
the two components to a value required for a particular purpose),
and/or with other materials appropriate to the intended application
400
w.
V. Titow
1850
430
1100
93
118
320
328
-51
26 x 109
11
401
11.3 COLOURANTS
11.3.1 General Nature and Functioning
Colourants may be broadly divided into pigments and dyes. Both terms
can have somewhat differing connotations in different industries, but
for the purpose of this section-and without attempting a comprehensive description-the following working definitions are valid. Pigments
are colouring materials which are insoluble (i.e. not dispersible on a
molecular level) in the base polymer of a plastics composition, and
therefore remain in particulate form when incorporated in the
composition by proper compounding procedures: dyes are colouring
materials which are soluble in the above sense.
402
W. V. Titow
11
403
1l.2.2(c)).
11.3.2 General Classification
404
W. V. Titow
plasticisers. For this reason they are relatively little used in flexible
PVC compositions in which their solubility can give rise to troubles
associated with migration ('bleeding', 'marking-off', 'blooming'). As
organic compounds with high degree of unsaturation the dyes (and
many of the closely related organic pigments) are fairly sensitive to
light (prone to fading or changes of shade). Their molecular state of
dispersion in PVC compositions also makes them more accessible to
light, and thus accelerates any photochemical effects they may suffer in
both pPVC and uPVc. Examples of commercial dye colourants for PVC
include Red HHR and Blue B (Hoechst) used in coloured gramophone
record compounds; Amaplast Yellow RRT (American Colour and
Chemical Corp.)-an azo yellow for use in rigid compos~tions; and
quinaphthalone yellows for uPVC (Mitsubishi Chemical Industries).
Rhodamine B has been evaluated53 as a fluorescent colourant for PVC
traffic cones, vacuum-formed emblems, point-of-sale displays, and the
like.
Commercial pigment colourants for PVC are discussed in Section
11.3.5; the main groups are listed, with some property data, in Table
11.7. In addition, the following general points may be noted. As with
other additives, the highest possible degree and uniformity of
dispersion* of a pigment in the PVC composition is very important, in
this case for maximum colour value and uniformity of coloration:
hence the form in which the colourant is used (see Section 11.3.3)
should be considered, inter alia, from the point of view of dispersibility.
Stability of PVC compositions may be reduced by some pigments
containing iron and zinc (especially salt-type pigments in which ions of
these metals are present, or pigments containing such ions as
impurities). Pigments containing barium, cadmium, lead, tin, or
calcium may have the opposite effect. Some pigments (notably carbon
black and titanium white-see Section 11.3.5) can improve weathering
resistance (d. also Chapter 12, Section 12.6, and Chapter 4, Section
4.4.1(g. Occasionally an interaction may be possible between certain
dyes and fillers: this effect is not very common, but in case of doubt
reliable advice can be had from the colourant supplier on this point.
Any colourant used should also be resistant to HCI which may be
liberated in the composition in processing or service: for example some
11
405
406
W. V. Titow
11
407
408
W. V. Titow
the monitoring and control of colour quality and uniformity, and shade
consistency in production. The following equipment may be mentioned
by way of non-selective examples: the Gardner XL-80S colorimeter
system;55 the Vibrochrom FFR 2 colorimeter with companion computer (Chemiefaser Lenzing AG, Austria);56 the 7842 Color Analyzer II
(IBM Instrument Systems, USA); Match-Mate 3000 (Diano Corp.,
USA); and ACS 500 (Applied Color System, USA).57
11
409
410
W. V. Titow
and Colourists, and Oil and Colour Chemists Association, and the
German Mineralfarben-industrie eV.
(e) Cost
This is an important consideration, applicable no less to the colourants
than to any other constituents of a PVC formulation.
11.3.5
100
50phr
8-10phr
as indicated
* This section, edited and supplemented for the present" edition, was originally
contributed (to the previous edition) by Mr H. G. White of ICI.
tThese tests were used by the compiler of Table 11.7. Other tests (some more
stringent) can be applied, e.g. those detailed by Ciba-Geigy in connection with
that company's rating of its pigments for PVc. 63
11
411
DCB/PCP
DCB-DA/PTMP
DCB/AA2MCA
DCB/PMP
TCB/AAMX
DCB/AAOA
DCB/AAMX
(A) Toners
Barium-2B
Strontium-2B
Manganese-2B
Calcium-2B
Calcium-4B
Ca-monoazo
Ba-monoazo
Ca-ONPSA
Ba-ONPSA
Ba-monoazo
(B) Disazos
Chemical type
P.Red 48
PoRed 48
PoRed 48
P.Red 48
P.Red 57
P.Red 134
P.Red 133
N.L.
P.Yellow 62
P.Red 151
P.Yellow 81
P.Yellow 17
P.Yellow 13
N.L.
PoYellow 83
Po Orange 13
N.L.
P.Red 111
P.Red 38
Vulcafor Red AS
FW Rubine Toner BOS
Rubine Toner 2BRS
Irgalite Red RC
Vynamon Claret YS
Irgalite Red HGL
Irgalite Red HBL
Irgalite Yellow WSC
Irgalite Yellow WSR
P.V.Red H4B
Brand name
050
010
010
010
005
010
0075
005
005
015
015
010
010
010
10
05
05
05
025
Amt
for!
ISD
(%)
TABLE 11.7
Pigments for PVC and Some of Their Properties
05
05
05
05
05
05
05
05
05
05
05
05
05
05
10
10
20
20
05
001
001
001
001
001
001
001
001
001
001
0 01
001
001
001
002
002
0 04
004
001
% in
patterns b
6-7
7
6-7
7
7
6
6
5
5
4
5-6
6D
5
4
6
6-7
6-7
7
6
6
6
5-6
6
6
4
4
3
3
5-6
1-2
2-3
3
3
1-2
-
Light
fastness C
5
5
5
4
5
4-5
4-5
5
5
5
3-4
5
2Y
3Y
5
5
5
5
5
4Y
4Y
4Y
3Y
3Y
5
5
5
5
4
4
4B
4B
2B
5
4-5
2Y
2Y
2Y
Heat
stabilityd
(E) Polycyclics
Indanthrone
Dioxazine
Dioxazine
Thio indigoid
Perylene
Perinone
Flavanthrone
Quinacridone {3
Quinacridone a
(F) Isoindolinones
7th FAT/PEC
Congress
(1964), p. 61
(D) Insolubilised
Monoazos
No disclosures
040
050
025
025
P.Yellow 109
P.Yellow 110
P.Orange 42
P.Red 180
Yellow 2GLT
Yellow 3RLT
Orange RLT
Red 2BLT
Irgazin
Irgazin
Irgazin
Irgazin
016
008
020
030
013
050
008
005
020
010
010
008
025
040
010
022
05
01
01
01
01
01
P.Blue 60
P.Violet 23
P.Violet 35
P.Red 88
P.Red 149
Vat Orange 7
P.Yellow 112
P.Violet 19
P.Violet 19
P.Orange 38
P.Red 185
P.Red 183
P.Red 171
N.L.
P.Yellow 105
P.Red 150
P.Red 187
P.Yellow 94
P.Orange 31
P.Red 139
P.Red 144
P.Red 140
P.Red 142
P.V.Red HFG
P.V.Carmine HF4C
P.V.Fast Bordeaux HFR
P.V.Fast Maroon HFM
P.V.Brown HFGG
Vynamon Yellow 8GS
P.V.Carmine HR
P.Y.Pink FL
Cromophtal Yellow 6G
Cromophtal Orange 4R
Cromophtal Red GR
Cromophtal Red BR
Cromophtal Red R
Cromophtal Rubine B
001
001
001
001
001
001
001
001
001
001
001
001
001
05
05
05
05
001
001
001
001
001
001
001
001
001
001
001
001
001
001
05
05
05
05
05
05
05
05
05
05
05
05
05
05
05
05
05
05
05
05
05
05
05
7
7
6
6
7
6-7
6-7
6-7
7
6
6
7
6-7
6-7
6-7
3
5
7
5
6
6
5-6
5
7D 6-7D
7D 7D
7D 7D
7D 7D
7
7
7
7
7
7
7
>7
>7
6-7
6-7
7
7
7
7
5
6
7
6-7
7
7
6-7
6-7
5
5
5
5
5
5
4-5
5
5
5
5
5
5
4-5
5
5
4-5
5
5
5
5
5
5
5
5
4-5
5
4B
5
4Y
4Y
4
5
1
3Y
4-5
3Y
4-5
4D
4Y
4Y
4-5
5
4-5
4Y
4-5
3-4
3Y
5
5
4-5
4-5
4Y
4Y
11
(G) Phthalocyanines
CPC, ll'form
CPC, stable ll'
CPC, f3 form
Chlorinated CPC
Brominated CPC
(H) Other Organics
Iron nitroso-f3-napthol
Aniline black
Carbon black
(I) Cadmiums
Cadmium sulphide
Chemical type
11
P.Yellow 37
Yellow P 3680
Primrose P 500
Lemon Yellow P 3682
Light Orange P 4701K
Deep Orange P 4702K
10
10
10
075
075
010
10
005
P.Green 8
P.Black 1
P.Black 7
Vulcafor Green LS
Monolite Fast Black LS
Kosmos 70
Cadmium
Cadmium
Cadmium
Cadmium
Cadmium
006
007
008
016
020
Amt
for!
ISD
(%)
P.Blue 15
P.Blue 15
P.Blue 15
P.Green 7
P.Green 41
Brand name
TABLE 11.7-eontd.
5
5
5
5
5
05
05
05
05
05
05
05
05
7
7
>7
7
7
6
7
>7
001
001
001
01
01
01
01
01
>7
>7
>7
>7
>7
001
001
001
001
001
5
5
5
5
5
6-7
6-7
6-7
6-7
6-7
5
5
5
5
5
3
5
5
4-5
5
5
5
7
>7
3Y
4Y
3-4Y
4-5
5
Heat
stabilityd
4-5
5
5
5
5
>7
>7
>7
>7
>7
P
F
Light
fastness C
%in
patterns b
P.V.Fast Brown G
20
075
03
10
10
10
10
10
15
10
10
075
075
075
075
= Darkening.
P.Green 17
P.Blue 29
P.Brown 6
P.Red 104
II
P.Yeliow 34
P.Red 108
11
Lead molybdate
II
(J) Chromes
Lead chromate
Cadmium selenide
11
Cadmium
Cadmium
Cadmium
Cadmium
Cadmium
Cadmium
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
01
01
01
01
01
01
01
01
01
01
01
01
01
01
01
>7
7
>7
7D
7D
7D
7D
7
7
7
7
>7
>7
>7
>7
7
7
7
7D
7D
7D
7
7
7
6-7
6-7
7
7
7
7
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
4Y
5
5
5
5
5
5
5
5
5
5
5
5
5
416
W. V. Titow
D. Insolubilised monoazo: These are types in which heavy substitution of the simple monoazo pigment has suppressed solubility to very
acceptable levels; usually this is obtained at appreciable financial
expense.
E. Polycyclic compounds: These are offshoots of the vat dyestuffs
used on textiles; this highly selected group of colours give very high
strength, fastness and brilliance but at a very high cost.
11
417
Plate A-<:ontd. (2) Four-roll laboratory calender ('inverted L' type, rolls
6 in x 15 in).
418
w.
V. Titow
J. Chrome pigments: For example, lead chromate and lead molybdate form a much less expensive greenish yellow to scarlet range of
pigments in which recent improvements have given light fastness
comparable with cadmium pigments, but they remain susceptible to
strong alkalies and to darkening by hydrogen sulphide.
K. Other inorganics: These include ultramarine, iron oxides and
chromic oxide, which are, respectively, the cheapest brightest reddish
blue, a source of very cheap and fast fawn to brown colours provided
very high processing temperatures are not involved, and the best base
for green colorations for the production of camouflage effects.
11
419
420
w.
V. Titow
421
a=EoK
where: ais the surface charge density (Cm- 2), K is the field strength
measured (V m- 1), and Eo is the permittivity of free space (8,85 x
1O- 12 Fm- 1).
Field meters can also be used qualitatively to detect the presence of
a charge or locate the point(s) of highest density. A convenient hand
instrument is the 'Statigun',7 a gun-shaped, valve electrometer. The
rate of charge decay can be measured with the aid of electrometers,
but the important point that the charging method must be standard and
reproducible is frequently overlooked. In more fundamental investigations charging by rubbing is not satisfactory. Measurement of charge
decay in, say, factory conditions (e.g. on sheeting charged in the
course of a particular process) can be meaningful in the limited context
of that process and can give an indication of the efficiency of antistatic
agents and treatments. The figure usually quoted in connection with
charge decay results is the 'half-time', i.e. time required for the charge
to be reduced by a factor of 2.
Good reviews of the generation, nature and measurement of
electrostatic charges on plastics have been published by Quackenbos,74
Ferraris,75 and Gale and Pacitti. 7o
As already mentioned, in practice the 'static' properties of a plastic
are most often gauged and indicated in terms of surface and volume
resistivity, and several standards lay down their requirements in those
terms. Thus, for instance, the maximum resistivity (as determined in
prescribed tests) of PVC conveyor belting for underground use in coal
mines is laid down as 3 x 108 Q by both BS 3289:1960 and the
422
W. V. Titow
11
423
424
W. V. Titow
10
10
630
-33
5
20
720
-25 -29
70 phr
-31
0
1000
640
-34
5
15
580
520
10
-37
80 phr
7
5
11
480
-36 -38
0
450
530
10
5
430
-40
90 phr
TABLE 11.8
Some Effects of 'Antistat A' in a pPVC Compound
-39
0
300
480
-41
5
7
420
100 phr
-43
10
4
390
Vl
i:>
3l::
ri
"t:l
to
~
1:;
~;::
!:;"
'"~
~
::i
......
......
426
w.
V. Titow
11
427
sufficient to maintain the high temperature required for, and the rate
of, pyrolysis at a level necessary to provide enough pyrolysate (in
suitable form-i.e. gaseous or fine mist) to keep the combustion going.
Any of the products of both pyrolysis and combustion (see Fig. 11.6)
may find their way into the smoke emitted by a burning plastic. In
terms of its physical nature smoke is a suspension of particles in a
mixture of air and the gases and vapours generated in the burning
process (and remaining uncondensed into liquid droplets or layers on
existing particles).8D-82 The particles of the particulate phase may be
solid or liquid (or some of each); some at least may have a solid
carbon 'skeleton'.83 Gases and vapours are invisible: hence, in any
given case (i.e. for a fixed total amount of matter in the smoke) the
smoke density, usually defined in terms of obscuration of light, will be
determined by the proportion of constituents present in the particulate
phase, and to some extent also by the particle size and size
distribution. In general, the greater the amount of pyrolysis products in
the smoke (i.e. the less complete the combustion) the greater the
visible smoke denisty (because the pyrolysis products tend to have
higher molecular weights than the final products of combustion and
hence condense more readily into droplets when mixed with relatively
cool air). In any particular case the actual nature and proportions of
the chemical constituents of the smoke will depend, in a complex way,
upon the chemical composition of the burning plastic and, given that,
upon the burning conditions (especially the temperature and the supply
of oxygen): the same factors also influence the parameters governing
smoke density.
11.5.2 Flame Retardance and Smoke Suppression in PVC
Compositions
It is the large proportion of chlorine they contain that is responsible for
w.
428
V. Titow
POLYMER
Pyrolysis +-
Liquid or
SlZmi-liquid
dlZgradation
products
('tar')
- - - - - - - -
GaslZous (vapour
phaslZ) dlZgradation
products
- - --
Solid or
SlZml-solid
dlZgradatlon
products
(primary 'char')
FurthlZr pyrolysis +-
--i
I
Solid
carbonaclZous
rlZsidulZ
(slZcondary 'char')
Combustion
\
\
Combustion
products (including
CO, CO2, H20 and
various oxidlZS)
I
I
I
I
I
\\
I
I
I
/" ,
<, HlZat ,/ - ,
/
I
-
_ ......
11
429
430
W. V. Titow
that of borax (historically one of the earliest flame retardants, first used
in textiles), i.e. by fusing to form a protective layer which impedes
access of oxygen and heat to the PVC material;25,84 the fusion also
abstracts some heat from the system.
As particulate additives insoluble in PVC compositions the metal
oxides and borates just mentioned all have some opacifying effect
(rather lower in general with the latter compounds): this is minimised
with ultra-fine (sub-micron) particle grades (d. Section 11.3.1 above)
which are becoming increasingly widely available.
Note: The opposite approach to the same end is represented by a
version of Sb 20 3 of particle size considerably larger than in
the common, regular grades (1O-40/lm as against 1-3/lm):86
this is offered as a low-reflectance 'non-opaque' grade on the
basis that the comparatively lower number of coarse particles
present at a given level of loading by weight causes a lower
overall amount of interference with light.
11
431
DOP
Epoxidised oil
{ Aryl phosphate ester
Chlorinated paraffin (52% Cl)b
{ Antimony trioxide
Zinc borate
Molybdenum complex c
{ Zinc/magnesium complex d
25
2
4
25
60
5
32
5
50
24
24
60
5
5
25
60
Smoke
suppressants
Flame
retardants
Plasticisers
Semi-rigid
formulations (phr)
TABLE 11.9
Outline Examples of Flame-retardant/Smoke-suppressant Systems for Flexible and Semi-rigid PVC
"'"
:::'1
o;;:
~
:'"
W
N
11
433
h' h
18
)
temperature
434
W. V. Titow
11
435
REFERENCES
1. Stapfer, C. H. (1969). Plast. World, 27(6), 76-7.
2. Pacitti, J. (1964). 'The Use of Lubricants in PVC', RAPRA Report No.
470, January.
3. Marshall, B. I. (1969). Brit. Plast., 42(8), 70-6.
4. King, L. F. and Noel, F. (1972). Polym. Engng. Sci., U(2), 112.
5. Oakes, V. (1970). 'Stabilisers and lubricants for PVC'. Plastics Institute
Symposium on Additives for PVC, Manchester, England, Feb. 1970; and
Oakes, V. and Hughes, B. (1966). Plastics, 31(347), 1132-4.
6. Di Francesca, A. (1966). Mat. Plast. Elast., 32(10), 1035-47.
7. Gale, G. M. (1973). In Developments in PVC Technology, (Eds J. H. L.
Henson and A. Whelan), Applied Science Publishers, London, Ch. 3.
8. Andrews, K. E., Butters, C. and Wain, B. J. (1970). Brit. Plast., 43(10),
97-101; 43(11), 88-90.
9. Chauffoureaux, J. c., Dehennau, C. and van Rijckevorsel, J. (1979). J.
Rheo!., 23(1),1-24.
10. Logan, M. S. and Chung, C. I. (1979). Polym. Engng. Sci., 19(15),
1110-16.
11. Illmann, G. (1967). SPE J., 23, 71-8.
12. Worschech, K. F. (1978). 'Synergistic support of various stabilisation
systems during PVC processing by using lubricants', paper presented at the
PRI International Conference on PVC Processing, Egham Hill, Surrey,
England, 6-7 April, 1978.
13. Titow, W. V. (1978). In Developments in PVC Production and
Processing-I, (Eds A. Whelan and J. L. Craft), Applied Science
Publishers, London, Ch. 4.
14. Petrich, R. P. (1978). 'Effect of processing aids and impact modifiers on
processing characteristics of rigid PVC', paper presented at the PRI
International Conference on PVC Processing, Egham Hill, Surrey,
England, 6-7 April, 1978.
15. Wilson, A. P. and Raimondi, V. V. (1978). 'Poly-alpha-methylstyrene as a
process aid for rigid polyvinyl chloride', paper presented at the PRI
International Conference on PVC Processing, Egham Hill, Surrey,
England, 6-7 April, 1978.
16. Blake, W. T. and Onufer, R. J. (1966). C. W. Brabender Instruments,
Inc., Data Sheet 11.
17. Bottner, E. F. and Rosenthal, C. (1972). Kunststoffe. 62(10),685-7.
18. Jacobson, U. (1961). Brit. Plast., 34, 328-32.
19. Riethmayer, S. A. (1965). Gummi, Asbest, Kunst., 18(4), 425-32.
20. Stapfer, C. H., Hampson, D. G. and Dworking, R. D. (1968). SPE
Technical Papers, 14, 26th ANTEC, 276-8.
21. Sahajpal, V. (1973). In Developments in PVC Technology, (Eds J. H. L.
Henson and A. Whelan), Applied Science Publishers, London, Ch. 4.
22. Wilson, A. P. and Raimondi, V. V. (1976). 34th ANTEC SPE
Proceedings, p. 513.
23. Wilson, A. P. and Raimondi, V. V. (1978). 'Poly-alpha-methylstyrene as a
process aid for rigid polyvinyl chloride', paper presented at PRI
436
24.
25.
26.
27.
28.
29.
30.
31.
32.
33.
34.
35.
36.
37.
38.
39.
40.
41.
42.
43.
44.
45.
46.
47.
W. V. Titow
437
438
W. V. Titow
CHAPTER 12
TITOW
12.1 INTRODUCTION
All properties of a PVC material depend, in a more or less complex
way, upon the formulation, and to some extent also on the effects of
compounding and processing (including the 'heat history'). However,
some properties are more directly associated with the nature and
amount of a particular class of formulation component: for example,
softness, extensibility, tensile strength and modulus are particularly
strongly influenced by plasticisation, many mechanical properties are
substantially upgraded by incorporation of fibrous reinforcing fillers,
flame resistance improvement can depend directly on the incorporation
of suitable flame retardants, and so on.
In this book, properties linked in such a manner with individual
formulation components and factors are considered in conjunction with
them in most cases. Some general information and numerical data on
properties are also given in Chapter 1 and Appendix 3. The properties
discussed in this chapter are either those which might be described as
more 'composite' in nature or origin, or which are relevant in some
special context or application.
440
w.
V. Titow
441
442
W. V. Titow
12
443
w.
444
V. Titow
100
~ 60------~
I
~
I
I
&
i!-
T(60),
I
I
The time for the chosen test property to drop to the pre-selected
percentage retention value at a particular temperature can be read off
the curves of either of the two plots. The expected service time after
which the test property will reach the value at room temperature can be
found by extrapolating the curve of Fig. 12.2.
445
446
W. V. Titow
12
447
= k(~+ ~)
(1)
w.
448
V. Titow
2
L =0205 ( %- .008)
01
02
03
04
05
Fig. 12.3 Volatile loss from calendered PVC film in test according to Method
B of ISO 176:1976(E), as a function of nominal thickness (~, dotted line).
Solid line: plot of eqn (1) with appropriate constants (PIA = 008 mm- 1 for
standard specimens in the method used; b = 2 for a sheet with both sides
exposed). PVC film formulation:
100
PVC resin (emulsion type)
70phr
Plasticisers: DIDP
45 phr
Polymeric
3phr
Stabiliser
05 phr
Lubricant
449
(i.e. up to about 40% volatile loss from this particular compositionsee caption of Fig. 12.3).
Cable compounds are rated, inter alia, according to the conductor
temperature to be withstood in continuous service, but the effects of
still higher temperatures which may be experienced occasionally (e.g.
heat shock resulting from a short-circuit) are also relevant. The
pertinent standard tests typically involve heating specimens (which may
be under mechanical stress) for relatively short periods at high
temperatures-e.g. 1 h at 150C (the heat-shock test of BS 6746:1976,
in which no visible cracks must be caused by the treatment), or 40 to
120 min (depending on the type of insulation material) at 200C (the
thermal stability test of VDE* 0271/3.69, in which the pH indicated by
a standard indicator exposed to the volatile products evolved must not
be less than 3). Heat-ageing tests are also applied in which specimens
are heated for longer periods at somewhat lower temperatures, with
pass requirements in terms of permitted volatile loss and property
change maxima (as in BS 6746:1976) or absence of cracks (as in VDE
0271/3.69 after 7 days at 120C). Although such requirements may be
coupled with particular service-related temperature rating (e.g. for a
nominal 90C cable sheath compound, suggested volatile loss limit of
25 mg m- 2 on heating for 7 days at 115C9 ), the test results do not, in
the main, provide a reliable basis for firm predictions of behaviour in
service.
Apart from the question of thermal degradation and ageing
generally, the thermoplastic nature of PVC, coupled with its
comparatively low softening temperature (lowered still further by
plasticisation), is a limiting factor on the maximum service temperature. The limit for most types of cable compound is 70C (conductor
temperature). Some special, high-temperature cable compounds are
rated at 85C (and even up to 105C for limited periods under certain
conditions) but at high temperatures external damage to, or distortion
under pressure of, the heat-softened material, as well as the possibility
of outward penetration of the hot conductor through it, become
serious considerations. Susceptibility to damage, at room temperature,
by hot objects or materials (e.g. soldering irons, hot oil splashes) may
also have to be considered. The performance of PVC cable compounds
can be substantially improved in these respects by cross-linking the
* Verband Deutscher Elektrotechniker (specification of the German Electrical
Engineers Association).
450
W. V. Titow
cable covering, and this has been receiving attention in recent years,
with special reference to irradiation techniques, including the use of
electron beams. 10,11
Some of the direct (i.e. non-degradative) effects of heat on the
properties of PVC are illustrated by the data of Figs 12.4-12.6. As with
thermoplastics in general, mechanical properties are reduced at
elevated temperatures, as is resistance to creep and fatigue; however
90
80
1...
If
70
~60
Coo
::l
1/1
~40
~30
:g20
10
o
Fig. 12.4 Effect of temperature on tensile strength and BS softness number of
PVc. 6, uPVC (normal impact strength grade); 0, pPVC (50phr noP).
12
451
gmil
10
'"'Eu 10
-52
..x
I:
". '
3"
"~
....
.
1i
.....
Q,
I:
12
10
20
30
40
50 60 70
Tllmpcrraturcr. c
80 90
452
W. V. Titow
uPVC is more thermally sensitive in this sense than the other common
'engineering' thermoplastics, and its softening temperature is comparatively low (see Appendix 3). The reduction of some of the mechanical
properties can be counteracted to some extent by incorporation of
fibrous reinforcement. Whilst improvement in the heat deflection
temperature under load is only moderate with, say, 30% glass-fibre
reinforcement (increase of 5-10C in some cases) creep at elevated
temperatures can be significantly reduced (see Fig. 12.6).
A non-degradative (though irreversible) effect of heat, which can be
a practical problem in service, is the longitudinal shrinkage of extruded
cladding and beading (finishing strip) sometimes occurring on buildings
and caravans. This is attributable to retraction of stretch imparted
during manufacture (extrusion and take-off).
The principal ways of securing the best practicable resistance of PVC
materials to heat degradation are proper stabilisation (by suitable
stabilisers in appropriate quantities, properly dispersed in the compound by suitable mixing-see also Chapters 4, 9 and 10) and-where
possible-the use of fillers and pigments which can afford additional
protection.
Volatile loss can be counteracted by proper choice of plasticisers
(polymeric plasticisers are particularly useful); use of polymeric
additives with plasticising action (e.g. copolymers of the Elvaloy* type,
highly chlorinated polyethylene, or nitrile rubber); ensuring that
plasticisers and all other constituents of the compound are of good,
consistent quality; and by general attention to the mutual compatability of all constituents.
12.4 PERMEABILITY
453
= P(F/L)
(2)
In this expression J is the flux of the penetrant, i.e. the amount (in
suitable units, e.g. of mass or volume, or in moles) passing through the
barrier in unit time; A is the area through which the passage takes
place; F is the driving force actuating the passage, e.g. the difference
between the concentrations (~c), pressures (~p), temperatures (~e)
or chemical potentials (~Il), of the penetrant at the 'upstream' and
'downstream' boundaries of the barrier; L is the barrier thickness, and
P is the permeability coefficient which embodies (i.e. whose value will
reflect) the effects of chemical and physical interactions in the system
(themselves dependent on the chemical nature and fine structure of the
barrier material).
As can be seen, F/L is the driving force gradient within the barrier.
The various quantities in eqn (2) may be expressed in any convenient
units, so long as those are mutually consistent; their choice will
determine the units (and hence will influence the numerical value)
of P.
In practice the permeability of plastics is commonly determined by
measuring-in standardised, steady-state conditions-the flux of a
penetrant (usually water vapour, oxygen, carbon dioxide or nitrogen)
through a film or sheet. Loss of contents (in terms of weight loss over a
period of time, i.e. average flux) through the walls of a container is
also often measured.
454
w.
V. Titow
Even if the same basic units are used (for flux, driving force,
film thickness, etc.), expression of the result of one and the
same determination (or results of separate determinations for
the same plastic/penetrant system in identical conditions) can
entail different combinations of the units and have different
numerical values, depending on the choice of the 'index' of
permeability (Le. whether permeability coefficient, rate of
transmission, permeance, etc.-see Table 12.1).
(ii) The same 'index' of permeability, expressing the result of the
same determination, will have different numerical values if given
in different units.
(iii) Values are sometimes quoted simply as 'permeability' without a
clear statement which 'index' is being used, so that units have to
be scrutinised to ensure correct interpretation of the figures.
Moreover, the same name is sometimes used for different
permeability indices.
This situation is illustrated by Table 12.1 in which the more common
ways of expressing permeability are listed, with the associated units
and an explanation of their mutual relationship (in terms of eqn (2)).
Since for a given penetrant/barrier system in defined conditions the
permeability coefficient should be a constant, expressing the relevant
intrinsic properties of the barrier material, this coefficient should-in
theory-be the best value to use as an index of permeability, especially
when comparing different plastics materials. It is often used for these
purposes, although here again the variety of units employed can cause
some confusion. The forms of permeability coefficient which are either
fairly widely used, or are of a more standard or fundamental nature,
are given in Table 12.2. A useful discussion of gas permeability
coefficients has been published by Yasuda. 12
However, the permeability coefficient is by no means solely or
universally employed as an index of permeability, because in practice
most plastics are multicomponent (often multiphase) materials; they
may be heterogeneous not only by virtue of these features per se, but
12
455
(3)
J/A
J/A
J/A
J/(A.~p)
(J.L)/(A.~p)
Transmission
rate
'Permeability'
1. Transmission
rate
2. Permeance
3. 'Permeability'
Film or thin
sheet
Flexible
sheet
Sheet up to
about 1/8 in
thick
Water
vapour
Water
vapour
Water
vapour
Le. =P
J/A
Transmission
rate
Name
Description
19.cm
m2.24 h.(mm Hg)
1 grain.in
ft 2.h.(in Hg)
Perm-inch =
Metric permcentimetre =
19
m2.24 h.(mm Hg)
1 grain
ft2.h.(in Hg)
grain
ft2.h
Metric perm =
Perm =
or
WVT
g
m2.24h
g
m2.24h
g
m2.24h
g
m2.24h
units
Constituent
simple
Special unit
name and/or
symbol
htdex of permeability
Film or thin
sheet
Plastics
barrier
Water
vapour
Penetrant
TABLE 12.1
Relevant determination
methods,
references and
remarks
Temperature
RH
E 96-66(1972)
~ASTM
BS 3177: 1959
BS 2782:Part 8:
Methods 820 A to G
(in preparation)
ISO/R 1195-1970
Barrier thickness (L)
Pressure difference (~p)Q
Temperature
RH
Data required
in
conjunction
:<::
:::l
0
.j:>.
'-"
a..
J/(A.t.p)
(J.L)/(A.t.p)
i.e. =p
J/(A.t.p)
J/(A.t.p)
(J.L)/(A.t.p)
1. Permeance
(for boards
with surface
skins)
2. 'Permeability'
(for boards
without
surface skins)
Transmission
rate
Transmission
rate (also
termed 'permeability')
1. Transmission
rate
2. Permeability
coefficient
Expanded
polystyrene
(board)
Films and
thin sheet
Films and
thin sheet
Film and
sheeting
Water
vapour
Gas
Gas
Gas
i.e.
=P
J/(A.t.p)
J/A
Water
vapour
Punit
barrer
GTR unit
also
Temperature
RH
10- 10 P unit
1 cm 3 (at STP)
m2 24 h.atm
ml (atSTP)
m 2 .24h.atm
cm 3 (at STPj"
m2 .24h.atm
--
1 fm b
Pa.s
ng.m
N.s
SI unit
ng
N.s
g
m2 .24h
WVT
ASTM 01434-75
NB This specification
also recognises (and
gives conversion factors for) the following
units of P: (cm3 .mil)/
(m 2 .24 h.atm);
(cm 3 .mil)/(lOO in 2 .24 h.atm);
(cm 3 .mm)/(m2 .24 h.atm)
BS 2782:Part 5: 1970
Method 514 A (in
1979 replaced by new
method 821A of BS
2782 Part 8: 1979-see
also ISO 2556)
ISO 2556-1974
(identical with BS
2782 Part 8: Method
821A 1979)
BS 3837:1977
(prescribing tests by
the method of BS
4370: Part 2: 1973)
technically similar to
ISO/R 1663
ISO/R 1663-1970
...
-..l
Vl
!:;
"
$::
I::>..
;:<
I::>..
I::>
l:;-
...5'~
I::>
()
'"0
~
S
["
S'
.g>
'"
1'"?to
......
tv
Plastics
barrier
Resistance factor
Any plastics
lamina (in
practice film
or sheet)
Permeability
factor
Name
(A.t1p)/J
i.e. = lI(P/L)
(J.L)/A
Description
p1
Special unit
name and/or
symbol
Index of permeability
Any
(but
mainly
fluids)
Walls of
Any
(consti.
plastics contuents
tainer
of contents of
a plastics con
tainer)
Penetrant
N.s
mol
--
g.cm
m 2.day
Constituent
simple
units
TABLE 12.1-eontd.
Temperature
RH
Data required
in
conjunction
Ref. 90
ASTM D 2684-73
Relevant determination
methods,
references and
remarks
:;;
:::J
00
Pressure"
difference (dp)
m2
g (24 h)-I
Water
vapour
Pressure"
difference (dp)
100in2
Gas or
vapour
cm 3 (24 h)-l
Gas or
vapour
Pressure"
difference (dp)
Pressure"
difference (dp)
cm 2
m2
mols- I
Concentration
difference (dC)
Concentration
difference (dC)
Nature
Pa(=Nm- 2 )
mol cm- 3
molm- 3
Units
mmHg
atm
cmHg
(F)
Driving force
cm3 S-I
cm 2
mols- I
Any
Gas or
vapour
m2
Area
(A)
units
mols- I
Flux
(J)
units
Any
Physical
state of
penetrant
in contact
with
barrier
(L)
cm
mil
cm
cm
units
Thickness
g
(mm Hg)
--=
p
24h.m 2
cm
mol
N
-=
Ps.m 2
m2 .m
b cm 3
(cm Hg)
--=
p--s.cm 2
cm
b cm 3
atm
=P24 h.l00 in 2
mil
mol
mol
--=
Ps.cm 2
cm 3 cm
mol
mol
-=
Ps.m 2
m3 .m
Equation (2)
in terms of
the units
TABLE 12.2
Some Common Fonns and Units of the Permeability Coefficient
g cm (24 h)-I
m- 2 (mm Hg)-I
cm 2 s (cm Hg)-l
"tl
molms- I N- 1
.,..
ID
v.
I;;;
'"
i:
;:s
l::l
;;;-
l::l
:::!.
(j
-.::::
~
S
~
....
S-
'"~
"-
"....
::>.
.g
......
'"
cm 2 S-I
m 2 s- 1
Resulting
units of
permeability
coefficient
(P)
w.
460
V. Titow
coefficient (assumed to be constant or dependent only on concentration) and S is a solubility factor expressing the equilibrium content of
the penetrant in the plastics barrier material at the relevant
temperature.
If S is given in the form of a ratio, viz.
S
12
461
= K[~p/(L1])]
(4)
462
w.
V. Titow
12
463
(5)
O2
N2
CO 2
H2O
Polyolefins
66
11
HDPE
LDPE
PP
03
07
06
8
06
06
04
2
4
25
75
03
22
44
36
01
57
146
125
04
22
36
30
03
464
W. V. Titow
12
465
TABLE 12.5
Water Vapour Transmission of Breon Films 0004 in Thick,
Containing Various Plasticisers
(Room temperature, dish method at 100% RH)
Plasticiser
DOP
Oetyl deeyl phthalate
Trioetyl phosphate
Tritolyl phosphate
Dioetyl adipate
Cresyl diphenyl phosphate
115
135
161
170
177
191
466
W. V. Titow
The rate of transmission of water vapour (in a dish test with desiccant,
at room temperature and 100% RH) through some commercial PVC
sheeting products is illustrated by the following figures (grams per
square metre per 24 h):
Rigid sheet (homopolymer-based) 0050 in thick:
Pipe-wrapping PVC tape with polyisobutylene adhesive layer
(PVC thickness 0013 in, adhesive layer 0008 in):
General purpose adhesive tape (PVC layer 0010 in thick):
01
06
25
It will be clear from what has been said in this section, that the
results of permeability tests are valid and their numerical expression
meaningful only for strictly standardised test conditions, which should
be specified. Moreover, even when these requirements are met, and
the results are given in appropriate units, comparison between sets of
data from different sources should be made with caution, as materials
of apparently the same kind (say two rigid PVC films of comparable
thickness) may differ in composition or nature of individual constituents (e.g. different lubricants, processing aids, stabilisers, may be
present), processing history and fine structure. Differences in the
performance of basically the same equipment in two different
laboratories may also be significant.
12
467
468
W. V. Titow
12
469
470
w.
V. Titow
12
471
Temperature
Water
(including
atmospheric
precipitation,
i.e. rain, snow,
hail, vapour
and condensate)
Sunlight
Factor
(environmental
agent)
1,5,7,8
1,8,9
1,3
6,8
1, 2, 3, 4, 5
1, 2, 3, 4, 5, 6,
7, 8
Main observable
effects a
Remarks
TABLE 12.6
Some Factors Instrumental in the Natural Weathering of PVC, and Examples of Their Main Effects
~;0
:0::::
reduced extensibility;
surface buckling or rippling;
distortion (various degrees and kinds);
development of microporosity;
environmental stress cracking or
crazing.
1,2,3,4,
5,6,8,9,10
Atmospheric
pollutants
(in vapour,
liquid and solid
particle form)
1,
2,
3,
4,
5,
1,2,4,5,6
Air
1,2,4,9
-.I
W
.$>.
f}
I'>..
0;-
~.
~
~
'1:l
~
~
~
~
~.
'1:l
~
.....
N
474
w.
V. Titow
12
475
476
w. v.
Titow
liquid condensate or spray). * Exposure to radiation (light of wavelengths extending from about 280 nm into the visible region) is the
basic feature of all such tests: in most procedures this is combined with
the other two factors.
Radiation sources commonly used are listed in Table 12.7: the
emission characteristics of such equipment are discussed in a paper by
Allen et at. 48
It is generally recognised that, as far as radiation effects in the
normal weathering of plastics are concerned, it is the UV component
of sunlight which is the main operative factor.47-49 This is the basis of
the widely held view that the spectral distribution in the UV region of
the light used in accelerated laboratory weathering tests should be as
similar as possible to that of sunlight, t to reduce the possibility that
radiation-induced chemical (and any other) changes in the test
speCimens may differ in kind from the corresponding effects of natural
weathering. However, a strong case has also been made out for the use
of a source (fluorescent UV lamp) emitting intensely and almost
exclusively in the 290-340 nm region, where the intensity of sunlight's
spectrum is in fact comparatively low. This approach is based on the
view that most of the photochemical changes suffered by plastics in
natural weathering are attributable to the 290-315 nm UV band,47 and
that therefore exposure to a source with strong emission in this region
is both sensible and particularly effective as a means of accelerating
radiation effects in artificial weathering. Test apparatus employing this
type of illumination in conjunction with means of subjecting the
specimens to condensed moisture and elevated temperatures (see entry
No.4 in Table 12.7) has been claimed47 to give particularly rapid
accelerated weathering, and results which correlate well with those of
outdoor exposure (within the general limitations mentioned above).
477
Atlas Electric
Devices Co.,
Chicago, Ill. 60613
USA
Carl Zeiss Inc.
New York, USA;
Quartz-Lampen
GmbH, Hanau,
West Germany;
John Goodrich,
Ludlow, Shropshire,
England
(ii) Xenotesta
(xenon arc)
Weather-Omete~
(i)
Close
Atlas Electric
Devices Co.,
Chicago, Ill. 60613
USA
2. 'Sunshine'
carbon arc
(open carbon
arc with
'Corex D'
filters)
Weather-Ometera
(Sunshine arc)
Poor
Fairly close
Suppliers
Atlas Electric
Devices Co ..
Chicago, Ill. 60613
USA
Name or
designation
Fade-Ometera
Approximation of UV
spectral distribution
to sunlight
1. Enclosed carbon
arc
Nature
Radiation sources
TABLE 12.7
Radiation Sources in Common Use in Laboratory Weathering Equipment
ASTM D 2565
ASTM G 23;
ASTM G 25.
ASTM G 23;
ASTM G 25.
Remarks
and
References
o~
:::;j
:0::::
00
Close
Fair
(more intense
below 320 nm)
Fair
5. Mercury/tungsten
lamp
6. Fluorescent UV
lamp combined
with UV fluorescent
'black-light' source
(FSB unit)
7. High-pressure
mercury/quartz
arc with 'Corex
D' filters
GP UVA ultra-violet
accelerometert
GP-PS/BL b
o-U-V accelerated
weathering tester
4. Fluorescent
UV lamp
(mercury arc
lamp phosphor
coated)
General Products
Manufacturing Co.,
Morristown, NJ,
USA
General Products
Manufacturing Co.,
Morristown, NJ,
USA
Microscal Ltd,
Ealing, London,
England
Refs 46 and 48
Refs 48 and 50
One hour FSB exposure sometimes
approx. equated to
one day outdoors
in the UK c
Ref. 48
ASTM G 53;
Ref. 47
.$>0
-.J
\0
I ;;
"
!}
I:l..
;:0
s::>
5'
1:;-
~
~
"tl
S'
-t'
i;.
1"'
tv
......
480
W. V. Titow
481
482
w.
V. Titow
12
483
484
W. V. Titow
12
485
biological attack.
ASTM G 21-70 (Re-approved 1980): Standard recommended
practice for determining resistance of synthetic polymeric materials to
fungi.
ASTM G 22-76: Standard recommended practice for determining
486
W. V. Titow
u.7.2
12
487
S
S
S
Reducing agents
Detergent solutions
Inorganic salt solutions
:}
Remarks
Rigid PVC
No attack up to 60C;
allowable design stress
should be substantially
reduced
Allowable design stresses
should be substantially
reduced
No attack up to 60C
:1
General
resistance
rating
Oxidising agents
Concentrated
Organic acids
Alkalis:
Dilute
Oxidising
(concentrated)
Concentrated
Inorganic acids:
Dilute
Reagents
S
S
S
:}
General
resistance
rating
No attack up to 60C
No significant attack up
to 20C; plasticisers and
some fillers may be affected
at higher temperatures
Plasticiser and some
fillers may be affected
Short-term contact may be
acceptable in some cases
Remarks
Plasticised PVC
TABLE 12.8
General Chemical Resistance Characteristics of PVC at Room Temperature
:::l
0
.j>-
oe
oe
U
U
U
M
M
M-U
U
S
U
U
U
U
U
M
M
S-M
U
Aliphatic hydrocarbons
Aromatic hydrocarbons
Chlorinated
hydrocarbons
Esters
Ethers
Ketones
Aldehydes
Amines
Liquid fuels
Turpentine
Oils:
Mineral
Vegetable and animal
Fats
See also Table 12.10
S
S
S
U
U
Water
M-U
M-U
M-U
U
U
U
M
U
U
U
S
Bromine
Fluorine
Iodine
Aliphatic alcohols
Halogens:
Chlorine
.j>.
-a
00
1:;'
'"
l::
$::>
;:::
0;-
$::>
::I.
()
"l:I
-.::::
;:-
'"~'"
~
~
'"~.
.g
......
N
TABLE 12.9
Chemical
Tensile
strength
(lbfin- z)
Weight
change
5200
4500
3600
5800
5900
5800
5300
4900
5700
5550
5450
081
199
448
050
043
022
032
040
048
004
5500
5600
5400
30-day immersion
at 60"C
Tensile
strength
(lbfin- Z)
Weight
change
329
825
1539
164
226
014
-007
-001
5000
2450
1450
5800
5700
4900
4700
5450
4200
4950
5250
4800
5900
5800
5700
148
098
659
172
-019
354
004
058
1278
4600
4100
5400
5200
5600
120
121
014
002
-002
2150
2400
5400
5900
5400
514
317
022
-005
-011
Carbon tetrachloride
Trichloroethylene
1850
1550
5914
10321
Excessive swelling
Excessive swelling
Benzene
Castor oil
Cotton seed oil
Glycerine
Hexane
Linseed oil
Salt solutions (sat.)
Barium sulphide
Ferric chloride
Potassium chloride
Sodium dichromate
Trisodium phosphate
5000
5300
5150
5450
3000
5150
73-11
044
018
007
424
007
Excessive swelling
5000
007
5400
026
5900
018
5000
5100
5000
5400
5050
061
025
022
023
046
5000
4700
080
153
2850
5200
387
061
Acetic acid
Chromic acid
Hydrochloric acid
Nitric acid
Oxalic acid (sat. soln)
Phosphoric acid
Stearic acid
Sulphuric acid
Butyl alcohol
Ethyl alcohol
Sodium hydroxide
Formaldehyde
Hydrogen peroxide
Phenol
Turpentine
Distilled water
20%
80%
(glacial)
10%
30%
40%
30%
30%
60%
75%
100%
20%
50%
80%
10%
30%
50%
(%)
(%)
4800
044
5450
4750
4800
5150
4800
311
032
020
018
078
4200
357
4800
167
Excessive swelling
1850
3549
5100
094
Acetaldehyde: 100%
40%
Acetone
Aluminium fluoride
Ammonia liquid, 100%
Ammonium hydroxide,
088
Ammonium fluoride, 20%
Ammonium sulphide
Amyl acetate, 100%
Aniline, 100%
Barium chloride
Benzaldehyde
Benzine
Bleach lye, 10%
Bromine gas, weak
Bromine liquid
Bromic acid, 10%
Butyl acetate
Butyric acid: 20%
cone.
Butanol: primary
secondary
Calcium chlorate
Calcium hypochlorite, soln
Carbon disulphide
Chloracetic acid, 100%
Chemical
S
S
U
U
S
U
S
S
S
S
S
S
S
S
S
U
S
U
S
M
S
S
S
U
S
U
S
S
U
S
U
M
U
60
20
(0C)
Temperature
Chemical
TABLE 12.10
Further Data on Chemical Resistance of Rigid PVCa
S
U
U
U
S
S
U
U
S
S
S
U
U
S
U
U
S
S
S
S
S
S
S
S
20
(0C)
U
U
U
S
S
S
S
U
S
S
U
U
S
S
S
U
U
S
U
S
U
U
U
S
S
60
Temperature
l:>..
.;..
\0
I;;
'"
l'::
l:>..
Cl
"'tl
;:,
'"
/;;'"
1:;'
;;;
....
a::
'"
(')
'<::
"'tl
-s
;;;
....
'"
'"
:
~
~
'"....
:::-.
.g
......
N
Ethylene glycol
Ethylene oxide
Fatty acids
Ferric sulphate
Ferrous chloride
Ferrous sulphate
Fluosilicic acid
Formaldehyde, 40%
Formic acid: 50%
conc.
Fruit juices
Fuel oils
Furfural
Glucose
Glycerine
Glycol
Heptane
Hydrobromic acid, 50%
Hydrochloric acid, 30% +
Hydrocyanic acid
Hydrofluoric acid: 40%
conc.
Hydrogen bromide, 10%
Hydrogen peroxide
Hydrogen sulphide
Hypochlorous acid
Chemical
S
U
S
S
S
S
S
S
S
S
S
S
U
S
S
S
S
S
S
S
S
M
S
S
S
S
M
M
S
S
S
S
S
S
U
S
S
S
U
U
S
S
S
S
S
S
M
U
Temperature
(0C)
60
20
Chemical
Kerosene
Ketones
Lactic acid: 10%
90%
Lead tetraethyl, 100%
Magnesium chloride
Magnesium hydroxide
Maleic acid, sat.
Mercuric chloride
Mercuric cyanide
Mercurous nitrate
Methyl alcohol, 10%
Methyl bromide
Methyl chloride, 100%
Methyl ethyl ketone
Methyl isobutyl ketone
Methylene chloride, 100%
Milk
Mineral oils
Molasses, commercial
Naphtha
Naphthalene
Nickel chloride
Nitric acid: 1-30%
70%
98%
TABLE 12.1().......ontd.
S
U
S
U
S
S
S
S
S
S
S
S
M
M
U
U
U
S
S
S
S
U
S
S
S
U
S
S
S
S
U
S
M
M
U
U
S
U
M
U
S
S
S
M
S
S
S
S
U
Temperature
eC)
20
60
<:;
:0::::
tv
\D
U
M
S
S
S
S
U
S
U
U
S
S
U
S
S
S
S
S
S
U
S
S
S
S
S
S
S
S
U
S
S
S
U
S
S
S
S
S
S
S
U
S
U
M
S
M
S
S
U
M
Sodium cyanide
Sodium ferrocyanide
Sodium fluoride
Sodium hypochlorite
Sodium sulphide, sat.
Stannic chloride
Stannous chloride
Sulphur dioxide: dry
wet
liquid
Sulphuric acid, 90%
Fuming sulphuric acid
Tanning extracts
Tartaric acid, sat.
Tetraethyl lead
Tetrahydrofuran
Thionyl chloride
Toluene
Transformer oil
Trichlorethylene
Triethanolamine
Turpentine
Urea, up to 30%
Vinegar
Xylene
Zinc chloride, sat.
Zinc sulphate
Key: S = Satisfactory.
M = Moderate (dependent on formulation and conditions).
U = Unsatisfactory.
Nitrobenzene
Octyl cresol
Oleic acid
Oxalic acid, sat.
Perchloric acid, up to 70%
Petrol, aliphatic
Petrollbenzene, 80/20
Phenol, 90%
Phenylhydrazine, 100%
Phosgene, liquid
Phosphoric acid
Phosphorus pentoxide
Phosphorus trichloride
Picric acid, 1%
Potassium bichromate
Potassium chromate, 40%
Potassium cyanide, sat.
Potassium hydroxide, cone.
Propyl alcohol
Propylene dichloride
Silver cyanide
Soap solution
Sodium acetate
Sodium bisulphite
Sodium bromide
Sodium chlorate, sat.
Sodium chromate
S
S
S
S
S
S
S
S
S
M
S
U
S
S
S
U
U
U
S
U
S
U
S
S
U
S
S
'"
"1:1
S
S
l:>..
'D
W
.j>.
"
l=:
0;
l:>..
<3
;:s
I:;"
::1.
"'"
~
~
"1:1
"s~
S'
"~'"
.g>
'"~.
~
~
tv
......
U
U
U
S
U
S
U
S
M
S
S
S
S
S
S
S
S
S
U
S
-
494
W. V. Titow
12
495
496
w.
V. Titow
12
497
levels have undergone a considerable change in the past few years with
increasing volume and availability of relevant data.
The first limits recommended in the UK (in the mid-1970s) for
maximum VCM concentration in factory atmospheres started with a
time-weighted average figure of 25 ppm (by volume), soon to be
brought down to 10 ppm with the further proviso that wherever
possible zero concentration should be aimed at. 75 At the same time in
West Germany (North Rhine-Westphalia) the maximum concentration
limits for factories were being lowered from an initial 50 ppm to
5 ppm,76 whilst in the USA a limit of 1 ppm was being demanded, with
the US Food and Drug Administration (FDA) concurrently framing
regulations to prohibit the use of rigid and semi-rigid PVC for
food-packaging applications (bottles, films) unless it could be shown
that no migration of VCM into the contents would occur. Attention
was focused on unplasticised PVC, because available evidence
indicated that plasticisation reduces residual VCM contents to
undetectably low levels. A temporary standard was put out in the USA
by the Occupational Safety and Health Administration (OHSA) in
1974, followed by a finalised version in 1978: in the same year relevant
rules, limiting VCM emission in industrial plant, were formulated by
the US Environmental Protection Agency (EPA), and EEC directives
issued in Europe on VCM content in food-packaging materials.
These moves made themselves felt in the industry in several ways.
PVC resin production, as well as that of packaging films and bottles,
was curtailed by some manufacturers unwilling to face the difficulties
and expense of reducing VCM concentrations in their plants and
products in the face of uncertainty as to what limits might finally be
laid down. Prices of some PVC resins and products were affected as
production became more expensive where removal of VCM and tighter
control over its concentration were being instituted. Some resins, in
which the VCM content was reduced by heat treatment ('stripping'),
became more glassy and harder to process as a result of this addition to
their 'heat history'. On the positive side, R&D work was stimulated
towards methods of reducing VCM concentrations in PVC materials
and factory atmospheres, methods of determining such concentrations,
and the ways in which they were affected by production conditions.
Towards the end of the 1970s the practical improvements achieved in
production and processing, coupled with the results of the R&D
effort, led to a brighter outlook on the VCM risk. Further confirmation
has been forthcoming for the relative safety of plasticised PVC
498
W. V. Titow
Aside from the effects of VCM, the main health hazard is possible
toxicity in food-contact applications involving such PVC products as
films and containers: this hazard is usually considered from the point of
view of the properties of the individual components of a formulation.
It is normal to 'clear' these, before the formulation is finalised and
made up, on the basis of experience, and/or information from the
manufacturers, and/or the relevant recommendations or rules of the
appropriate national authorities and organisations. In the USA the
organisations most directly concerned are the ones referred to in the
previous section (FDA, OHSA, EPA): the US Department of Health,
Education and Welfare (HEW) may also be mentioned in this
connection. In the UK and Europe the bodies with related interests
and functions (albeit largely different constitutions, and scope and
nature of operations) include the UK Health and Safety Executive,
British Plastics Federation (BPF) , the UK Chemical Industries
499
Association, the West German Federal Health Office, and corresponding organisations in many other countries. Some of these organisations
(e.g. FDA, BPF) issue lists of materials (e.g. plasticisers, stabilisers,
colourants) approved (or forbidden) for food-contact applications:
such applications constitute the area of primary concern in the context
of this section.
Some aspects of the subject of toxicity of PVC materials are
discussed in a brief paper by Estevez. 82 An earlier review, by Phillips
and Marks,83 is also still of some interest. In the UK the BPF publishes
a code of practice for safety in use of plastics for food-contact
applications, based in part on extensive evaluation tests carried out by
the British Industrial Biological Research Association (BIBRA).
It is normally assumed that PVC homopolymers, vinyl chloride/
acetate and vinyl chloride/vinylidene chloride copolymers are non-toxic
in compounds. Several lubricants (in particular stearic acid) are
regarded as safe, as are some of the other two principal formulation
components, plasticisers and stabilisers, when used in prescribed
concentrations: acceptability, especially the concentration limits, may,
however, vary according to the conditions. For example, more
stringent requirements arise for food-packaging films to be used with
fatty foods (e.g. bacon, butter, etc.) capable of leaching out
plasticisers, than for non-fatty foods with a high water content (e.g.
fruits, vegetables). The packaging of children's toys is also an area of
special concern. Detailed, up-to-date information and guidance can be
obtained from the organisations mentioned in this section. Some
further general information is also given in the chapters on stabilisers
and plasticisers.
SOO
w.
V. Titow
The kinds of hazard that may be mentioned under this heading are
relevant to PVC, although not exclusive to it, * as they can arise in the
production and processing of other plastics. They are:
(i) fire and explosion hazards;
(ii) respiratory hazards;
(iii) toxic hazards;
These occur in the storage and handling of additives and other
formulation components (especially in powder form), and in processing
operations involving the use of solvents (e.g. making up PVC
solutions, printing on PVC materials, preparation and application of
solvent-based lacquers for PVC sheet materials).
The appropriate precautions are nowadays generally reasonably well
known in the industry, but it should also be remembered that many are
prescribed by law, and that the statutory requirements vary in different
countries. Advice and guidance is available from the organisations
mentioned in Section 12.9.2. Relevant information may also be found
in the current editions of the following publications:
Industrial Hygiene and Toxicology. F. A. Patty (Ed.), Interscience
Publishers.
Encyclopaedia of Occupational Health and Safety. International
Labour Office, Geneva.
Health Hazards of the Human Environment. World Health Organisation.
Kirk-Othmer Encyclopedia of Chemical Technology. John Wiley &
Sons (under 'Industrial Toxicology' and other relevant headings).
* However, two specific points may be made regarding PVC: under certain
conditions the presence of fine PVC resin dust can lower the explosive limit of
VCM/air mixtures; potentially ignitable levels of VCM may arise in high-speed
mixing equipment. Guidance on safety in the operation of high-speed mixers is
provided in a booklet published jointly by the British Plastics Federation and
501
502
W. V. Titow
and materials'.
12
503
TABLE 12.11
Oxygen Index Values of Some Plastics Materialsa
Material
Oxygen indexb
(typical or
representative value)
45
40
40
30
21-26
60
95
23
23-27
17-18
17-18
17-18
22
21
18
25
22
18
24
19
22
26
Flammability
1. ISO 1210-1982
2. BS 2782: 1970
Method 508D
Burning time and/or rate and/ 1. BS 2782:1970:
or extent
Method 508A
2. BS 2782:1970:
Method 508B
3. ASTM D 635-81
1. ISO 871-1980
2. ASTM D 1929-77
Ignition properties
Standard
specifications
Property or
characteristic determined
Material
or product
Remarks
1. and 2. technically
equivalent: self-ignition and
flash-ignition temperatures
determined (in a hot-air
ignition furnace)
TABLE 12.12
Standard Burning Tests Relevant to PVC Materials
;;
is
:::'1
VI
Plastics: cellular
Smoke generation
Horizontal burning characteristics
Smoke generation
Vertical burning characteristics (flame height, burning
time, mass loss)
BS 5111:Part 1:1974
ASTM D 3014-76
BS 4735:1974
1. ISO 4589-1985
2. BS 2782:Part 1:
Methods 141 A to
C: 1978
3. ASTM D 2863-77
ASTM D 2843-77
4. ASTM D 1433-77
1. ISO/R 1326-1970
2. BS 2782:1970:
Method 508Ca
3. ASTM D 568-77
4. UL subject 94
Parts A & B
5. IBM CMH 6-0430102
2. Restricted to solid
(non-cellular) specimens
NB Method D for electric cable insulation or sheathing-see below
Employing the XP2 smoke chamber
2. Relates specifically to
thin flexible PVC sheeting
3. Vertically suspended strip
specimen: test results
sensitive to thickness
4. Strip specimen supported
on 45 incline
2S
lJl
~
~
1:;
"'-
;::
'"
l:;'"
~.
r3
S'
"l:I
.:
S'
~
~
~.
.g~
.....
N
Property or
characteristic determined
Combustibility
Material
or product
Remarks
BS 2782:Part 1:
Method 141D:1978
1. BS 4066:1969
Standard
specifications
;e
:::J
c;
:0::::
Vl
Coated fabrics
ISO 3795-1976
(based on US Federal
Motor Vehicle Safety
Standard 302)
2. DIN 53 438-1977
1. ASTM E 162-81
4. DIN 54332-1975
3. ASTM D 2859-76
1. BS 3424:1973:
Method 17
2. BS 5790:1979
Vl
I:l..
;::
I:>
5'
l:;-
~
~
"ll
~
~
;;-
~
~
~.
~
~
.....
N
W. V. Titow
508
45
40
25
03
004
el,
wt fraction
0-5
06
12
509
REFERENCES
1. Eftis, J. and Liebowitz, H. (1975). Engineering Fracture Mechanics, Vol.
7, Pergamon Press, Oxford, pp. 101-35.
2. Plati, E. and Williams, J. G. (1975). Polym. Engng. Sci., 15(6), 470--7.
3. Brown, H. R. (1973). J. Mat. Sci., 8,941-8.
4. Williams, J. G. (1975). 'The determination of fracture toughness from
impact tests on polymers', Paper 2 at the PRI Conference on New
Developments in Impact Testing, London, 2nd December.
5. Williams, J. G. (1975). 'The fracture mechanics of polymers', Ibid. Paper
14.
6. Titow, W. V. (1977). In Developments in PVC Production and
Processing-l (Eds A. Whelan and J. L. Craft), Applied Science
Publishers, London, Ch. 4.
7. Reymers, H. (1970). Mod. Plast., September, 78-80.
8. Titow, W. V. Unpublished work.
9. Wilson, A. S., Biggin, I. S. and Pugh, D. M. (1978). 'The influence of
volatility on the selection of plasticisers to meet new and developing
performance requirements', paper presented at the PRI International
Conference on PVC Processing, Egham Hill, Surrey, England, 6-7 April,
1978.
10. Ranney, M. W. (1975). Irradiation in Chemical Processes: Recent
Developments, Noyes Data Corp.
11. Scalco, E. and Moore, W. F. (1983). Radiat. Phys. Chern., 21(4),389-96.
12. Yasuda, H. (1975). J. Appl. Polym. Sci., 19(9),2529-36.
13. Titow, W. V. (1978). In Adhesion 2, (Ed. K. W. Allen), Applied Science
Publishers, London, Ch. 12.
14. Fujita, H. (1961). Fortschr. Hochpolym.-Forsch., 3, 1-47.
15. Meares, P. (1965). Polymers: Structure and Bulk Properties, Van Nostrand,
London, p. 316.
16. Meares, P. (1958). J. Polym. Sci., 27, 391-404.
17. Meares, P. (1966). Eur. Polym. J., 2,95-106.
510
w.
V. Titow
12
49.
50.
51.
52.
53.
54.
55.
56.
57.
58.
59.
60.
61.
62.
63.
64.
65.
66.
67.
68.
69.
70.
71.
72.
73.
74.
75.
76.
77.
78.
79.
80.
81.
82.
511
512
W. V. Titow
83. Phillips, I. and Marks, G. C. (1961). Brit. Plast., 34, 319 and 385.
84. Edgerley, P. G. and Pettett, K. (1981). Plast. Rubb. Proc. Appl., 1(2),
133-7.
85. Iida, T., Nakanishi, M. and Goto, K. (1975). J. Polym. Sci. Polym. Chem.
Ed., 13(6), 1381-92.
86. Mitera, J. and Michal, J. (1976). Chem. Prum., 26(8),417-20.
87. Clark, C. A. (1972). SPE J., 28(7), 30-5.
88. Fennimore, C. P. and Martin, F. J. (1966). Mod. Plast., 44(3), 141-8.
89. Isaacs, J. L. (1970), J. Fire Flamm., 1(1), 36-47.
90. Oswin, C. R. (1975). Plastic Films and Packaging, Applied Science
Publishers, London.
91. BS 6336:1982. Guide to the development and presentation of fire tests and
their use in hazard assessment.
92. Grieveson, B. M. (1976). 'The fire hazard of polymers', paper presented at
the Polymer Symposium, British Association for the Advancement of
Science, Lancaster, England, 3rd September, 1976.
93. Cullis, C. F. and Hirschler, M. M. (1981). The Combustion of Organic
Polymers, Clarendon Press, Oxford University Press.
94. Titow, W. V. and Lanham, B. J. (1975). Reinforced Thermoplastics,
Applied Science Publishers, London.
95. Ahrens, H. W. and Zahradnik, B. (1973). 'Oxygen index rating of plastics
as a guide to their behaviour in fire', CSIR Special Report BOU 29.
CHAPTER 13
13.1 INTRODUCTION
The compounding process represents the link between raw material
production and finished-article manufacture. Its function is to combine
the PVC resin with the various additives required for processing and
for the service properties of the final product, in accordance with the
formulation.
There are five general types of industrial PVC compounding
514
COmpounding
(mixing)
Compounding
,Extrusion
,Blow moulding
d
I compoun Ing
I and .
~~~J~~_~~
i
1
1
Extrusion
caltlndtlring
II
..J
Furttitlr
compounding
and dirtlct
(in-lintl)
ftltldlng
to caltlndtlr
~~~~~
'Extrusion
i,Blow
Injtlction moulding
moulding
Rtl-cycling
calJdtlrlng
into
I
I
,
~O~~~I~ ~~~..J
In terms of the amounts used in PVC compounding, these are the two
principal solid raw material components; both are in powder form.
515
r--T------------------,
~
RAW MATERIAL
STORAGE
5
a
w
RAW MATERIAL
HANDLING AND
CONVEYING
!L _~_
RAW MATERIAL
WEIGHING
a::
I t/)
r--T-------I
I
r - - - -.......- - - ,
I
t:
_..w-1
I
l-
Izl
I :::> 1
I
I
I <.9 I
1z 1
101
I z I
1
:::>
I ~ I
101
101
1L _ _ ...i.I
COATING
_
r~T-------I
I ~ I
151
I@I
I
~ I
: ~:
I~ !
I ~I 1
II II
L __
--------1
PRODUCT
COOLING
PRODUCT
CONVEYING
PRODUCT
STORAGE OR
BAGGNG
I
I
I
:
:
I
:
J
._-
.. {9.
D
Fig.13.3 Typical PVC compounding line. 1, Storage silo for PVC polymer; 2,
production or holding silo for filler; 5, storage tank for plasticiser; 6,
station; 8, weighing station for solid components; 9, weighing station for liquid
cooling; 13, storage silo for pellets; 14, bagging and palleting; 15, plant control
-_
t .._
_.1
15
~o ~~C ~
storage silo for filler; 3, production or holding silo for PVC polymer; 4,
production or holding tank for plasticiser; 7, minor components (additives)
components; 10, premixer; 11, melt compounding and pelletising; 12, pellet
system.
518
TABLE 13.1
Proportions of Important PVC Products Produced, Respectively,
from Pre-mix and Pelletised Compounds (World-wide)
Products
Produced from:
pre-mix (%) pellets (%)
Extrusions
(pipes, profiles, tubes, hoses, siding)
Injection mouldings
Cables
Records
Blow mouldings (bottles)
Film and sheet
Plastisol products
90
25
75
70
100
100
10
75
100
25
30
Properties
Kvalue
(DIN 53726)
Processing
Particle shape
Particle size (/lIIl)
M-PVC
S-PVC
E-PVC
57-71
55-71
65-75
Sprayed
by special
process
Spherical, whole
and broken spheres
Riven,
porous
Bead-shaped, Flaky
compact,
glassy
60-250
60-250
60-500
4~20
600-700
300
up to
200
30Q--4()()
Good
Good
Good
Poor
Good
J-5
05-1
J-5
up to
60
13
519
520
521
-less labour;
-no loss of material in transport;
-lower raw material prices;
-no contamination of the materials and dust-free working conditions.
The filling of raw material silos is always accomplished with
pneumatic conveying systems. Both road tankers and rail tank cars are
used. The vehicle tanks are generally designed to resist conveying
522
w.
523
524
VI~W
A-A
v~nl
Qlr conl'lK\lon
flUldlSQ\lon
con~
525
unit. The only exceptions are cases where the same product is stored in
a number of silos.
The filters are provided with fully automatic or semi-automatic
purging, depending on the dust loading and throughput. The difference
between the two is that fully automatic filters are purged by dust-laden
air during service, while semi-automatic filters are cleaned only when
the filling operation is complete. Either bag or sheet filters can be
used. The advantage of the sheet filter over the bag filter is that it
occupies less space. For lower dust loadings and coarse-particle dusts,
filters with mechanically actuated purging devices are generally
sufficient. For very highly loaded filters and those handling fine dust,
jet-type filters with pneumatic purging are generally used. In this case,
the dust is purged from the outside of the bags by applying compressed
air at about 6 bar pressure to the inside of the filter elements for
back-purging. Cotton can be used for the filter fabric, but synthetics
such as polyacrylonitrile or polyester are usually favoured. The filter
area to be provided is governed by the admissible filter surface loading.
Rule-of-thumb figures are: in the case of mechanically purged filter
elements, 1 m2 of filter area can handle 1 m3 min- 1 of dust-laden air: in
the case of pneumatically purged jet filters, 1 m2 of filter area can be
loaded with 3 m3 min- 1 of dust-laden air.
13.3.2 Conveying of PVC Polymer and Fillers
-1500
Piston
compressor,
radial
blower
Radial blower
Short to
medium
distances
30
150
Silo filling
Filling of production or
holding silos from
storage silos or from
bag-dumping stations
Filling of holding silos
Application
This system offers special advantages in conjunction with such process steps as drying and cooling.
Suction/pressure
conveyor
Suction conveyor
Vacuum of about
-5000
Piston
compressor
Up to 50
(very limited)
Radial blower
<2000
200
Piston
compressor
4000-8000
Low pressure
Long
distances
Screw
compressor
15 000-25 000
(m)
High pressure
(generally employed
for high conveying
rates)
Medium pressure
Conveying
distance
Operating
pressure
range
(mm w.g.)O
System
Compressor
TABLE 13.3
Main Features of Conveying Systems
Cyclone with
rotary valve,
filter
Cyclone with
rotary valve,
silo filter
Material
delivery
Picked up
by suction
Picked up
by suction
Filter,
cyclone with
rotary valve
Rotary valve,
Cyclone with
pendulum flap rotary valve,
filter
Rotary valve
Pressureresistant
silo
Material
pick-up
'"
;::
'"
;::
I'>..
'"
;:,-
"~
a..
Ul
527
528
13
529
c~
dlstoncu only
R~lallVf'
Un$
0-
<l
~"9
'i'
\;V
CO!W!Y'..!.'9
Variabl~ ~I
on ConVf'Ylng gas
Fr..
"'"w
'ir'9
= 10 kg h- 1 solids
kg h- 1 air
530
kg h -1 solids
20 to 25 k h-1 .
g
au
Fillers: Mainly suspension conveying, though for abrasive materials
such as untreated chalk, plug conveying is possible with solids loadings
of
1
60 to 80 kg h- sol~ds
kg h- 1 au
PVC pellets: Suspension conveying, though ftuidised conveying (low
velocity) is more effective in avoiding pellet abrasion. Pipe diameters
generally lie between the nominal sizes of 80 and 125 mm. Aluminium
alloys are usually used for the straight pipe sections while bends (with
radii between 1000 and 1500 mm) are normally made of stainless steel.
531
Tanks
-corrosion-resistant steel;
-steel with paint finish resistant to the plasticiser;
-steel, sand-blasted, internal walls sprayed with plasticiser;
-aluminium;
-glass-fibre reinforced Palatal.
Pipes
-corrosion-resistant steel;
-steel;
-aluminium;
-glass-fibre reinforced Palatal.
Pumps:
-cast iron.
The pumps should be equipped with single-acting mechanical seals,
because packing cords are attacked by the plasticiser.
(c) Plasticiser Delivery
Small consumers normally receive the plasticisers in drums, and
large-scale production plants in road tankers holding l(~20 tonnes (or,
under certain conditions, in tanker compartments holding 5 tonnes), or
in rail tank cars holding between 15 and 30 tonnes.
Road tankers normally have an outlet nozzle of 80 mm nominal size,
and are equipped with a pump or a compressor for emptying the
plasticiser. Maximum delivery head is 10 m, provided the piping is
straight.
Most rail tank cars have outlet nozzles of 100 mm nominal size. Here
the customer must provide the pump for emptying the car. A properly
dimensioned pump will drain a tank car in about one hour. The storage
tanks should be installed in the immediate vicinity of the siding.
532
533
534
535
BATCH WEIGHING
mechanical
batch scales
II
II
hybrid
Ilelectromechanical
floor scales
Ir
vehicle scales
road vehicle
scales
I
I
container scales
solids
railway
scales
I bagging scales I
II
liquids
gross weight
baqqinq
net weight
baqqinq
CONTINUOUS
WEIGHING
I
I differential weighers I I
electromechanical
mechanical
belt weighers
w.
536
A.
a
I
~7
B.
f
(9
Ii
!l _._
c.
'
E-l r-icii
II
CJ
_._._ -'
~I
i
i
IL _e_ .
c
Fig. 13.8 Weighing systems. A, Mechanical; B, electromechanical; C, hybrid.
Key: a, load receptacle; b, lever system; c, force detector; d, junction box;
e, cable; f, weight display.
537
538
Fig. 13.9 Weighing system for solids. 1, Container for solids; 2, discharge
plate; 3, metering screw, 4, pneumatic closure flap; 5, container scale; 6,
beater, 7, elastic collar; 8, vent.
539
Liquids: Figure 13.10 shows the main metering methods for liquids.
The most accurate metering is obtained by weighing the liquids as
indicated in Fig. 13.lO(A). In this case the material being metered
flows by gravity out of a storage tank into the scale tank, or else is
pumped into it from a lower level. Temperature, density and viscosity
fluctuations have no effect on metering accuracy here. Highly viscous
liquids are usually heated.
Where liquids are metered by volume, as illustrated in Fig. 13.lO(B),
they are again conveyed by gravity or a pump into a collecting tank. In
this case, the feed is cut off when a certain filling level is reached. This
is a very simple metering method, but density fluctuations result in
metering errors. Flow measurement, as illustrated in Fig. 13.10(C), is
based on measuring the volume of liquid delivered by a pump. Because
most flow meters react sensitively to fluctuations of the liquid's
A.
Weoighing
B.
Volumetric measuremeont
- -T-
flowmeter
\
C.
metering
pump
D.
Volumeotric displac~ment
540
w.
13
541
View A- A
level devIce
A
3000 d,a up to 16 contaIners
of O'S m3 each
3800 d,a up to 16 contaIners
of 10 m3 each
542
Ulhmal.
conl,oll.d
,",I .al~
13
543
w.
544
Real valuE'
oj
Convl'ntional
electrical
136
control systeom
247
conVE'ntional
.... eolE'ctrical
-,
control systeom
b)
[=-
Real valuE'
rE'COyding
Ig
0
545
Simplest scale
control system
for 1 weigher and
few formulations
Material balances
Output of
process data
Storage of
process data
Arithmetic
data processing
Supply of
process data
Control
functions
Printout after
each batch
Remote digital
display of real
weight
Punch card
Punch card
Keypunch
Conventional scale
control system for
a number of weighers
and formulations
Microcomputer
Microcomputer,
call-up via code
Microcomputer
Material matrix
General possibilities
Supplementary
possibilities
Error acquisition
and diagnosis
Extension of
control system
for peripheral
functions
Microprocessor technology
Hardware possibilities
TABLE 13.4
Possibilities of Conventional Control Systems and Microprocessor Technology
'"~
""-
So
Vl
547
(a) Introduction
The processing of PVC compositions for the manufacture of products
(e.g. mouldings) or semi-products (e.g. sheeting) always involves
powder blending as an early process step. During this operation PVC
polymer powder is blended with the additives (fillers, lubricants,
stabilisers, pigments, plasticisers etc.) called for by the particular
formulation, plasticated to a greater or lesser extent and gelled, and
possibly agglomerated or pelletised. Depending on the way the
operation is carried out, the resulting blend of particulate formulation
components (and any liquid components present) can take one of the
following three forms, which are then processed further as indicated:
(i)
548
549
w.
550
TABLE 13.5
Effect of the Physical State of Components upon the State of the Mixture and
Difficulty of Mixing
Physical state
Main components
Additives
Mixture
Solid
Solid, coarse-grained
(granulate)
Solid
Solid
Solid
Solid
Solid, fine-grained
(powder)
Liquid, viscous
Liquid, thin
Liquid
Liquid
Solid
Liquid
Liquid, viscous
Liquid,
viscous
Liquid
Liquid, viscous
Liquid
Liquid
Liquid
Liquid
Liquid
Degree of difficulty
in mixing
Solid
Solid
Easy
Fairly difficult
Solid
Solid
Liquid
Difficult
Fairly difficult
Easy to difficult,
depending on
particle size of
solid component(s)
Easy to fairly
difficult
Fairly difficult
to difficult
Easy to fairly
difficult
Easy
551
552
13
553
Because these forces tend to act selectively, they hinder the actual
mixing process. In some cases they can even render optimal mixing
impossible.
1&
1....1
T_1hel1
moeer
mixer
00l.tlIe ..".
1::-
a GyrootleeI
~-
Dn.wn
tumbler
belrrel
TlA'IlIlIong
Name
II. . . .
m,xong
IoIIrbcal scr_
solo lTIIXer
Orbbng_bcd
SC,....., lI'OXer
Low-I!l"d
tank mtx.,.
HIgh-speed
tonk m.....
Olonge-Qlf'I
nux..
I'IougI-.hore
A>ddle lTIIXer
mix.,.
RIbbon bar
m_r
...
II
~II
~-
~
~
f5?:l
II'"
II
~JkSi
IIOX.
mIX8'f'.
muun;
gronulat.
m.xlng
granulat.
c::dd
cold nuxer
hot mlx
PVC po5t"
cold
holnuxor
or
--
cold m,_
PIIC QlllllocotiOn
~- -
lI~trohon
Nome
lY0nulat.
pr-ong
pc>UIbly lor
oddll....
PIIC Qlllllocobon
""xer
c'rcUobng
PneumatIC
Name
j
ll~trotiOn
miXing
granulot.
P/C Qlllllcobon
PNEUMATIC MIXERS
Fig. 13.14 Batch mixers for bulk material in solid overall phase.
JS2D
~
n'\./
"1
Ml
~
~
ll~trotiOn
MECHANICAL MIXERS
'"
:"tI
;::
l:>
~s.
"'"
Ul
Ul
555
Gyrowheel mixer
PVC application
Granulate mixing
Possibly for
additive premixing
Name
50-10
2-30
60-70
50-10
(2-3)
2-30
(up to 60)
50-70
3-40000
(max. 100000)
2-30000
30-20
(up to 10)
5-10
50-75
30-20
Commonly
5-300
(max. 900)
5-10
(min)
Speed of
mixing
container
(r min-i)
50-75
(%)
(litres)
Mixing time
50-300
Filling level
Size,
total volume
TABLE 13.6
Technical Data for Rotating-tank Mixers
01--40
01-50
(up to 100)
01-10
(up to 30)
05-10
(kW)
Drive power
;:,
I:>
:-t'
;:,
I:l..
I:>
;:,~
(")
0\
Ul
Ul
13
557
Category
Name
60-70
40-50
80-90
40-50
200{}-{)000
100-3500
10-1500
25-4500
5-12
5-10
5-12
15-30
Size,
Filling level Mixing time
total volume
(litres)
(%)
(min)
TABLE 13.7
Technical Data for Rotating-tool Mixers
350-50
1000-250
350-100
50-15
rotational
(r min-I)
(10)
8-4
50-20
10-4
15
peripheral
(m S-I)
15-45
3-300
5-45
10-25
(kW)
Drive power
U1
U1
;,.
s:>
:"t'
s:>
;,.
I:>...
00
13
559
, ....-1
5000
.000
3000
2000
1000
500
.00
300
200
100
50
.0
30
20
10
5
o-l---+--.-;..--I--...-----4-------l---;
:;m
.al
800
Mlx~r
800
1lXXl
tZlO
1.00
1800
1800
:IOOOmm
dl<lm~l~(
Fig. 13.15 Speed ranges of some mixers with rotating mixing tool.
560
Paths of
product
mov.m.nl
561
affords positive self-release of the material from the tank wall: build-up
on the internal wall surface is thus made more difficult, and cleaning of
the tank is facilitated.
The mixing tank of an intensive mixer is usually provided with a
jacket for heat control, and can be equipped with degassing
attachments. High-speed intensive mixers of the tank type are
sometimes built with a removable mixing tank or with a machine
superstructure that can be raised and lowered. The latter includes the
tank cover, rotor with mixing tool, and the entire drive.
The mode of operation of the intensive mixer stems from the speed
and shape of the mixing tool. The material particles are accelerated so
sharply by the mixing tool that they exceed the aeration velocity of the
fixed bed and are fluidised. The high peripheral speed of the mixing
tool imparts impact and friction forces to the material in the tangential
direction and centrifugal forces in the radial direction. The latter drive
the material against the tank wall in such a way that it can only escape
upwards: upon reaching the cover, it falls back into the centre of the
tank, which has been emptied of material. The result is the familiar
whorl of material, i.e. a circulating flow that is otherwise found only in
liquids.
Intensive mixers with long mixer shafts and high-set mixing tools
provide larger useful volumes (up to 90% of the total volume) than
low-set tool combinations (Fig. 13.18).
The high-speed mixers just described are generally used for batch
mixing, with drive ratings of 04 to 06 kW per kg of material. For
emulsion PVC blends with high percentages of plasticiser, drive ratings
as high as 1 kW per kg of material are employed. Extrapolation of
"
MIXing tool set high
562
~"p~al
Fig. 13.19 Hot/cold mixer combination with hot mixer vertical and cold mixer
horizontal.
563
-,
Cold m,"rr
:/
r~s
Joe rt lor
wolrr
eool~
:
:
-- --j
":.:: =:"
Fig. 13.20 Hot/cold mixer combination with both hot mixer and cold mixer
vertical.
564
(i)
(ii)
(iii)
(iv)
(v)
(vi)
(vii)
565
566
w.
567
,..- I
6,36
20,2
40.3
Effective (projected)flight area
oI
1.25 I
6O.5cm 2
:J
I
01
C
Q.
...
a>
min.
m:Q653 kg
39.5
r;:
40,3
6,36
2Q2
Effective (projected) flight area
~:
P: 760 Torr
60,5cm 2
Fig. 13.22 Power input and heating-up time to 90C as functions of the projected area of the mixing tool flights. No,
power consumption of the mixing tool without material (kW); N, total power consumption of mixing tool with material
(kW); P, pressure in the pre-mixer; OK, shell wall temperature.
Q.
t~
.E
'[ 2,5
kW
3,75 I
;:
I:>
;:
I:>..
I:>
";:,~
i;
Vl
569
tools. In this case, of course, the shape and configuration of the tools
must be adapted to the lower mixing speeds.
The mixing of a rigid PVC composition will normally proceed as
follows. The associated changes in power input (motor amperage) are
shown in Fig. 13.23.
The particulate components are homogenised by the turbulent
mixing motion immediately after the high-speed mixer motor is
switched on. As this occurs, the mechanical energy of the mixing tool
is converted into heat by material friction. The friction, and particle
impacts, bring about the particle surface changes previously mentioned
and the material flows more freely, causing the energy consumption
level to drop until a temperature of about 8SoC is reached. Around this
temperature the lubricants melt, and the material becomes sticky andflows
less freely, which again raises the energy consumption; this peaks when
the liquefied lubricants are being absorbed by the PVC grains:
thereafter the material again flows more freely and the energy
consumption falls. Another energy peak, this time a small one, is
observed at temperatures above 12SoC when the metallic stearates
melt.
A
I
I
I
I
III
Blending time
IV
VI VII :I
min.
Fig. 13.23 Power input during the blending of rigid PVC in a high-speed
mixer. Phase I, mixing and abrading; II, increase in free-flowing property; III,
melting of lubricants; IV, dry mixing; V, melting of metallic stearates; VI, hot
mixing; VII, cooling of blend in cold mixer.
I
5
10min.
f"/
15
I
I
20
tl50
:r
40-+
60-t
80
100
A! C
I \
1\
10min.
-----
--
15
-A
_oc
I
20
Fig. 13.24 Amperage input and temperature as functions of blending time in a high-speed mixer. A, Emulsion PVC
blend with 35% plasticiser; B, suspension PVC blend with 35% plasticiser. (Source: L. Schaffel, G. Spangenberg Co.)
oI
20-+
404
604
150
200
100
80
:>
~
l:l
l:l..
:>
l:l
'";:s~
Vl
-..J
571
When the motor amperage levels off, the mixing operation is over
and it is time to discharge the material into the cold mixer. Continued
mixing in this temperature range, but below the melting point of the
PVC, would merely impair the flow properties as a result of further
size reduction, accompanied-perhaps surprisingly-by a drop in bulk
density. Thermal degradation would also be initiated.
Changes in material temperature in the course of mixing are
illustrated, for various PVC compositions, in Figs 13.24-13.27.
Figure 13.24(A) shows the energy input and temperature curves of
an emulsion PVC blend with 35% plasticiser. In this case the cold
plasticiser was fed continuously into the preheated mixture. The start
O(OC)
120
110
100
90
80
70
60
50
40
30
20
10
0
10
11 I (min)
23'
A -.
o
Cool,n<l I,me
8m,n
Heohn<l lime
9m,n
17
Fig. 13.26 Temperature as a function of time in a hot/cold mixer combination (at approx. 15C cooling water inlet
temperature). A, Rigid PVC pipe blend; B, plasticised PVC shoe compound. (Source: MTI.)
60
70
80
90
100
110
120~
C
130
VI
i:l
s:>
s:>..
~
~
s:>
;:s
~
~
9-
id
60
10
20
30
40
UIII'I:;"
4
5
--
~ 1- ..... ~
1-
I'll...
.-
10
1-
11
Cooling time
I",
12
14
17
'. ~-
Cooling time
16
15
,~
~plasticised
IIV"IU ..........
"'
...
13
,.~
........
,~
"Coil""
~ ........
L/ I'
" "-
I~'
W'
~ l
"
=vr
I"
t;'ITIUlV,IN
rigid PVC-/
IILI,nll.
18
~.
19
,...~
PVC
20
2 min.
Fig. 13.27 Temperature as a function of time in a hot/cold mixer combination. (Source: J. Bornemann, Rheinstahl
Thyssen.)
ell
~
f 50
Q.
Gi
~ 80
2 70
90
100
110
120
130
VI
-.]
"'tl
'"
!:;.
::>::I
~
~
;::
So
~o
......
574
and finish of plasticiser feeding are apparent from the energy input
curve. Figure 13.24(B) is a similar plot for suspension polymer, but
with the cold plasticiser charged all at once into the mixture. Again,
the point at which this took place is reflected in the temperature and
energy curves.
Both diagrams indicate that the quality of a blend is affected by the
method and timing of the plasticiser addition. To obtain homogeneous
dispersion of the plasticiser, it is necessary to achieve a mixer
temperature of 70 to 80C. In this temperature range, the PVC
particles swell and absorb the continuously fed, and possibly
preheated, plasticiser more easily.
Figure 13.25 shows the temperature changes as a function of mixing
time for rigid and plasticised PVC with various amounts of plasticiser.
Figures 13.26(A) and (B) show the temperature curves, respectively,
for a rigid PVC pipe blend and a plasticised (60:40) PVC shoe
compound blend, both processed in a hot/cold mixer combination.
Figure 13.27 illustrates, in a generalised and highly simplified form, the
temperature changes of rigid and plasticised PVC compositions as
functions of mixing time in hot/cold mixer combinations.
Among factors contributing substantially to the achievement of
optimal properties in a PVC composition are the timing, sequence and
method of additive admixing, as well as the speed programme of the
high-speed mixer, mixing time and final temperature. It is therefore a
serious mistake to underestimate mixing technology and to regard the
mixing step as an unimportant preliminary to subsequent processing.
Influence of raw material components and processing conditions on
the properties of hot blends:
-PVC polymer. Particle structure, shape and size affect the blend
flow properties. Suspension and bulk polymers with porous
particles absorb the plasticiser easily. Fine-grained emulsion
polymers containing emulsifier, and their large-grained clusters
which are broken down in the mixer, usually result in pasty stock
when the plasticiser is added: this can only be used to produce
agglomerate.
-Type of plasticiser. Dry mixes are difficult to produce with
plasticisers of limited compatibility (which are poorly absorbed by
the polymer particles), and with slow-gelling plasticisers. Primary
plasticisers with good gelation effect give the best results.
-Plasticiser quantity. This is a crucial factor in producing a hot
575
dry blend. The maximum amount of plasticiser that the hot mixer
will tolerate depends on the type and K value of the polymer, as
well as the plasticiser type. In some cases high percentages of
plasticiser can only be handled by hot mixers to produce
agglomerate. The temperature of incipient agglomerate formation,
and then that of lump formation, decreases with increasing
plasticiser content. In other words: the higher the plasticiser
content, the lower the admissible final temperature. Cold mixing
at high plasticiser contents will normally result in damp or wet
mixtures lacking the ability to flow freely.
-Plasticiser viscosity. This mainly influences the diffusion rate into
the PVC particles (see Fig. 5.3 in Chapter 5). Medium- to
high-viscosity plasticisers therefore require longer mixing times,
unless their viscosity is reduced by heating before addition.
-Admixing the plasticiser. Understandably, it makes a difference
whether the plasticiser is placed in the mixer first and the solid
components then added or whether it flows into the cold or hot
pre-mix of the other components, and whether its introduction
into the running mixer is made in one shot, in portions, or
continuously. The best results are obtained by allowing the
plasticiser to flow slowly into the pre-mix of the solid components
at an elevated temperature (about 7o-S0oq. The feed rate should
be set in such a way that the amperage drawn by the drive motor
does not rise sharply. After the plasticiser has been added, mixing
should be continued for about one minute to make sure all of it
has been completely absorbed. If plasticiser is added to suspension
or bulk PVC of medium absorption capacity faster than it can be
absorbed by the particles, a highly viscous paste will form which
will then gel to produce large, tough lumps if mixing is continued.
This may cause the drive to cut out because of overloading: in any
case, the mixture is unusable and cleaning of the mixer is
unpleasant and time-consuming.
-Mixing temperature and mixing time. Mixing time depends upon
the required final temperature, which is given in the temperature/
time diagrams earlier in this section. For high-speed mixers it
ranges between 10 and 20 min, depending on the formulation and
whether a hot or hot/cold mix is involved. A reliable rule-ofthumb is that a temperature rise of more than 15C min -1 should
be avoided during mixing: otherwise local overheating can damage
the mix. Furthermore, the correct final temperature of the mix is
576
577
mixers are:
-optimal mix quality and homogeneity;
-short cycle times and high output rates;
-very free-flowing blends;
-pneumatic conveying of dry blends or agglomerates without
product segregation;
-up to 20-40% increase in bulk density as a result of sintering, thus
raising the output rates of processing machines;
-low-cost and effective lowering of the residual VC content, partly
because of the high mixing temperatures of more than 80C;
-nearly complete elimination of residual moisture in the material.
578
104.11
T.mp.,otur.
(OC)
50
75
100
579
the rheological behaviour of the material. Raising the stock temperatures and residence times results in more severe structural disruption,
and unravelling of the macromolecules, ultimately leading to a higher
degree of gelation. Where pellets are being fed to an extruder, for
instance, a higher degree of gelation requires higher melting energies
during extrusion. Because modern final-processing extruders are
pushed to the performance limit, raising the melting power may make
certain extrusion operations unprofitable as a result of reduced output.
Thus the compounding process has to be matched to the operating
conditions in the final processing (production) step, whilst achieving its
fundamental objective, viz. the maximum homogenisation and degree
of dispersion of the additives in the PVC resin, with the lowest possible
input of thermomechanical energy and minimum residence time, so
that the 'heat history' (and hence degradation) of the resin is kept to a
minimum.
Besides homogenising the composition, compounding converts it
into a physical form suitable for subsequent processing. In recent
years, too, sharply increased processing speeds on calenders and
extruders have added effective de-gassing of the PVC compoundoriginally effected on mixing rolls and in internal mixers-to the list of
the functions of compounding.
Whilst they are still in use in laboratories and in some small-scale
operations, mixing rolls and internal mixers find only limited
application in present-day industrial melt-compounding of PVC, which
is now largely the domain of screw-type compounding machines.
Continuous compounding on such equipment was introduced about 30
years ago with a view to better control of residence times, improved
efficacy of mixing, reduction of compound quality fluctuation (and
hence better reproducibility), process rationalisation, and elimination
of the effects of chance in batch and intermittent operation. In view of
this, the discussion in this section is confined to compounding processes
involving continuously operating screw-type machines.
In such machines, 80-90% of the energy required for fluxing the
polymers and homogenising the mixture is obtained by the conversion
of mechanical shearing energy. Only 10-20% of the total energy
requirement is provided by heating the barrels and screws. The main
job of the heating system is to ensure that the screw and barrel surfaces
in contact with the material are kept at a desired set-point
temperature; inter alia this prevents overheating and scorching of the
PVC stock as a result of wall slippage: thus the heating system must be
580
capable of both supplying and dissipating heat. For this reason systems
based on the circulation of liquid heat-transfer media, such as water or
HT oil, in screws and separate barrel zones have gained wide
acceptance in industrial practice.
(a) Compounding and pelletising
Both rigid and plasticised PVC compositions are melt-compounded.
The general types of compound produced are shown in Fig. 13.29. The
characteristic curves of various rigid and plasticised PVC compositions,
obtained on a high-pressure capillary rheometer (Fig. 13.30), demonstrate the wide differences in rheological behaviour that have to be
coped with during the compounding process to obtain the necessary
degree of gelation.
The graph shows that with plasticised PVC compositions high
outputs are obtained within a relatively narrow (and generally low)
pressure range. This applies in melt compounding, so that-in the
context of this process-plasticised PVC may be regarded as relatively
insensitive to pressure and shear. For rigid PVC the graph shows a
pronounced influence of pressure on output, i.e. in this sense rigid
PVC compositions are sensitive to pressure and shear. Because energy
dissipation in screw-type machines is essentially a function of shear rate
and system pressure, adjustment of the degree of gelation of rigid PVC
calls for special elements to control these parameters in this kind of
equipment (see also further discussion below).
MELTCOMPOUNDED
PVC
COMPOSITIONS
FLEXIBLE
BOTTLE
EXTRUSION CABLE
COMPOUNDS COMPOUNDS COMPOUNDS
INJECTION
MOLDING
COMPOUNDS
EXTRUSION
COMPOUNDS
13
plasticised PVC
[k~] Oulpul
581
rigid PVC
6
21)
1,5
1,0
0,5
10
20
30
40
so
60
70
582
w.
Fig. 13.31 PVC pelletising: flow sheet. 1, Silos for solid components (resin,
filler); 2, tanks for plasticisers; 3, discharge and conveying devices; 4,
plasticiser supply pumps; 5, batch weighing station for solid components; 6,
batch weighing station for plasticiser; 7, pre-mixer; 8, compounding and
pelletising unit; 9, vacuum pump; 10, pellet cooler.
583
Another portion of the shear energy is used for breaking down and
dispersing the additives. The ways and means of imparting the energy
to the material are discussed in Section 13.4.4(a) ('screw-type
machines').
Homogenisation is one of the three objectives of the compounding
process, the other two being de-gassing and conversion of the
compound into a form suitable for further processing. In practice,
cylindrical pellets with diameters of 25-4 mm and lengths from
1 to 4 mm have proved optimal for feeding final processing machines.
To produce the pellets, it is necessary to force the plastic PVC stock
through a multi-hole die plate. One way to do this is to incorporate in
the screw-type machine a suitable metering and pumping zone, and to
mount the pelletising die plate directly on the end of such a machine.
This approach represents a rigid combination of compounding and
forming (i.e. pelletising).
Research and development work started at the end of the 1960s
demonstrated, however, that the optimal design and operating
parameters for compounding and forming, respectively, are often
diametrically opposed, so that it makes more sense to separate the two
stages clearly from one another in high-production compounding lines.
This approach resulted in the development of two-stage compounding lines, with one screw-type machine for compounding and a second
one for pelletising. Usually the pelletising screw is set up in cascade
fashion following the compounding screw. Pelletising machines are
normally single-screw designs, but the compounding step may be
handled by either single-screw or multi-screw machines. In some
cascade compounding units, the homogeneously fluxed PVC stock
drops in lump form through a connecting tube from the outlet end of
the compounding stage into the feed opening of the pelletising screw.
Vacuum can be applied to the connecting tube to de-gas the PVC
stock.
The pelletising screw proceeds to build up the pressure required for
extruding the compounded stock through the pelletiser's die plate.
With this separate arrangement, design and process parameters such as
speed, shear and temperature profile can be selected in such a way that
a minimum amount of energy is dissipated during the forming phase,
which is probably the most critical phase of the entire compounding
process.
As already mentioned, when compounding rigid PVC compositions
it is necessary to control effectively the system pressure in the
584
PELLETISER
585
Centreline
olugilulol shults - -
586
COMPRESSED AIR
~+-"'T'"-DC::.t---
WATER
587
DIE PLATE
PACK
588
crosslinkable polyethylenes, either the traditional, peroxidically crosslinkable polyethylene or Sioplas (developed by Dow Corning, UK). A
modern compounding line must therefore be sufficiently versatile to
compound and pelletise these crosslinkable polyethylene compounds as
well as a broad range of PVC formulations.
The specific energy normally dissipated in the compounding step
is about 006-008 kWh kg- 1 for rigid PVC formulations and 004006 kWh kg- 1 for plasticised PVC formulations. In the forming step, i.e.
in the pelletising screw, additional specific energy is expended for
pressure build-up and extrusion of the PVC stock through the die
plate. A rule-of-thumb from actual practice indicates that the specific
energy requirement for extrusion through the die plate equals about
1/10 to 1/5 of the energy dissipated during compounding. The
introduction of energy causes the stock temperature to rise as it moves
through the kneader. Figure 13.39 shows typical stock temperature
profiles for various PVC formulations.
Compounding lines now available on the market cover a production
band from 100 kg h -1 to 6 t h -1. Besides these production units,
scaled-down laboratory units are offered for formulation development
and colour matching as a basis for production. Such units must employ
T (e)
200
180
160
140
120
100
eo
60
40
20
I.ENGlH
('tttot )
13
589
590
These requirements apply to the entire range of PVC film and sheet
formulations, which can be classified into three main groups according
to their plasticiser content:
-rigid (substantially without plasticiser);
-semi-rigid (10-25% plasticiser-Shore A hardness 95-85);
-plasticised (25-40% plasticiser-Shore A hardness 85-60).
For plasticised PVC film and sheet, a standardised calendering
practice has emerged in which a 'rolling bank' is set up in the calender
nip.
In the case of rigid PVC, processed at temperatures higher than
those in plasticised PVC lines, one of two calendering methodsrespectively known as the high- and low-temperature processes-may
be used, depending on the type of sheet or film being produced.
In the high-temperature process, the calender bowls are heated to
progressively higher temperatures with-typically-the intake bowls at
about 160C, and the last nip at about 210C. The film or sheet is then
passed through the usual cooling roll train.
In the low-temperature process the reverse heating order is used.
The temperature drops from, say, 175C at the intake to 145C at the
last bowls, i.e. the fluxed stock is formed in a relatively cool state.
Normally, the films produced by this method are fed directly to an
orienting calender, where they are heated rapidly on melting rolls
heated to about 240C, and then cooled sharply down to 110C. This
provides optimal film orientation. Known under the name of the
'Luvitherm process', this low-temperature process has gained acceptance in Europe for the production of tearproof films.
The calendering method also determines how the temperature will
be controlled in the compounding step. For the high-temperature
process, the PVC stock must be delivered to the calender fully
plasticated; for the low-temperature process, it should be barely
plasticated (crumbly), i.e. it has to be fed to the calender at a lower
temperature.
The calender design is determined essentially by the type of film and
sheet to be produced on it. The design determines, in turn, the overall
layout, position of the compounding unit relative to the calender, and
the necessary conveying and feeding elements.
Figure 13.41 shows the bowl arrangements in various four-roll
calender types. At the present time, the 'L' and inverted 'L' (also
called 'F') types are dominant.
13
(i)
(iv)
(iI)
(v)
591
(Iii)
(vi)
Fig. 13.41 Bowl arrangements in 4-bowl calenders. (i) Inverted 'L' type
(sometimes referred to as 'F' type); (ii) 'z' type; (iii) inclined '5' (or 'Z') type,
down-stack; (iv) inclined '5' (or 'Z') type, up-stack; (v) 'L' type; (vi) vertical
stack. Arrangements (i), (ii) and (iii) are widely used in PVC sheet production.
592
593
Fig. 13.42 A typical compounding train for PVC calendering: flow sheet. 1,
Truck unloading station for solid components; 2, debagging station for solid
components; 3, pneumatic conveying system; 4, silos for solid components
(resin, filler); 5, day bins for solid components; 6, day bins for plasticisers; 7,
batch weighing station for solid components; 8, batch weighing station for
liquid components; 9, minor ingredients proportioning station; 10, pre-mixer;
11, buffer silo; 12, compounder; 13, conveying belt with metal separator; 14,
two-roll mill; 15, conveying belt; 16, calender; 17, edge trim cutter; 18, silo for
cut edge trimmings.
594
-~
~
BUSS-KNEADER
13
595
simpler and more uniform nip feeding, the strands can be sliced into
chips with a cutting device working in conjunction with the die (Fig.
13.45).
Straining of the stock may be desirable, particularly for the production of plasticised PVC sheet and film, to remove foreign objects such
as fibres, paper cuttings, wood chips, etc., which may have entered the
mixture from the raw material packages.
596
w.
13
T (OC)
597
ZXl
180
1iO
v.o
lZ)
eo
60
IIJ
Z)
}1.
Fig. 13.46 Temperature profiles, PVC sheet and film stock. 1, Plasticised
PVC; 2, rigid PVc.
Fig. 13.47
iii
...
-~ill
1'---
1--11
11
.111,,1
_~~_I
Bj
IlL
,
I
.-
--
f--------L.........
----
.
=
~-
r---l
PVC cascade extruder with sheeting line. 1, Extruder; 2, flat sheet die; 3, triple-roll smoothing system;
4, roller conveyor; 5, edge trimmer; 6, twin-roll haul-off unit; 7, length cutter; 8, sheet deposit.
Wren . .
n~r1l
Ul
\0
~
l:>
;:s
:"l'
l:l.
;:s
l:>
;,~
"
i;
00
599
(d) Recycling
At the time of writing, no general strategy for recovery of plastics
scrap has yet gained wide acceptance. Undoubtedly this is attributable
-..
-
600
601
PLASTlC~ ~
~~Wl
STRAINER
602
w.
INNER SHEATHING
REINFORCEMENT
Fig. 13.49 Cable design.
parts of chalk filler. At this level of loading the PVC acts mainly only
as binder for the filler. The reground PVC scrap, with a particle size of
5-10 mm, is fed into the first inlet of a compounding unit designed
specifically for this application (Fig. 13.50). The regrind is plasticated
homogeneously in the first kneader zone, enabling it to absorb the high
filler loading metered in at the second inlet opening without any
problems. To plasticise the filler cores further (for increased flexibility)
plasticiser is injected into the kneading chamber by a pump. The
homogeneous stock is pelletised as described in Section 13.4.2(a).
PVC SCRAP
FILLER
PlASTIC~ ~
Fig. 13.50 Compounding of cable filler cores.
603
Batch
Vertical
Low speed
Horizontal
Dissolver
Roll mills
Vertical
3-Roll mill
Dissolver
Buss mixing turbine MT
604
rationalisation efforts led to the first trials with such mixers: the use of
dissolvers with infinitely variable speed control eliminated such
recognised shortcomings as limitations on mixing tool speed and
inadequate coverage of the entire mixture volume, and marked a real
improvement in the efficiency of producing pastes on a batch basis.
Today, changing economic conditions have again evoked demands
for improved efficiency and automation, for better working conditions
and anti-pollution measures, for improved space utilisation and higher
per capita outputs.
To meet these demands, continuously operating units such as
continuous dissolvers and the Buss Mixing Turbine were developed.
Regardless of whether the continuous or batch approach is used,
industrial preparation of stock pastes can be broken down into the
following stages (Fig. 13.51):
-silo storage of components;
-metering of components;
-pasting-up and dispersion;
-filtering;
-de-gassing (de-aeration);
-ageing.
The preparation of pigment pastes, and stock paste colouring, run in
parallel with the preparation of stock pastes.
(a) Silo Storage
This is practised as described in Section 13.3.
(b) Metering
Because of the special nature and mixing requirements of PVC pastes
it is necessary to charge the components into the mixer in fractions. In
the simplest case, the components are batch-weighed and the portions
charged into the mixer manually.
In automated processes this manual operation has been replaced by
gravimetric metering devices for the bulk materials and metering
pumps for the plasticisers. For the bulk materials, either belt weighers
or differential weighers (loss-in-weight feeders) can be used. While the
metering devices used for batch operation operate intermittently, i.e.
are switched off after the desired amount of a component has been fed,
metering devices for continuous operation supply an uninterrupted
flow of material that remains constant per unit time.
TANK)
pASTE
BUFFER
AGEING
DE-GASSING
FIL TERING
DISPERSING)
(WETTING,
PREPARATIONI
METERING
Fig. 13.51
_g
_PL_A_STlCISER
I
I
I
----,-
FILLER PLASTICISER
STABILISER
9-~9~-c-Q -.~T~r~
PVC
CONTINUOUS
I-M_:_~_Y_~_:_IG_AE_L_~__~_~__s_TA9_~E_R
BATCH
0;'
~.
:::!:!
I::>.
0~
~
::>;,
oQ.
~
;;;'
s.
~c
.:
::;
......
c..,
606
w.
607
because in the Buss Mixing Turbine the mix components come into
contact at individual particle (or plasticiser droplet) level. This
accelerates both the pasting-up and dispersion operations (particularly
the latter).
Batch mixing in the dissolver and continuous mixing in a turbine
both produce pastes so smooth that they are ready for use and
normally require no additional grinding step on mixing rolls (as
practised in some traditional, or small-scale, paste preparation
methods).
(d) Filtering
Paste quality can be impaired by the kind of contaminants mentioned
in the discussion of melt compounding, or by the presence of isolated
undispersed lumps. In cases where the paste is passed through mixing
rolls for grinding, partly gelled particles (small lumps) of paste can
cling to the ends of the rolls and get into the product at the end of the
grinding operation. All such impurities must be filtered out.
Although a number of filter devices are available, the vacuum filter
described below is the one most frequently used. It can either be
moved around the workshop on a portable frame and fitted onto the
vacuum-tight mixing and transport tanks as required, or set up for
stationary use between mixer and de-gassing tank. The PVC paste fed
into the hopper of the device (Fig. 13.52) passes through a screen pack
mounted in a quick-change frame: the screen packs are much the same
as those employed in automatic screen changers for thermoplastics
608
processing. One pack is in operation while the second waits its turn.
The paste is drawn through the screen by vacuum in the tank below.
When the screens become clogged, the two packs are reversed and
the contaminated one replaced by a new pack. Clogging of a screen is
indicated by an increase in tank vacuum. The screen pack mesh must
be fine enough to retain particles larger than 200 tlm. The filtered paste
passes directly on to the de-gassing step.
(e) De-gassing
Air enters the mixing unit with the bulk materials. In addition, the
PVC particles contain air and moisture as a result of their structure.
Steadily rising quality requirements have been forcing producers of
imitation leather, floorings, toys, etc., to de-gas their PVC pastes
effectively, and this has how become standard practice. Low-viscosity
pastes are de-gassed by the application of a 5-50 mbar vacuum for
about 10 min (about 20 min for high-viscosity pastes).
Effective de-gassing requires that the surface of the stock be
continuously renewed, thus shortening the diffusion paths and the
evacuation time. That is why vacuum dissolvers or vacuum planetary
mixers are employed for the de-gassing of PVC pastes. For continuous
operation, appropriate continuous degassing units are available on the
market.
(f) Ageing
The procedure just described is typical of the preparation of medium
to large batches of stock (uncoloured) PVC pastes. Directly after
preparation the stock paste is pumped into a storage tank where it is
kept-under slow stirring-to serve as buffer stock between paste
production and subsequent processing. The storage may also serve as
an ageing period (of up to about 24 h) during which the paste viscosity
attains a desired value (see also Chapter 21).
(g) Colouring
PVC pastes are coloured by the addition of colour pastes, produced by
dispersing colourants in plasticisers (batchwise in planetary mixers or
dissolvers, or by the continuous method in mixing turbines), and
homogenising by milling (in ball or roll mills). The method of
preparation is thus similar to that used in the paint and varnish
industry.
Colour pastes are added to PVC stock pastes in high-speed mixers or
dissolvers with average mixing tool peripheral speeds of 10-12 m S-l,
609
~achinery
Manufacturer
Twin screw
Kombiplast
Buss-Kneader
Cascade extruder
Single screw
Plastifikator
X
X
X
X
X
X
X
X
X
X
X
Rigid PVC
Process
Extrusion
feeding
+ pelletising Calender-
X
X
Plasticised
PVC
Compounding
TABLE 13.9
Typical Screw-type Compounding Machines
.....
'"
l::l
;3
:-0
l::l..
l::l
;3
~
~
g.
0\
13
611
612
2 1
flow
Fig. 13.54 Working principle of the Plastifikator. (See text for details.)
Temperature control system: The cone housing is equipped with an
electric heater. The barrel of the discharge screw is also electrically
heated, but is fitted with an air cooling system in addition. If the
machines are separate, the discharge screw can be cooled with a
separate heat transfer medium.
De-gassing: Where the plastication machine and discharge screw are
separate, a vacuum of 400 to 550 mbar can be applied to the transition
section between the two to de-gas the stock.
Operation and cleaning: During starting, a diverter can be placed
between the plastification section and discharge screw to remove any
PVC powder emerging; this prevents clogging of the die plate or screen
pack (if any). For cleaning, the plastification section and discharge
screw are run empty and purged of residual powder by passing warm
pellets through. The pelletiser head can be swung out to permit easy
removal of any product remaining on the screw tip or back of the die
plate. For extreme colour or formulation changes that call for a
thorough cleaning, the discharge screw with pelletising head of the
smaller models can be rolled away on an assembly dolly. Then the shear
cone can be pulled out in front of the barrel on a bar sliding in the
main shaft. On the larger models, the cone is rolled away together with
the transfer tube on guides, making the parts in contact with the
product freely accessible.
Energy input:
Production rate:
Plasticised PVC (kg h -i)
Drive rating:
Feed screw (kW)
Main drive (kW)
Pelletising (kW)
Fan (kW)
Separate pelletising screw (kW)
Speed range:
Feed screw (r min-i)
Shearing (r min-i)
Pelletising (r min-i)
Fan (r min-i)
Separate pelletising screw (r min-i)
Heating:
Cone barrel (kW)
Extruder barrel (kW)
Pelletising (kW)
Cooling:
Fan (m 3 h- i)
Water cooling, bearing (litre h- 1)
Water cooling, cone barrel (optional) (litre h- 1)
Water cooling, gear-box (optional) (litre h- 1)
Weight:
Plastifikator (kg)
Control cabinet (kg)
4
25
125
800
4
25
125
800
3200
270
3500
270
60
20-120
52
240-900
2800
20-120
42
204-900
2800
60
4
30
075
037
4
22
075
037
250-350
Model
PKlOOIV11
150-250
PK lOOIVI
TABLE 13.10
Technical Data for the Plastifikator
10
4
2
4500
500
800
100
-
30-150
88
230-1150
2800
4
55
15
037
450-900
PK 400/111
13100
700
2 x 800
200
500
500
20
16
48
29-117
75
312-1560
2800
35
55
160
3
2 x 037
37
1200-2400
PK lOoom
..
Vol
a......
(")
-<::
'1:l
$:>..
1:;'
'"
'"
::t.
'1:l
$:>..
l:>
..
:>::I
.Q,
;:0-
'"
;;;'l
s::
~c
f:..
s.
t:;
S'
$:>..
...........
614
THE BUSSKNEADER
Applications:
-compounding and pelletising of (i) plasticised PVC blends (cable,
shoe, profile, hose, flooring compounds), and (ii) rigid PVC
formulations (bottle, profile, record compounds);
-compounding of rigid, semi-rigid and plasticised PVC blends for
calender feeding (packaging, deep-drawing, decoration, upholstery and engineering film and sheet).
13
615
616
screw flight shaded in the figure is considered for this purpose, together
with the four marked kneading teeth which work in conjunction with
it. The sequence of drawings in Fig. 13.56(A)-(F) shows the tracks of
the kneading teeth relative to the screw flights. Each consecutive
drawing represents a quarter-turn of the screw shaft, i.e. the rotation
positions of 0, 90, 180, 270 and 360 angular degrees. In the drawings,
the screw rotation corresponds to movement of the screw flights from
bottom to top; the product is conveyed from right to left. The starting
position is shown in the first drawing.
In the course of a turn through 90 (Part (B, the dark kneading
tooth, which started at the top flight tip, has wiped past the long
left-hand flank of the screw flight. As it did so, the product was
sheared in the gap between the kneading tooth and shaded screw
flight, and the flank of this flight was cleaned at the same time. The
other marked teeth have not yet 'moved into action with the shaded
screw flight, but they have been working with other flights.
0
617
Fig. 13.55 The screw and barrel of: a, conventional single-screw machine; b,
the Buss-Kneader.
618
c::::::::::::
619
c:::::::
-~~
620
Temperature control system: The barrels of both the kneader and the
621
pelletising screws are fitted with jackets divided into several zones. The
screws are hollow right up to the tip. This design permits accurate
control of screw and barrel temperatures by means of liquid
heat-transfer media, usually HT oil. Pelletising die plates are heated
either electrically or with liquid.
De-gassing: On the KG and WKG models, which are used for
compounding and pelletising, de-gassing of the stock takes place at the
transition point between Buss-Kneader and pelletising screw. On
PRKlE models for feeding calenders, the Buss-Kneader is equipped
with its own de-gassing zone at the outlet end.
The de-gassing systems provide for vacuum as high as 50-60 mbar.
Operation and cleaning: When the KG and WKG pelletisers are
started up, the initial material can be eliminated with a diverter
between the Buss-Kneader and pelletising screw. In calender installations, the starting material can be eliminated at the kneader outlet.
Buss-Kneaders and pelletising screws are cleaned by running them
empty and purging residual powder with cleaning pellets. The
pelletising head can be swung out to allow easy removal of material
remaining between screw tip and die plate. For extreme product
changes requiring a thorough cleaning, the Buss-Kneader barrel flaps
open (Plate E), so that both screw and barrel are freely accessible. The
barrel of the pelletising screw can be drawn off the screw on an integral
roll-away chassis. Because all parts are fastened to the machine base
and therefore remain properly positioned, this cleaning procedure
requires no special tools, hoists or specially trained personnel.
Energy input:
Applications:
622
Plate E
623
Equipment and operational sequence (Fig. 13.58 and Plate Cl): The
cascade extruder is made up of two single-screw extruders, the fluxing
extruder and the discharge extruder. PVC pre-mix is fed into the
former through a simple inlet hopper without any agitator or metering
device. The fluxing screw mixes the blend and partly agglomerates the
stock into particles of approximately uniform size. The production rate
depends on the momentary bulk density of the pre-mix and the screw
speed. When the agglomerated stock emerges from the fluxing
extruder, it drops through a de-gassing tube (to which vacuum as high
as 80 mbar can be applied)' into the intake section of the discharge
extruder. Retention time in the de-gassing tube can be regulated by
altering the agglomerate level in the tube. The discharge extruder's job
is to complete plastication of the partially fluxed material, homogenise
it, and force it through the outlet die.
Working principle (Fig. 13.59): The energy required for agglomeration
and plastication of the PVC stock is supplied by heating the barrel and
by shearing the stock between screw core and barrel wall. The screws
are provided with a 'heat pipe' to prevent overheating and scorching.
To improve its intake characteristics, the fluxing extruder is fitted
with a cooled, grooved bushing in the inlet area. The intake section of
the discharge extruder is designed in the form of a tapered slot.
Temperature control: The barrels are heated electrically. Screw
temperature is controlled by the heat pipe system.
De-gassing: In the transition tube between fluxing and discharge
extruders.
Output and technical data: See Table 13.13 and Fig. 13.60.
THE KOMBIPLAST
Production rate:
15
40-300
46
7
4
06
16-80
46
2
40
75
1000
3
30
PR
ET
GS
11
120-600
2
3/36
05
3
20-80
70
6
3
WKG46-7
18
7-47
80
2
ET
400
750
4500
3
30
70
40-240
100
7
4
PR
GS
15
120-600
2
3/36
17
11
10-47
140
4
3
WKG1Q-14
3
4-30
140
25
ET
1500
BOO
1oo
3
60
107
40-120
140
7
4
PR
58
10-40
140
25
2
RS
KG 14-18
22
12(}..6()()
2
3/36
3
24
8-40
180
6
3
GS
45
4-30
215
2
ET
1600
3000
17500
3
60
210
40-120
200
7
4
PR
125
5-39
200
25
2
RS
KG2Q-25
TABLE 13.11
Technical Data For Buss-Kneader Models KG and WKG
3
120-600
2
3/36
4
52
8-40
250
6
3
GS
75
4-25
300
2
ET
3200
S-7ooo
38500
6
120
510
40-120
300
7
4
PR
23
5-35
300
25
2
RS
GS
75
100-1000
2
3/36
7
95
6-30
320
6
3
KG3Q-32
;:,
'"
;:,
!'>..
'"
";~,-
1;;
0"-
a
b
GS
ET
PR
70
40-240
100
7
4
750
18
7-47
80
2
75
11
12lHiOO
2
3
05
3
20-80
70
6
3
4500
3
30
IS
40-300
46
7
4
15
12Q-{;()(J
2
3
17
11
10-47
140
4
3
GS
WKGIO-14
1000
3
30
PR
ET
06
16-80
46
2
WKG46-7
ET
3
4-30
140
25
1500
8700
3
30
107
40-240
140
7
4
PR
22
12lHiOO
2
3
3
24
8-40
180
4
3
GS
WKGl4-18
Approximate figures, not including heating/cooling units, pellet cooling installation, control cabinet or main drive motor.
Approximate figures; may vary depending on formulation and operating conditions.
ET
45
4-30
215
2
3000
60
15800
3
210
40-240
200
7
4
PR
3
12lHiOO
2
3
4
52
8-40
250
4
3
GS
WKG20-25
ET
75
4-25
300
2
6-7000
35000
4
120
510
40-120
300
7
4
PR
75
100-1000
2
3
7
95
6-30
320
4
3
GS
WKG30-32
Ul
'"tl
It
~.
0;.
;:,
I'>.
""
Ii;:
::tl
a;;.
g.
s::
~o
so
....
.......
626
TABLE 13.12
Technical Data for Buss-Kneader Models PRK and PRK/E
PRK, PRKIE
PRK, PRKIE
PRK, PRKIE
100
140
200
Feed hopper:
Capacity (litre)
Screw diameter (mm)
Screw drive (kW)
Screw speed range (r min-I)
150
100
18
67-47
280 or 430
140
44
22-44
430 or 830
215
55
14-28
Buss-Kneader:
Screw diameter (mm)
Screw length PRK (LID)
Screw length PRKlE (LID)
Screw speed range (r min-I)
Gear box model
Kneader drive (kW)
100
7
12
120
G20
60
140
7
11
120
G45
120
200
7
11
120
G130
200
Heating/cooling equipment:
No. of units
Installed heating capacity (kW)
2
20
2
36
2
36
3800
6300
11700
the pelletising die. Cutting knives mounted next to the die plate chop
the emerging strands into pellets, which are conveyed pneumatically to
the pellet cooler.
Working principle: The ZSK is a twin-screw machine with intermeshing, co-rotating screws equipped with kneading discs (Fig. 13.62)
which shear and knead the product and change the local direction of
stock flow as it passes the barrel wall. The shearing occurs, and energy
is imparted to the stock, as a result of the velocity drop between the
kneading discs and the barrel wall and in the saddle area between the
two screws. Shearing intensity is determined both by the speed of the
screws and the inherent resistance of the kneading discs.
The configuaration and arrangement of the discs shown schematically in Fig. 13.62 give rise to squeezing forces which pass the material
forward along the screws while it is subjected to shearing and mixing
by the consecutive disc elements. The design ensures that the root of
each screw is wiped by the flight tip of the other. This self-cleaning
13
Output in kg h- 1
Model
PRK/E
2000
Output in kg h-1
Model
PRK
3000
1670
PRK/E 200
1350
1000
/~
670
330
o
o
627
-",
V
10-""-
~RK200
2500
2000
1500
PRK/E 140 ~
J/"
~ PRK140
-- -
20
40
60
80
Speed of Buss-Kneader screw
PRK/~ 100 I
1000
500
PRK100
100
r min- 1
120
Fig. 13.57 Output diagram for Buss-Kneader models PRK and PRKlE.
profile eliminates dead spots and normalises the residence time of the
material.
Temperature control system: The ZDS-K and ES-A barrels are
electrically heated. The ES-A unit is cooled by an air blower, whilst
the barrel of the ZDS-K unit has channels for cooling with liquid
heat-transfer media.
De-gassing: De-gassing is carried out at the transition point between
the ZDS-K and ES-A units.
Operation and maintenance: The starting product can be diverted
between the ZDS-K and ES-A units. For cleaning, both units are run
empty, and residual powder is purged with a cleaning material. The
pelletising head can be rolled away, which facilitates the removal of
product between screw tip and die plate. The barrel sections of the
ZDS-K and the barrel of the ES-A can be dismantled for more
thorough cleaning work.
628
u
>
p..
...
sa...
-...
0
'0
;:I
>0<
0
'0
~
u
en
~
....0
U
l=:
.~
en
0
00
V)
~
......
oil
629
Standard Extruder
n
Process Steps
Applications:
630
TABLE 13.13
Cascade Extruder: Technical Data
Data
Model
1000
kg/h
900
E6K
E9K
E12K
2 x 60
2 x 90
2 x 120
2 x 150
9D
13D
9D
13D
9D
13D
9D
13D
100
80
70
60
20
12
5
144
48
32
5
273
87
60
5
486
140
100
5
740
4
1
2
4
1
2
4
1
2
4
1
2
20000
4000
30000
8000
40000
12000
50000
12000
36
12
023
46
19
026
97
22
045
97
22
045
800
700
.... 600
....5.500
::l
0400
300
200
100
~
E9K
E15K
E12K
E15K
Extruder size
Fig. 13.61 The Kombiplast machine. 1, Screw barrel; 2, two co-rotating screw shafts; 3, thyristor controlled DC motor;
4, reduction gear; 5, duo gear which distributes the drive capacity between the two screw shafts; 6, screw barrel; 7, single
screw; 8, eccentric pelletiser; 9, die plate; 10, neck connecting the two machines; 11, quick acting lock; 12, pole-changing
three-phase motor; 13, spur gear.
0\
ri
t;;.
,,'
'[
;:
'"
I:>-
:;.;,
~
~
o
0-
;:
g.
;::
;:
~o
'""
......
632
Production rate:
Plasticised PVC (kgh- I )
Rigid PVC (kg h- I )
Screw:
Diameter (mm)
Length (UD)
Drive rating:
Main drive (kW)
Fan (kW)
Pelletiser (kW)
Speed ranges:
Screw (r min-I)
Fan (r min-I)
Pelletiser (r min-I)
Temperature control:
Barrel (kW)
Die plate (kW)
Heating cabinet (kW)
Cooling capacity of beating
cabinet (kcal/h)
Water consumption (m 3 h- I)
Air consumption (m 3 h- 1)
Weight:
Machine (kg)
Control cabinet (kg)
KP5(}(}
200-350
100-200
500-1100
350-700
ZSK57M23
ES-Al(}(}
ZSK90M58
ES-A150
57
13
100
6
89
115
150
6
3&-17
7/10
037
11
11-:>-50
17f27
82-360
21/42
2800
156-780
82-360
16/32
2800
23o-U50
96
30
3-15
45
10000
180
70
50
45
10000
45
14000
037
15
45
22000
04
01
800
07
015
800
1400
500
1500
2400
600
1900
13
633
KP 1500
KP 2500
KP 3500
1200-2200
700-1300
1800-3600
1100-2100
3000-5000
1400-2800
4500-7500
2100-3800
ZSK 130M325
ES-A250
ZSK130M325
ES-A3oo
ZSK130M650
ESA350
89
115
200
6
130
14
250
6
130
14
300
6
130
14
350
6
10-100
25/36
2 x 037
22
1ll-180
40/56
2 x 15
4
24-240
62/90
2 x 15
55
355
90/132
36-360
16132
266-266
15130
36-360
15130
30-300
15130
2800
155-750
ASK90M120 ES-A200
2800
180
45
22000
160
72
45
10000
2800
200-1000
230-1150
320
45
22000
200
84
120
14000
2800
75
270-780
320
45
22000
220
96
150
14000
320
120
40000
120
360 + 180
30 000 + 14000
10
03
1600
15
05
2000
20
07
2000
30
30
3900
700
2500
5500
700
7500
5500
700
12000
6500
800
18000
634
w.
Section A-A
Section B-B
Mixing
Feeding
13
635
TABLE 13.15
Volume (dm )
Max. torque (Nm)
Standard gear box:
Max. rating (kW)
Max. screw speed (r min-l)
Special gear box:
Max. rating (kW)
Max. screw speed (r min-I)
Dimensions with drive:
Length (m)
Width (m)
Height (m)
2FCM
4FCM
6FCM
9FCM
0344
187
270
1432
913
7162
308
28640
22
1150
735
100
257
350
882
300
1102
375
20
15
28
2050
Production rate:
Plasticised PVC (kg h- I)
Rigid PVC (kg h- l)
165
90
42
16
2730
60
15
13
6700
70
20
16
9600
550
300
2000
1100
5000
3750
1-1
THE MPCIV
636
SCrews
Vacuum
Connection
Extruder
To Pellellser
13
637
50mm
80mm
100mm
125mm
160mm
PVC
Drive
rigid flexible
(kg h- 1 )
(kW)
130
500
700
1400
2800
250
1000
1500
3000
6000
11
45
55
110
225
THE BITRUDER BT
638
Plate F
Bitruder GTlOO-18G.
639
TABLE 13.17
BT80-12G
BT 80-16G
BT 100-14G
BT 100-18G
BT 150-17G
Screw
diameter
(mm)
Screw
length
(LID)
77
77
12
16
14
18
17
98
98
150
Screw Heating
rating capacity
(kW)
(kW)
25
25
33
37
133
17
17
31
36
88
Output
rates
(kg h- J )
120-230
200-400
300-550
450-750
650-1200
Because the two makes listed in Table 13.9 are basically very similar,
they are discussed together in this section.
Applications:
-compounding and pelletising of rigid and plasticised PVC: ZSE
(EKK Kleinewefers);
-compounding of rigid and plasticised PVC film/sheet formulations
for calender feeding: PWE-AK and PWE-EV (EKK Kleinewefers); WE (Hermann Berstorff).
Equipment and operational sequence (Fig. 13.65): A force-feed
hopper feeds the PVC pre-mix into the filling zone; the material is then
passed into the planetary screw section for plastication and
homogenisation. This section is closed off with a retention ring which
prevents axial displacement of the planet screws (Fig. 13.66).
Models PWE-AK and WE typify the machines used for feeding
calenders without any de-gassing; the homogenised stock emerges from
the retention ring of the planetary screw section in the form of helical
strands, which are fed to the calender. If intensive de-gassing of the
stock is required, model PWE-EV is employed (Fig. 13.66). Basically,
this is a PWE-AK machine with a single-screw extension with
de-gassing and discharge zones. Here again, the planetary screw
section is terminated by a retention ring.
ZSE lines (Fig. 13.67), widely used for compounding and pelletising
rigid and plasticised PVC compositions, are basically cascade systems
made up of a PWE-AK machine followed by a single-screw discharge
extruder, with a de-gassing tube between the two units. The strands of
640
compound forced through a multi-hole die plate are cut into pellets by
the hot die-face cutting method and conveyed pneumatically to a
cooler.
Working principle (Fig. 13.68): The plastication and homogenisation
process takes place in the planetary screw section, which comprises
four interacting elements, viz. the driving main spindle, the follower
planet screws, stationary barrel, and retention ring.
13
641
30
When the main spindle is rotated, the planet screws rotate along
with it and roll around the inside of the barrel. As a result, the PVC
stock is sheared and squeezed between the tooth flanks and roots of
the main spindle, planet screws and barrel. Mechanical energy is
converted into heat and the stock is plasticated. External heating is
employed to aid the plastication work.
642
643
Screw length
6 to 12
25-50 (70, 100,
120 and 150 EV)
3-60 (200 EV)
35-70 (170 EV)
6 to 18
2-40 (ZSE 300)
to
35-70 (ZSE 100)
5D1twin helix
6D (ZSE 300)
to
85D (ZSE 150)
500-1000
13D (170EV)
to
165D (100 EV)
260-1000
150 to 350
150 to 315
70 to 206
2nd stage
Single-screw system
PWE
70 EV to 200 Eva
(6 models)
1st stage
Planetary system
WE
100 to 2900
(5 models)
138 (120 AK)
to
315 (300 AK-N)
62D (300 AK-N)
to
88D(150 AK)
500 (100 AK-N); 700
(120 AK); 900 (150
AK); 1000 (all other
models)
7 to 18
2-40 (300 AK-N)
3-60 (all models)
to
35-70 (100 AK-N)
TABLE 13.18
Technical Data for Planetary Compounders: Summary Table
9 to 40
6 to 22
12 to 49
9 to 31
Screw
Heating capacity (kW):
Barrel
85 to 2300
40 to 700
60 to 1400
77 to 81
12 to 280
Range limit data apply respectively to these range limit models, unless otherwise indicated.
b Approximate ranges.
c Figure for PWE 120 AK (the output of PWE 100 AK-N is the next lowest).
400 to 2800
500 to 3300
700 to 4000
1 to 2
Screw
Output ratesb (kg h- 1 ):
Rigid PVC
Semi-rigid PVC
Plasticised PVC
PVClABS blend
23 to 130
60 to 320
300c to 2800
350c to 3300
450c to 4000
21 (100 AK) to 72
(170 AK and 200 AK)
2 (100 AK) to 3
(all other models)
60 to 320
36 to 90
3 (all models)
50 to 400
646
comparison in the controller between the desired and actual tempertures and subsequent correction, either by cutting-in electric heaters or
passing cooling water through the heat exchanger.
Electric heating systems are controlled in similar fashion. Thermocouples detect the temperature of the barrel wall in each zone, which is
then compared with the set-point. If the wall is too cool the electric
heater is switched on; if it is too hot, a liquid cooling medium is passed
through the particular jacket or else fans are switched on to provide air
cooling. Each heating zone represents a closed control loop with the
set-point temperature acting as command variable.
In contrast to final processing systems, compounding operations
generally do not require the command variable, i.e. the set-point
temperature, to be altered in line with the momentary stock
temperature.
Depending on the physical layout of a compounding operation, it
may be advisable to display the various zone temperatures in the
central control room or even to record them.
METERING RATE AND SCREW SPEEDS
647
ENERGY INPUT
N(kW)
= G (kgh-I)
648
HEAT-TRANSFER MEDIUM
PVC stock (Fig. 13.71) and virtually take on its temperature. Thus the
thermocouples, which are inserted in the teeth and reach close to their
ends, are able to pick up the actual stock temperature at any point
along the barrel.
Because the stock temperatures are very important in assessing heat
history--or even only as reference data-it is advisable to record them
at the central control station. Multicolour chopper-bar recorders are
normally used for this purpose.
A-A
649
PRESSURES
650
651
"0
8
Q)
"a
I
Q)
.0
652
Planetary mixers (Fig. 13.73) are suitable for mixing stock pastes and
for colouring virgin pastes with colour concentrates. Because little
energy is imparted, no temperature problems arise, but this mixer is
not capable of dispersing solids thoroughly: additional sifting and
grinding steps are required for exacting specifications. Planetary mixers
are usually built as vacuum mixers to de-aerate the paste prior to final
processing. Anywhere from 6 to 40 mbar of vacuum is sufficient for this
purpose. Mixing aids, such as internal pin mills (Fig. 13.73(b)), can be
added without difficulty. Mixing tools can be raised up to permit
removal of the mixing tank and to facilitate cleaning. Planetary mixers
are particularly suitable for medium-size operations with a broad
product range.
HORSESHOE MIXER
Because of cleaning expense, these mills are used only for long
production runs.
653
~ .~
L.--
L.-.
t'--- L-----"
Fig. 13.74 Horseshoe mixer.
RIBBON BLENDERS
654
13
655
Ribbon blenders are used preferably for very long runs with
infrequent colour changes.
PADDLE MIXERS
The mixing tools of the paddle mixers (Fig. 13.77) dip down and bring
large, cohesive quantities of paste to the surface. In addition, the tool
surfaces beat alternately into the paste. The kneading and squeezing
processes combine to produce the mixing effect. However, for effective
operation the mixer should be no more than about 70% full. Because
the energy input is at the thermally tolerable limit, the mixing tank is
equipped with a jacket for cooling.
To reduce the labour required for cleaning, the mixing tools can
normally be withdrawn axially.
Though pin mills may be installed to improve the efficiency of
mixing, they should be used cautiously because of the energy
dissipation involved.
If the mixing tool speed is changed, paddle mixers can also be
operated under vacuum. Conversely, pressure can be applied to
accelerate emptying (even with the mixing tool stopped) and to feed
the contents to pressure or vacuum strainer units.
656
ROLL MILLS
Three-roll mills with two shearing nips (Fig. 13.78) are normally used
for producing PVC pastes on this type of equipment. Nip pressure, roll
speed and roll speed differentials (which produce the shear) must be
set appropriately for PVC pastes. If the settings are not appropriate to
their rheological properties, the paste films carried on the rolls may be
broken in the nips.
I \...- '
t\
f\
./
13
657
Unlike the mixers described thus far, the Buss mixing turbine is a
continuously operating unit for the production of stock, finished and
coloured pastes. The equipment (Fig. 13.80) consists of a vertical
stator containing a high-speed rotor. The solids are fed by a metering
device through the inlet tube, 2, into the atomisation zone, a, where
they are aerated and disintegrated for passage to the centre of the top
rotor, 4. While the solids are spun out radially by the rotor, the liquid
components are injected through nozzles on the bottom of the stator
658
Fig. 13.80 Buss mixing turbine MT. 1, Drive motor; 2, inlet for solids; 3,
rotor shaft; 4, rotor; 5, stator ring; 6, casing; 7, spray nozzles for liquids; 8,
product outlet; a, atomisation zone.
659
rings. The rotors are shaped in such a way as to propel the product
downwards as well as radially outwards.
The next stator ring directs the already wetted or partially dissolved
solid material toward the centre of the following rotor, and the process
is repeated. In some applications the entire quantity of liquid is
metered in through the top nozzle ring. In others, it is fed in fractions
to the successive mixing chambers.
The mixing turbine can be connected directly to a vacuum filter
system, in which case de-gassing can take place at the same time. The
finished PVC paste is then pumped continuously out of the vacuum
tank to the next operation.
The two-piece rotor can be swung open for easy cleaning when
drastic changes of formulation or colour are scheduled. Because the
machine is compact and easy to clean, it is economical for both short
and long production runs. Some technical data are given in Fig. 13.81.
I
r i1
~
I
Ii
I~
L.--
t:::
il-t
""f
H(mm)
B(mm)
T(mm)
I
i
i
:
i
Ii
Ii
Weight (kg)
Output (kg h- 1)
._.*
T
MTIOO
MT250
1200
300
500
110
lOG-2oo
2000
700
MT400
2800
1200
900
1100
1300
2000
60(}-1000 150G-25oo
660
13
661
A
or
I coolpr
rolar
YClIVPS
Fig. 13.82 Granulate discharge and cooling units. A, Suction conveying unit;
B, pressure feed unit.
662
altering the rotary valve speed to match the momentary output of the
compounding line. Each of the suction conveying pipes contains a
butterfly valve for adjustment of optimal air conditions in the
conveying pipe and cooling chamber.
The alternative design (Fig. 13.82(B is similar to the first, except
that there are no mechanically moved parts (rotary valves) in the
cooler. Here again, the pellets are collected in a casing as they leave
the pelletiser. They are then blown by a fan directly into the cooling
chamber through a pipe attached to the casing (pneumatic 'push'
conveying). The conveying air escapes to the atmosphere through an
oversized pipe capped by a filter basket. A second fan blows cooling
air into the cylindrical cooling chamber up through the perforated,
conical base. Because the air velocity and pressure in the cooling
chamber are lower than those of the conveying air in the pipe, cooling
air cannot penetrate the pipe projecting into the cooling chamber. The
cooling air also escapes through the exhaust air nozzle at the top of the
cooler. A butterfly valve is provided to permit adjustment of the air
flow so that the pellets are kept in a state of gradually sinking
suspension. The cooled pellets leave the cooler through an adjustable
slide valve at the bottom.
Two other pellet cooler designs are shown in Fig. 13.83. Both are
chute conveyors employing the ftuidised bed principle, and both use a
cyclone separator ahead of the cooler to isolate the pellets from the
conveying air, a rotary metering valve at the bottom of the cyclone,
and adjustable diverter plates over which the pellets pass on their way
to the chute. The two designs differ in the mechanism employed to
obtain forward movement of the pellets in the chute.
In the version shown in Fig. 13.83(B), the chute, which has a finely
perforated sheet-metal base, is mounted on elastic vibration elements
(such as vibration mounts or helical springs): it thus functions as a
vibrating chute conveyor (here actuated by an eccentric motor) in
which the pellets are moved forward by micro-propulsion under both
horizontal and vertical acceleration, being whirled periodically upward
from the bottom of the chute in parabolic trajectories whose size and
shape depend upon the frequency and amplitude of the drive.
A fan connected by a pipe to the top of the chute conveyor draws
cooling air up through the perforated base, at right angles to the
conveying direction. Because the air flows over the entire surface of
each individual pellet, an intensive cooling effect is achieved. Pellet
residence time on the chute is adjustable over a broad range by
changing the chute's inclination or altering the amplitude of the
13
tr~,,
edlausl
OJr
~1~15
from
663
-"""""'........_b...1
~1~lo~r
cool~d
p~II~ls
~xhousl
OJr
~II~IS
from
~n~los~r
. ._-- -.......
8
coolong OJr
fan
Kcenlroc molor
I oor fan
Fig. 13.83 Horizontal granulate cooling units with: A, feeding system using
pulsation of air; B, feeding system using mechanical vibrations.
w.
664
eccentric motor. The rate of cooling is regulated by varying the air flow
in conjunction with the pellet residence time. The pellet temperatures
normally achieved are some 5 to 10C above the ambient air
temperature.
In the Biihler-Miag design shown in Fig. 13.83(A), the pellets are
moved along the chute by means of pulsating cooling air, which is
blown into the chute by a fan, through a finely perforated base plate.
A pulsator in the form of a butterfly valve (driven by a variable-speed
motor) in the intake duct between the fan and the perforated base
produces an intermittent air flow that moves the pellets along the
chute. The cooling air leaves the chute through an oversized exhaust
pipe. Pellet residence time can be varied by altering chute inclination
or pulsation rate.
13.5.2 Pellet Mixing and Storage
The mixing of pellets with different characteristics or the homogenisation of pellets of a given type from different production batches calls
for large containers with useful capacities up to 1000 m3 .
Note: Another type of mixer, not included in Fig. 13.84, is the pure
gravity mixer: the bulk material is withdrawn simultaneously
from various levels of the mixing silo and fed to a common
chamber, or else silo cells formed by vertical partitions are
filled successively and then simultaneously emptied. These
mixers, which require no energy input, cannot produce an
ideal (random) mixture but are adequate for certain purposes.
Mechanical mixers such as the orbiting vertical screw mixer (Fig.
13.85) are built with useful volumes as large as 75 to 80 m3 . This type
of mixer has a hopper-shaped container with a screw set parallel to the
hopper wall. The screw is supported at the bottom of the hopper and is
13
665
10000
1000
~
01
C
15
L-
a.o
10
L-
.
0.1
10lXlO
Capacity
m3
driven by a crank arm at the top so that it both rotates and circles the
inner wall of the hopper simultaneously. (In the epicycloidal mixer, the
screw describes an epicyclic curve between the hopper wall and centre
instead of travelling in a circle around the periphery.) The PVC pellets
are carried upward by the screw to reach ever higher levels within the
hopper.
Double-cone mixers are built with capacities as high as 100 m3 . So
are vertical screw silo mixers of the type shown in Fig. 13.86.
In vertical screw silo mixers, the pellets are raised to the upper part
of the silo by a screw conveyor in the central pipe. Spreader arms
distribute the material evenly over the silo cross-section. The material
then proceeds to move downward in the silo, at a rate which is a
function of the conveying rate of the screw in the bottom part. A
hopper-shaped insert divides the pellets as they slide downward.
Ultimately they pass through the outer and inner annular spaces to the
bottom of the screw and are raised once again.
666
P4!'II4!'llnl4!'1
from P4!'1l4!'1 cool4!'r
US4!'fui capacIty
Standard siz4!'s
0.05 to 30m 3
SP4!'cial SIZes
75 to 80m3
OrIY4!' rohng
1.51010 kW/m 3
- To sloraQ4!'
- To shipping
PNEUMATIC MIXERS
667
P~Il~1 Inl~1
from
~II~I cool~r
S~od~r
U~ful
arms
copaclly
) 10 100m)
C~nlrol lub~
wllh
conv~y,ng scr~w
Orov~
roling
0.5 10 2kW/m)
Hopp~r-shop~
Ins~1 tor
dIvIdIng flow
01 ~1I~ts
Homo~nis~d
p~Il~IS
Fine bulk materials with particle sizes between about 30 and 200 J.lm
can be homogenised very economically in fluidised-bed silo mixers of
the kind originally developed for the cement industry, in which the
mixing process depends on different degrees of aeration of (different
rate of air supply to) different sections of the base of the silo. The main
design parameter is the fluidisation line. If a fluidised bed is aerated at
an air velocity above the point of incipient fluidisation, the bed
expands. The base of the silo mixer is designed to permit individual
sections to be aerated more strongly (or 'actively') than other
('inactive') sections. This causes the bulk material above the actively
aerated sections to expand and rise higher in the silo, so that it flows
down onto the material in the inactive sections. The material in the
w.
668
Filtt'r
".
USt'ful capacIty
up to 1000m)
and lar9t'r
...
,,
"'
:
'
II
,,
,
U
,
, .,
,.
,
I.
,
I
Circular a,r
Intakt' channt'ls
A,r
inactivt'
aCllvt'
bottom of the 'inactive columns' also tends to flow into the actively
aerated sections, because the actively fluidised 'columns' have lower
bulk density. The resulting circulation produces mixing, which can be
promoted by activating and de-activating a given section at regular
intervals. Fluidised-bed mixers of this type are used for homogenising
PVC powder following polymerisation.
Because the rate of air flow required for fluidisation rises with the
square of particle size, fluidised bed mixers become uneconomical for
coarse bulk materials with particle size larger than 500 pm, including
669
Aor oullE'1
PE'IlE" InlE'1
trom pE'IIE'1 coolE'r
a
b
c
d
E'
f
g
h
51,52
R'SE'r tubE'
MIXIng hoppE'f
Milling conE'
ChokE' SE'cl,on
Fan
Mlxong hE'Od
BUIIE'rfly valvE'
BailiE' conE'
ME'tE'f1ng gop
"
".
..
b
USE'ful capacIty
up 10 1000m)
and largE'r
-O,1kW/m)
HomogE'n,sE'd
V pE'IIE'IS
670
...
....
0
l/l
l/l
'"c:
.2
a
0.
D
'0
0
a:
..
...
~
jj
c
0
iii
ii
a.
E
0
AJ
11'1
30m
Mixer height
671
CHAPTER 14
LANHAM
and W. V. TITOW
14.1 INTRODUCTION
674
Hopper
- - t -....
675
676
Fig. 14.3 Some general features of a screw and associated definitions. Depth:
the perpendicular distance from the top of the thread to the root surface.
Flight: the space enclosed by the thread and the surface of the root in one
complete turn of the screw. Helix Angle: the angle between the screw thread
and the transverse plane of the screw. Land: the surface at the radial extremity
of the screw thread constituting the periphery or outside diameter of the screw.
Lead: the horizontal distance travelled by the material in one complete
revolution of the screw, assuming 100% efficiency. It is equal to the pitch
multiplied by the number of starts. Number of starts: the number of separate
threads traced along the length of the screw. Pitch: the horizontal distance
between corresponding points of two successive lands. Root: the continuous
central shaft, usually of cylindrical or conical shape.
677
678
needs to be cored for cooling. For PVC this facility should be available
along the whole length.
As mounted in place in the extruder, the screw is driven by a motor
through a set of reduction gears to ensure sufficient torsional power
and to transform the high rotational speed of the motor into the much
lower rotational speeds required of the screw. A thrust bearing at the
rear end serves to accommodate the substantial back-thrust experienced by the screw as a result of back-pressure built up in operation,
by the restricting action of the die upon the forward movement of the
melt which the screw actuates.
Screws are made of steel, and surface-hardened (most commonly by
nitriding) for increased resistance to wear and some corrosion
protection. For increased protection against corrosion in PVC
processing the screw may be chromium-plated (at least on the flights 4 ):
hard chroming will also confer some wear resistance. Other means of
increasing resistance to abrasive wear are nitrogen ion implantation (a
relatively new treatment developed in the UK at AERE, Harwell, and
now in commercial useS), or coating with special alloys (of the kind
also used for lining extruder barrels-see below).
Note: It has been claimed that a Z-Core (Z-Core Inc., Trenton, NJ,
USA) alloy coating can increase the life of screw and barrel
by a factor of 35 over that of an otherwise comparable
nitrided set in a twin-screw extruder processing PVC pipe
compound and regrind containing untreated calcium carbonate filler. 6
679
680
Qex:D 2 LhN
(1)
681
smooth, fully streamlined flow channels, free from hang-up points for
the material. Requirements are less critical in this respect with flexible
PVC compositions, and the use of crosshead dies (that turn the melt
through 900 in relation to the extruder screw axis) is quite common.
Dies may be of the fixed type, in which no adjustment of the aperture
is possible, or they may be so constructed as to allow adjustment
during extrusion. Adjustment is usually necessary on dies of annular
cross-section (e.g. for pipe or channelled profile), where it is achieved
by displacement of either the control mandrel or the outer ring (the
two elements defining the aperture-see Chapter 19, Fig. 19.8). On
flat-sheet dies the die lips are normally adjustable, in automatically
controlled lines on signal from on-line product control devices (d.
Chapter 19, Sections 19.3-19.5).
For PVC processing, especially uPVC, the walls of the die channel
must be protected against acid corrosion, e.g. by chromium plating.
(d) Heating and Cooling
In extruders used for PVC processing, barrel heating is generally
achieved by electrical resistance heaters cast into aluminium or
aluminium/bronze blocks clamped around the barrel. The blocks also
contain cast-in stainless steel tubes for circulation of cooling liquid.
Some resistance heaters still in use are insulated in ceramic material
supported in ceramic wedges.
Note: The heaters form a number of heating zones along the barrel,
with temperatures separately controlled. Fairly typically,
there may be five heating zones for a 24: 1 LID extruder, and
six for a 30: 1 LID. Heaters on the die adapter and the die
form separate heating zones.
Mains frequency induction heaters-which entail a continuous coil
round the barrel-are also occasionally encountered, but they are not
common: such heaters give very good control of temperature, but are
expensive and can fail by short-circuiting initiated by various causes.
The barrel can be cooled by passing mains water through the cooling
pipes, incorporated in the heater blocks as just mentioned, or situated
in the barrel wall under the heaters. A closed-circuit liquid system may
also be used: in this, the cooling water (or another liquid) is circulated
through the barrel-cooling pipes and any channels in the screw, and is
itself cooled by passage through a heat exchanger. 10 Air cooling, which
is also practised on some machines, is effected by blowing cold air over
the extruder barrel from blowers situated underneath.
682
683
This has already been briefly mentioned in Sections 14.2.1(a) and (b).
With many plastics materials vented extruders are used in order that
volatiles and moisture may be extracted before the melt is metered to
the die. With PVC, however, removal of moisture and voaltiles,
though relevant, is not the major consideration: venting is important
primarily in the extrusion of rigid compositions from powder blend
feeds, where its main function is to get rid of occluded air. The general
arrangement of a vented single-screw extruder is schematically shown
in Fig. 14.4: it will be seen that the screw is of the two-stage type, with
a decompression section immediately following the first metering
section. At this point the stock fills the flights of the screw only
partially, and is subjected to a vacuum applied through the venting
port. In a vented twin-screw extruder the vent may be positioned
before the compression zone. Two venting ports spaced along the
barrel are provided in some cases.
Decompression
zone
r---
684
Note: Machines with the so-called 'by-pass' venting arrangementinvolving a seal at the end of the first metering zone and a
separate channel in the barrel wall through which the melt
passes to the decompression zone-are not recommended for
use with rigid PVC. In such systems the by-pass channelling of
the melt entails the possibility of material hang-up and
consequent decomposition. Moreover, the amount of working
undergone by the material is increased, although an experimental investigation 14 indicated that the increase can be
relatively small.
GEAR PUMPS
685
COEXTRUSION
686
(i)
687
FORMULATION OF
PLATE-OUT
688
These can take various forms. Inadequate overall gelation (see Section
14.3 below) impairs the mechanical properties of the product.
Inhomogeneity of the melt arising from variation in the degree of
gelation produces corresponding differences in melt rheology, whichif sufficiently pronounced-ean be manifested as transverse undulations (in more drastic cases lines of transverse weakness) in the
product: such effects can show up, for example, as waviness in the bore
of an extruded pipe. This can take the form of a regular pattern, being
associated with release of strain (whose degree will be influenced by
melt rheology) imposed on the melt in the screw flights, and hence
related to the flight pattern. Given that the required degree of gelation
and homogenisation of the melt is being achieved in the process, the
pattern can be reduced or eliminated altogether by ensuring that the
die design and adjustment is fully suited to the pipe size being made
and the production rate (d. Chapter 19, Section 19.3.2).
Fine porosity may sometimes appear in the extruded product even
with adequate venting of the machine: this is usually caused by the
screw speed being too high, which can cause either some decomposition of the polymer (or of an additive) due to excessive shear, or
incomplete gelation (because the material moves out of the barrel
689
690
Microgranule
(primary
particle)
size
'Approaching 1 JJrn'*
'Subrnicron'
'About 2 JJrn'
02-15 JJrn
05 JJrn
Approx. 1 JJrn
Grain (aggregate
particle)
size
About 100-500 JJrn*
50-250 JJffi
100-150 JJrn
100 JJrn
100 JJrn
Approx. 200-300 JJrn
Type of
polymer
Author
Mass
Suspension
Suspension
Unspecified
Suspension
Suspension
Marks29
ChartofPO
Surnrners et al. 31
Parey and Menges 32
Menges et al. 33
Benjamin34
691
692
693
694
695
696
This lower density of molecular ties is also the main factor in the
lower weathering resistance: photochemical disruption by incident UV
light of a number of these, even though small in absolute terms can,
because of their relative scarcity, cause cracking at the inter-grain
boundary under, say, normal thermal stresses.
As with PVC paste products, the relatively sophisticated methods of
morphological study are too time-consuming and elaborate to be
widely used in monitoring the completeness of gelation in industrial
operations. It is largely for this reason that more straightforward,
direct determination of some property of the product, influenced (like
some of those just mentioned) by the degree of completeness of fusion,
is usually resorted to. Whilst such determinations have the merit of
relative simplicity-and the property determined may be directly
relevant to service requirements (e.g. the hoop strength of extruded
pipe, which is sensitive to the completeness of gelation)-the
functional relationships of their numerical results to the fine structure
of the product are not normally linear. Thus such results are only
relative indices of the degree of gelation, and-whilst each may be
satisfactory for a particular purpose-they are not readily quantitatively relatable to one another. This is well brought out in the results
obtained in a study by Benjamin34 of the degree of gelation of an
extruded pipe of a relatively simple formulation. Benjamin's data are
reproduced in Table 14.1.
For practical purposes the completeness of gelation of extruded
products (pipe, profile) is usually assessed in terms of a solvent
immersion test (ct. Chapter 19, Sections 19.3.3 and 19.4.4), or a
strength or impact test.
A rheological method, giving numerical values for the degree of
gelation, has been developed,32,34,51 foreshadowed by ideas of Gonze 52
and Lamberty.53 With a series of melt-flow determinations in a
capillary rheometer (a standard melt-flow index apparatus may be used
697
TABLE 14.1
32
44
68
90
Resistance to attack by
methylene chioride b
Severe
attack
Light
attack
No
attack
No
attack
Homogeneity
of microtome section C
Inhomogeneous
Some
inhomogeneity
Homogeneous
Homogeneous
54
108
55
133
56
115
56
58
381
3
624
15
706
15
763
19
711
16
733
18
656
12
697
16
Resistance to stress
cracking' 20C
Critical strain, Ec(%)
08
15
51
3-6
698
corresponds to 100% gelation, the gelation level similarly corresponding to the result obtained with the specimen in its original state can be
calculated.
699
of screw (at the lower end of the compression range quoted) had also
been used for uPVC. Subsequently metering screws with mixing rings
fitted in the metering section came to be employed,S7 and thereafter
many variants of 'mixing' screws which may be broadly classified into
three groups: screws containing 'smearing' sections designed to
improve homogenisation of the stock; 'pin screws' with lines of pins in
the metering section9 designed to break up the flow pattern of the
stock for better homogenisation; twin-channel screws in which the
material already melting is periodically temporarily separated ('drained
away') from that still predominantly solid, for more effective working
of the latter and generally better overall homogenisation. Sophisticated
designs of the last-named type are represented by the 'barrier' screw, *
and the 'double-wave' screw;t the latter is claimed to be more efficient
than pin-type screws, to operate effectively with stock temperatures
significantly lower than those typical of a conventional single-screw
machine, and to make the single-screw extruder competitive with a
twin-screw one in the extrusion of pipe from dry blend. 58 Among the
other developments in single-screw extruder features (some already
mentioned in Section 14.2 above) the following should be mentioned:
increase of barrel length, screw speeds and torques; low noise level
drives; improvements in power transmission; increase in heat output of
barrel heaters. Some modern single-screw machines are among those
discussed in Sections 13.4.2 and 13.4.4 of Chapter 13.
700
701
stock temperature in the screw flight prior to complete homogenisation: the material is coolest in the centre of the flight and-particularly
in the absence of the kind of special mixing arrangements mentioned
above-that part fuses last. Relatively high screw speed is necessary to
promote uniformity of temperature distribution by the resultant high
shear, but this also generates considerable shear heating making it
necessary, in some cases, to run the machine with cooling constantly
on to keep the temperature to a safe level. The twin-screw extruders
produce much less in the way of shear heating and rely more on the
input of heat from the barrel. Single-screw machines are dependentparticularly for any mixing action-on the development of relatively
high back-pressures. Hence, since they have no positive pumping
action, with die openings of large cross-sectional area the achievement
of such pressures may be difficult: also in practice-for a given screw
speed-the output tends to decrease with decreasing die opening. The
performance of the twin-screw machine is little affected by the
cross-sectional area of the die.
With reference to the above points, and generally to its performance
and operation in PVC (and especially upvq processing, the
advantages of a twin-screw machine in comparison with a single-screw
one may be listed as follows:
(i)
(ii)
These three features are consequent upon the positive pumping action
of the screws.
(iv)
(v)
These two points arise from the generally lower melt temperature in
processing.
(vi) better temperature control;
(vii) better mixing action and removal of entrapped air (hence
greater suitability for processing bulky feeds like dry blends);
(viii) insensitivity to the cross-sectional area of die opening in
operation.
702
AGM
Anger APM
Kesterman
LMP
Nouvelle
Mapre
Schloemann
Windsor
Screw
rotation
Type of screws
703
Manufacturer
S;T;M
S;T
Loreburn Engineering
Ltd, Sheffield
S;T;M;
cascade
General type
of machineO
Battenfeld (England)
Ltd, Chesham, Bucks
UK associate or
agent
Remarks
~40
Range of
screw sizes
(mm)
TABLE 14.3
Some Commercial Extrusion Equipment Widely Used for PVC Processing
~20
50-250
Range of general-purpose
PVC extruders and downstream equipment
Special gear-box design for high
screw torque performance
Incorporates former Anton
Anger operation; single- and
twin-screw (conical) extruders with dual-circuit screw
temperature control; downstream equipment and complete lines
Inter alia, supplies a complete,
compact twin-screw line for
the production of PVC window profiles (continuous
output up to 130 kg h- 1)
Extruder range, and complete
lines for sheet extrusion,
cable and wire covering, and
compounding
60-120
S
T
60-100
50-90
S
T
~70
52-132
~40
~20
706
Plate G Mapre twin-screw extruder Type E2.78.100: screw diameter 100 mm;
two models available, with LID ratios respectively 22:1 and 16:1. (Courtesy
Mr David Dryburgh-D. Dryburgh & Co Ltd., Epsom, Surrey, England.)
707
Map/an DS 80
Map/an DS 100
80
24: 1
16--315
2 x 4000
13-26
250-300
24: 1
16--32
2 x 7500
26--52
400-500
100
708
TABLE 14.4
Bitmder BT 7012-8016V Twin Screw Extruder: Some Technical Data for this
Model and for a Reifenhauser Window Profile Extrusion Line Based upon It
(Extracted, with the permission of A. Reifenhauser Ltd, from the technical
literature of Reifenhauser GmbH, Troisdorf, West Germany)
Technical and output data for Bitruder BT 70I280-I6V
Screw
diameter
length
(D, mm)
(D)
Nominal
torque
(daNm)
700
16
81
Drive
rating
(kW)
Screw
speed
range
(rmin- I )
Sections
42-250
52-310
220
160
Compressed
air with
supply
pressure
5-6 bar
(Nm3 h- 1 )
Net
weight
(kg)
BT701-2-80-16V
KKE-P0500-15-V3
A-P420D-2-175L
TSQ-P516A-220-450
ST-P710-00-300
Total
Description
Feed hopper
Twin-screw extruder
type 'Bitruder'
Temperature con
troller cabinet,
8 controllers
Profile die head
and sizing
Sizing unit base
with vacuum sizing
tank
Haul-off unit
Length cutting saw
with swarf
extraction
Discharge unit
Rail track
Installed
electric
rating
(kW)
Cooling water
consumption
with supply
water
12-I5C
(Nm 3 h- 1 )
700
05-08
10
3800
250
45
230
240
25-30
30
30
104"
30-38
2400
03
03-09
1800
520
01-03
450
250
07-1'2
9720
"The effective consumption for drives is up to approx. 75% and for heaters approx. 30% of the
installed rating.
Screw diameter
Length/diameter ratio
Number of heating zones
Total heating load
Cooling system
Barrel zones (optional)
Individual blowers rated at
Feed section
Gear ratio
Gear type
Lubrication
Thrust bearing
Dynamic load capacity
B-10 life at 100 r rnin- 1 and
5000 lbf in- 2 head pressure
Motor power (suggested)
Screw speed
Installation area (approx.)
Extruder (excluding drive)
Control cabinet
Weight (approx).
Extruder (excluding drive)
Control cabinet
Specification
S450-24
450 in
24:1
4
601 kW
Air
595 ft 3 min- 1
Water
10:1
Single helical
Force feed
482 000 lb
56 000 h
1OQ-150hp
Up to 125 r min- 1
184 x 33 in
47 x 22 in
7900lb
850lb
S450-20
450 in
20: 1
3
501 kW
Air
595 ft 3 min- 1
Water
10: 1
Single helical
Force feed
482000lb
56000h
100--150 hp
Up to 125 r min- 1
165 x 33 in
47 x 22in
7100lb
850lb
Imperial
3225 kg
386 kg
420 x 84cm
120 x 56 cm
56000 h
74-112 kW
Up to 125 r min- 1
219000 kg
Air
17 m3 min- 1
Water
10: 1
Single helical
Force feed
115mm
20: 1
3
501 kW
S450-20
TABLE 14.5
Melville Plastics Engineering (Scotland) Ltd 45 in Extruder
219000 kg
Air
17 m 3 min- 1
Water
10: 1
Single helical
Force feed
115mm
24:1
4
601 kW
S450-24
3590 kg
386 kg
468 x 84cm
120)( 56 cm
56000 h
74-112 kW
Up to 125 r min- 1
Metric
-.I
'J:)
I :;
"'"
i:l
'"~
'";:s
?Cl
"1:l
c'
;:s
.....
.to,
710
wire covering;
hose and flexible pipe production;
blown and cast film;
rigid pipe;
rigid sheet;
profiles, rigid and flexible.
711
712
Plate I-contd.
713
3 x 60 mesh
3 x 120 mesh
714
TABLE 14.6
eC)
Position in extruder
Type of extrusion
Hopper
end
Middle
of barrel
Head
end
110
120
130
140
125
140
140
155
135
150
150
165
Head Die
150
160
160
175
160
170
180
190
smaller the orifice so that greater heat input will be required. The
rotational speed of the screw will not yet be great enough to create an
excessive amount of heat. Higher temperatures are required on
twin-screw machines.
The cooling of the screw has to be controlled. Cooling is usually
unnecessary at the start of the extrusion since the aim is to build up
heat, not to take it away. After a time, however, a trickle of coolant in
the screw is often advantageous.
Before extrusion begins it is necessary to allow the extruder to
warm up to the required temperatures. The compound should then be
introduced gradually into the machine, the ammeter being watched
continually to ensure that the cold compound does not cause
overloading. If tubes are being made and a torpedo is in use, this may
also be capable of being heated. This is most advantageous and permits
really sensitive extrusion control, also allowing the barrel temperatures
to be kept lower than usual.
'715
Type of extrusion
eq
Position in extruder
Hopper
Head
end
Middle end Head Die
300
300
300
300
300
110
120
130
130
150
150
150
160
150
150
140
140
150
150
160
There are some noteworthy points about Table 14.7 in that they are
contrary to convention. First, in general, the temperature gradient has
virtually been eliminated. Sometimes a little extra heat is necessary
just behind the head. The die temperature, however, can be varied
quite independently of all the other heaters and this is purely to control
the surface finish. This temperature can be quite high without causing
decomposition of the compound, largely due to the high speed of
extrusion.
With slow extrusions it is necessary to heat the hard compounds
more than the soft ones. With fast extrusions the opposite is the case
since the internal heat developed with the hard grade is much greater.
Cooling almost always needs to be applied. Its application should,
however, be judicious: it is not good enough just to turn the coolant
full on. The correct flow must be found by trial and error and, once
established, should be kept fairly constant. A flow meter can and
should be installed in the line so that the rate of flow can be regulated.
The amount of heat is the prime factor which determines whether or
not a good or poor extrusion will be obtained. There are many
symptoms of poor extrusions, two of the most common being 'lumps'
in the surface, or a 'grey' background instead of a fine deep colour.
Both of these troubles are caused by external overheating, usually of
the barrel. If an extruder is stripped after obtaining lumpy extrudate,
unplasticised lumps will be found behind the screen-the trouble is this
pronounced.
The natural tendency on seeing lumps is to increase the heat to
716
717
necessary to find the best heat levels by a process of trial and error. In
doing this it should be appreciated that an increase or decrease in
temperature may achieve the desired results. These comments rarely
apply to the die (and often the head heats), which may be operated
independently of other heats to give the best finish.
14.8.3 Examples of Industrial Extrusion of Plasticised PVC
:Lcb=
14
~~
.1l'O'''~, ~
.~
""
""~
;:
""!:>.
is
:::1
;:-
;:
r-
!J:l
Fig. 14.5 A typical building-wire insulation and sheathing line. 1, Dual reel flyer pay-off for insulation or earth wire ;;;
when sheathing; 2, wire straightener; 3, rotating pay-offs for insulated core to make flat twin-sheathed cable; 4, cable
guides; 5, extruder; 6, hopper loader and colour masterbatch feeder; 7, control panel; 8, embossing unit; 9, multi-pass
capstan/cooling trough; 10, diameter control; 11, spark tester; 12, accumulator to control take-up speed; 13, high-speed
dual reel take-up; 14, stripping extruder. (Reproduced, with permission, from Ref. 9.)
~!
~-
, .."
;::J
00
719
REFERENCES
1. Anders, D. (1978). 36th ANTEC SPE Proceedings, pp. 726-31.
2. Fisher, E. G. (1964). Extrusion of Plastics, Illiffe Books Ltd, and The
Plastics Institute, London.
3. Titow, W. V. and Lanham, B. J. (1975). Reinforced Thermoplastics,
Applied Science Publishers, London.
4. Burbridge, J. (1973). In Developments in PVC Technology, (Eds J. H. L.
Henson and A. Whelan), Applied Science Publishers, London, Ch. 8.
5. Anon. (1982). Eur. Plast. News, 9(11), 3~.
6. Anon. (1982). Mod. Plast. Int., U(lO), 24.
7. McCandless, W. W. and Maddy, W. D. (1981). Plast. Technol., 27(2),
89-93.
8. Avery, D. H. and Csongor, D. (1978). 36th ANTEC SPE Proceedings, pp.
446-8.
9. Barnett, G. P. (1977). In Developments in PVC Production and
Processing, (Eds A. Whelan and J. L. Craft), Applied Science Publishers,
London, Ch. 8.
10. Grant, D. and Wilkinson, P. (1968). Plast. Polym., 36(124), 33~1.
11. Anon. (1979). Mod. Plast. Int., 9(1), 30-1.
12. Anon. (1982). Mod. Plast. Int.. 12(3), 20.
13. Anon. (1980). Plast. Technol.. 26(13). 62-4.
720
721
46. Press, J. B. (1978). 'The selection of PVC polymers, additives and fillers
and the choice of equipment to maximise output and quality and to
minimise cost,' paper presented at the PRI International Conference on
PVC Processing, Egham Hill, Surrey, England, fr-7 April, 1978.
47. Collins, E. A. and Metzger, A. P. (1970). Polym. Engng. Sci., 10, 57.
48. Logan, M. S. and Chung, C. I. (1979). Polym. Engng. Sci., 19(15),
1110-16.
49. Summers, J. W. (1981). J. Vinyl Technol., 3, 107-9.
50. Marshall, G. P. and Birch, M. W. (1982). Plast. Rubb. Process. Appln,
2(4), 369-79.
51. Parey, J. and Zajchowski, S. (1981). Plastverarbeiter, 32(6), 724-6.
52. Gonze, A. (1971). Chim. Ind., 104(4/5),422-7.
53. Lamberty, M. (1974). Plast. Mod. Elast., December, 82-9.
54. Lanham, B. J. (1969). Plast. Rubb. Wkly, (286), 10-11.
55. Martin, B. (1970). Plast. Polym., 38(134), 113-19.
56. Klein, I. and Tadmor, Z. (1969). Mod. Plast., 48(9), 16fr-70.
57. Sweetapple, L. (1968). Plast. Technol., 14(11), 75-83.
58. Anon. (1981). Plast. Techno!., 27(7), 15-17.
59. Wyman, C. E. (1975). Polym. Engng. Sci., 15(8), 60fr-11.
60. Prause, J. J. (1967). Plast. Techno!., 13(11), 41-5.
61. Prause, J. J. (1968). Plast. Technol., 14(2),29-33.
62. Prause, J. J. (1968). Plast. Technol., 14(3), 52-7.
63. Jewmenow, S. D. and Kim, W. S. (1973). Plaste u. Kaut. 20, 356.
64. Kim. W. S.,Statschkow, W. W. and Jewmenow, S. D. (1973). Plasteu. Kaut.,
20,696.
65. Korney, A. F. Jr. (1969). SPE J., 25(7),27-9; 25(9), 28-31.
66. Kramer, A. (1969). Kunststoffe, 59(7),409-16.
67. Anon. (1967). Brit. Plast., 40(12), 57-61.
68. Carley, J. F., Endo, T. and Krantz, W. B. (1978). 36th ANTEC SPE,
Proceedings, pp. 453-61.
69. Fenner, R. T. and Nadiri, F. (1979). Polym. Engng. Sci., 19(3),203-10.
70. Burton, V. A. C. and Clarke, J. J. (1978). 'Cable extrusion machinery for
PVC', paper presented at the PRI International Conference on PVC
Processing, Egham Hill, Surrey, England, fr-7 April, 1978.
71. Anon. (1979). Mod. Plast. Int., 9(1),20.
CHAPTER 15
15.1 INTRODUCTION
Injection moulding is a commonly operated melt process, more
extensively applied to thermoplastics other than PVC than to PVC
itself, chiefly because of two inherent features especially appertaining
to the unplasticised PVC compounds. These features are thermal
instability and high melt viscosity, both of which create situations
which those responsible for the process must anticipate and control
carefully. There is little doubt that as moulding technology improves
and as the position with regard to VCM becomes less hazardous the
injection moulding of PVC will extend.
Injection moulding is a cyclic process in which precision in repetition
yields significant applicational, economic and quality returns. The
procedure by which an injection machine is used to produce adequate
components can best be envisaged in distinct stages: feeding the melting
cylinder with compound; preparing plastic melt by thermal and
mechanical effects; forcing the melt from the melting cylinder into the
mould; cooling the contents of the mould; finally emptying the mould.
While post-ejection processes may need to be applied-jigging,
trimming, decorating, assembling, cementing-these will not be dealt
with here. The two features that have been emphasised above as being
particularly significant with PVC, are especially so during melt
preparation and mould filling. For this reason attention will be largely
devoted to the behaviour of PVC in these two stages of the overall
cycle of operations. It is here that the plastic melt reaches its maximum
temperature and is forced to flow through restricting features such as
cylinder nozzle, sprue, runners and gates.
723
724
L. W. Turner
725
230
220
V.
210
''"-
::J
,"200
'-
'"
a.
E
~190
180
lima,s
726
L. W. Turner
integration of a series of temperature-time steps which vary continuously as the plastic material proceeds from hopper to mould entry.
Shear-work, dissipated as thermal energy, raising the melt temperature, takes place in the melt in the forward zones of the screw and
barrel, in the nozzle, and finally in the gate. Thermal conductivity is
poor, and non-homogeneous build-up of temperature will occur. Poor
streamlining in the nozzle-to-gate region can exacerbate the situation
by causing local stagnation of flow, which adds seriously to the time
component of the thermal input.
The rheological behaviour of PVC2 is important in relation to
injection moulding because melt preparation usually involves an
extrusion screw and barrel arrangement. Melting and flow behaviour
during this heating process and flow during the moulding operation are
dependent on the rheology, which in turn depends on the composition,
i.e. the PVC polymer and the additives employed. Shear-work is
another feature dependent upon composition via slip and flow
behaviour.
15.2.1 Moulding Compounds
* e.g. Geon 110 x 346 (B. F. Goodrich); Ethyl 7042 (Ethyl Corp.).
727
728
L. W. Turner
729
730
L. W. Turner
731
732
L. W. Turner
l'S:l
20:1
2S: 1
G-1000 0-400 G-100
2G-100 2G-80 2G-SO
30: 1
G-SO
2G-30
15
733
Temperature settings
eC)
General-purpose easy
flow, high-impact
Pipe-fitting compound
(Type 1)
Universal pipe-fitting
compound (Type 1/2)
See Section 15.5.
Nozzle
heater
Melt
temperature
(0C)
Rear
(feed
section)
Middle
Front
135
160
170
170-175
200-210
140
155
170
170-175
190-200
145
160
175
175-180
200-205
734
L. W. Turner
15.4.1
The rate of injection should be the optimum for rapid, complete filling
of the mould, but consistent with avoidance of decomposition (first
manifested in the appearance of discoloration at and near the gate
point-d. Section 15.6) through excessive frictional heating.
Note: If the injection rate is reduced too far, weak weld lines, sink
marks, or even short shots may result. When the characteristic
signs of decomposition appear at a generally reasonable
injection rate, consideration should be given to enlarging (and
streamlining) at points where melt flow may be unduly
restricted (nozzle orifice, sprue, runners, gate). As a general
principle, automatic adjustment of injection rate (via a
closed-loop control arrangement) is highly desirable.
735
PVC and the acetal resins (e.g. Delrin-Du Pont; HostaformHoechst; Kematal-Amcel UK; Celcon-Amcel USA) interact strong-
736
L. W. Turner
ly at elevated temperatures, with resultant vigorous mutual degradation. The two materials should on no account be allowed to come
together in plastics processing equipment (injection-moulding
machines, extruders, melt-compounding mixers, etc.). It is highly
preferable that the same machine should not be used for the
processing-especially consecutive processing-of these materials: at
the very least extremely thorough purging must be carried out (with a
suitable purging compound-see above) before a change-over.
Two brief general summaries of considerations important in the
moulding of uPVC have been published recently by Whelan,13 and
Murrey and Dito. 14
15.5 MATERIALS AND APPLICATIONS
It should be obvious from what has been said concerning the rather
737
L. W. Turner
738
position (feeding the stock through a gap between the screw tip and
the rear face of the nozzle); provision for adjustment of the size of this
gap (where the main working of the material to produce plastication is
effected through the shear imparted) to regulate the amount of shear;
special provisions for screw and barrel cooling; and overall control of
temperatures and pressures.
The process is claimed to be particularly suited to heat-sensitive
materials such as PVc.
15.6 TROUBLE-SHOOTING
Many processing and material factors have to be balanced in order to
achieve high outputs of good quality mouldings. Achieving an
acceptable balance can sometimes be a difficult task requiring
experience and skill. Two principles are here emphasised: good
knowledge of the material concerned (this is perhaps more important
with PVC compounds than with any other thermoplastic) and use of
such control aids as the equipment can provide.
Three groups of considerations which arise in aiming at continuous
in-balance quality mouldings are distinguished below. They relate to
machine selection; to those processing features pertaining more
specifically to PVC; and to those features which are of general
significance in injection moulding of thermoplastics.
739
TABLE 15.2
Observation
1. Splay marks or
silvery streaks
emanating from
the gate position
2. Dark centre to
sprue or internally in gate area
Significance
May be due to condensed moisture
but, more important, could be initial signs of decomposition due
to thermal input
increased above
acceptable level
Progressive overheating of material
(sometimes associated with hot spot
at screw tip)
4. More prominent
areas of darkened
material on sprue
surface often extending from sprue
into the moulding
Some decomposition
of material due to
overheating
High shear or
stagnation in this
region
6. Dark decomposition
Local 'burning'
Adjustment
Choice of reduction of forward band heater settings (especially nozzle
temperature), screw
speed, back-pressure,
filling rate, singly or in
various combinations
740
L. W. Turner
REFERENCES
1. Tulley, F. T. and Harris, B. C. (1979). In Encyclopedia of PVC, (Ed. L. I.
741
CHAPTER 16
16.1 INTRODUCTION
Sheet thermoforming has been described as the one method whose
development sprang uniquely from plastics technological history and
was not picked up from metallurgy. This contrasts with the case of such
solid-phase forming processes as forging, stamping, and certain others,
originally developed for metals and only relatively recently explored in
the plastics context. 1 Now super-plastic metals technology has taken up
the sheet-forming idea from the plastics industry. Plastic sheet
thermoforming is a secondary process, depending on, as primary
process, sheet extrusion to supply its starting material. In fact it is well
to bear in mind that extruded forms other than sheet (e.g. tubes), or
sheet produced by methods other than extrusion (e.g. cast as is PMMA
sheet, or laminated) can be thermoformed. It was in the early
Celluloid or Xylonite days of the plastics industry that methods of
shaping various sheet, rod or tube forms first came into industrial use.
For PVC it is largely the forming of extruded and calendered sheet that
must be considered.
Additionally, though, there are combination processes which start by
converting granules to a dimensioned pre-form of planar solid sheet
geometry and then form this into a 'drawn' article (the 'Topformer,2,3
process for example). .
There are three basic methods of sheet thermoforming:
(i) vacuum forming;
(ii) pressure forming;
(iii) matched-mould forming.
743
744
L. W. Turner
pvc
745
746
L. W. Turner
pvc
747
Stoge I
Key
Heeter
B Clomping frome
C Plostics moteriol
o Former
E Gosket
F Vocuum box
G Pressure line
H Vocuum line
A
has been made. As in method (b) the temperature of the mould and
speed of ascent or descent is important. Speed is also essential in the
rate of air evacuation.
(d) Bubble Forming (Fig. 16.4)
In this method the sheet is heated, clamped over the vacuum box and a
specific air pressure applied to blow it into a bubble. A shaped male
plug is then forced into the bubble and vacuum is applied in the usual
way.
748
L. W. Turner
DT-.....IIIIIIIil_~iLE
'r-rSloge I
Stege 2
C-
c:..
Sloge 3
A
B
C
D
E
F
G
Heater
Plug
Plastics material
Clamping frame
Gasket
Former
Vacuum box
Stoge 4
Key
H Air inlet
I Air outlet
J Vacuum line
Stage 1 - Heater placed over sheet
Stage 2 - Plug partly down
Stage 3 - Plug fully down - no vacuum
Stage 4 - Vacuum applied
pvc
749
Stage 2
Key
A Heater
B Clamping frame
C
o
E
F
G
H
I
Plastics material
Gaskets
Former
Vacuum box
Air inlet
Air outlet
Vacuum pipe
750
L. W. Turner
Steg. 2
A
B
C
D
E
F
G
Heater
Clamping frame
Plastics material
Gaskets
Former
Vacuum box
Air inlet
Key
H Air outlet
I Vacuum pipe
Stage 1 - Heater over sheet
Stage 2 - Bubble blown
Stage 3 - Drape up, no vacuum
Stage 4 - Vacuum applied
pvc
751
or mould then enters this from above until it seals onto the sheet. The
vacuum is then released on the box side and applied to the male plug
side and the sheet 'snaps back' onto the mould.
752
L. W. Turner
700
..
o
c
i.,. 400
c
o
iii
20'Cl!:--=--~~-----:-'----""""o:---~""""-_--:-:!
ioo
/10
120
130
140
150
Temperature,OC
Fig. 16.5 Variation of elongation at break with temperature.
pvc
753
754
L. W. Turner
process the vent holes can be made by inserting wires into the wooden
pattern.
With large male moulds, particularly where large production runs
are involved, it may be necessary to have some method of cooling. The
mould is then cored for water circulation. Walls can never be exactly
upright; all must have a draft with a minimum of 3, a larger one giving
a better product. The radii should be as large as possible, certainly at
least the thickness of the material being moulded.
As with many moulding processes undercuts should preferably be
avoided. However, the comparatively simple moulds allow removable
parts to be used so that undercuts can be included. Inserts can easily be
incorporated in the mould surface and so can embossed lettering on
the surface.
In the case of large runs it is clearly preferable to trim the article in
the mould to avoid a subsequent deflashing process. For this purpose a
cut-off is required and the mould must be metal, preferably hardened
at the cutting edges.
16.3.4 Finishing
The finishing and decoration of vacuum-formed parts is frequently
necessary. In particular, it is necessary to remove flash, which can be
done by saw, trimmers, guillotine, or male and female dies in toggle or
clicking presses. Precisely which method is chosen will depend on the
size of the object and the rate of production.
Apart from deflashing, the cutting of various shapes in the
component is frequently necessary. It is advisable to employ .jigs for
such purposes to guarantee accuracy and speed up production; low- or
high-speed routers can be used for the cutting.
Other finishing operations are often necessary. Various parts have
often to be joined together; if high-frequency welding is not possible
(see Chapter 20) then parts have to be joined by adhesives. These may
simply consist of polymer solutions (in, say, cyclohexanone) or some of
the many proprietary adhesives available today (see Chapter 20). Some
impact adhesives may well be necessary if dissimilar materials are used.
Another type of finishing operation is the folding of edges, e.g. in
containers which have to receive a sliding top; for this purpose it is
possible to obtain heated folding or bending machines.
Decoration sometimes presents problems, but there is no problem in
decorating the finished object by masking and spraying or vacuum-
pvc
755
756
L. W. Turner
pvc
757
* e.g. the Shelley 'Linear Series' (M. L. Shelley and Partners Ltd, Huntingdon
in the UK, and Deacon North America, Bristol, cr in the USA).
TABLE 16.1
Engineering Developments
(Farnborough),
Belmore Road,
Farnborough,
Hants,
GUI47NW, UK
Ridat Engineering,
Fishponds Road,
Wokingham,
Berks, UK
Technoimpex,
Hungarian Foreign Machine Ind.
Trade Co.,
PO Box 183,
Dorottya u. 6 H,
1390 Budapest 62,
Hungary
Maschinenbau Gabler,
Niels-Bohr-Ring 5a,
PO Box 1690,
D-2400 Lubeck 1,
West Germany
VTM,
Ing Rudolf Wybranietz,
435 Recklinghausen,
Hubertusstrasse 41,
Postfach 1268,
West Germany
Meaf,
Groeninx van Zoelenstraat 33
(industrieterrein) ,
Yerseke 3622,
Netherlands
759
L. W. Turner
760
optimum
Strain
l~v~1
c
.~
[Crl'Kld
Ar~a of
ruptur~
tim~
iii
Incr~sing
straining
load
(Cold)
rupture
Holes
~
o
Discoloration
degradation
Details
not
reproduced
Temperature
Fig. 16.7 Quality aspects of correlation between draw ratio and temperature
(based on Ref. 15).
pvc
761
REFERENCES
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
762
L. W. Turner
CHAPTER 17
TITOW
764
W. V. Titow
765
(especially the high density polymer), polyethylene terephthalate, certain modified acrylonitrile polymers, polypropylene, and polycarbonate. Some of these-notably HDPE and PET-eompete with uPVC in
many applications (see Section 17.4.1). A few examples of their
non-competitive uses are: HDPE petrol tanks for certain makes of
motor car, large cans and drums; PP header tanks for truck radiators;
PC baby-feed bottles.
Blow-moulded containers with composite walls made up of layers of
different materials are produced from coextruded parisons or-more
recently-eo-injection-moulded preforms. This is done to secure sets of
properties not obtainable with a single material: often the combination
of properties achieved in this way is low permeability with good
mechanical strength and stiffness. Typical examples of such composites
are HDPE with polyvinyl alcohol or with an acrylonitrile polymer (in
both cases an intermediate adhesive layer is normally also present).
PVC is not used as a component of such products.
PLASTICS
extrusion
Fig. 17.1
FEEDSTOCK
PLASTICS
FEEDSTOCK
PLASTICS
in cavity:
)
complete silJlpmg of
pretonn round mandrel
mould,
stretch and blow, 0001
MOULDED
ARTICLE
PREFORM
(CLOSE-ENDED
TUBEWrrn
FULLY FORMED
NECK)
MOULDED
(ORIENTED)
ARTICLE
blow,oool
transfer to second
(article) mould,
HOT MELT
IN CAVrrY
PREFORM
(CLOSE-ENDED
TUBE WITH FULLY
FORMED NECK)
MOULDED
ARTICLE
(article) mould,)
blOW, 0001
transfer to second
MOULDED
ARTICLE
PREFORM
transfer to second
(CLOSE-ENDED (article) mould, ) MOULDED
TUBE WITH
(ORIENTED)
stretch and blow,
FULLY FORMED
ARTICLE
0001
NECK)
enclose in mould.
blow, 0001
enclose in first
(pretonn) mould,
blow
(possibly 0001)
OPEN-ENDED
TUBE
(PARISON)
DIP (DISPLACEMEN1)
BLOW MOULDING
INJECTION
STRETCH-BLOW
MOULDING
INJECTION
BLOW MOULDING
EXTRUSION
STRETCH-BLOW
MOULDING
EXTRUSION BLOW
MOULDING
Characteristic operational elements in the main types of blow moulding process. Schematic outline.
or injection
moulding
injection
FEEDSTOCK - - +
:-:::
::l
767
W. V. Titow
768
A - Feedhopper
B - Extruder
C - ElI1ru ,on head
D
Mould buring d'stributor
E - Blower head.
Stege I - EXTRUSION
The parilon is ell1ruded
between two halfmouldl.
Stage 3 BLOWMOULDING
The blown perison
upands end Ilanans out
on tha mould ~vity wall.
Stege 2 CLOSINGIN
The parison
Is clamped into the mould.
Stege 4 EJECTION
Once cooled.
tha bonia i. immediately
ajacted from the mould.
769
W. V. Titow
770
771
systems range from relatively inexpensive, simple thickness programmers offering control at a limited number of points, adequate for
long-run production of simple blow mouldings (e.g. the Moog* system
for to-point thickness programming), to sophisticated computerised,
fully automatic systems for control at up to 50 points (e.g. the 49-point
parison programming facility of the MACa Vlt integrated microprocessor control system for extrusion blow-moulding equipment5).
Other examples are the 30-point parison programmer used on some
Bekum+ machines,6 and the Hunkar programmers (some with 32 set
points and higher). In the modern thickness programming systems
operated by microprocessors, the required thickness values at the
number of points available are pre-set on the control unit, which then
continuously automatically computes and executes the necessary
adjustments of the movable die elements. Programming capabilities
other than parison thickness control offered by some of the modern
systems include parison length control, parison stretch compensation,
parison ovalisation, and what is sometimes called 'deformable die
control'-provision for programming (through automatic control of
mutual movement of the die mandrel and bushing) for minimising the
amount of material in the pinch-off area(s) of the moulding. It is
largely self-evident that the main direct object of parison programming
is optimisation of the wall thickness and thickness distribution in the
finished moulding. The advantages this brings are two-fold: better
structure (with the attendant improvement in strength properties and
resistance to damage), and cost savings. The savings are in two
areas-reduction of the amount of material, and more effective
processing (especially easier and quicker cooling of mouldings which
contain no unnecessarily thick areas, and generally only the necessary
minimum amount of material). In an informative article (published in
1976), Hunkar7 gives, inter alia, the following figures (based on
p~rformance studies of over 800 blow-moulding machines) for the
economic gains resulting from parison thickness programming in the
* Moog Inc., Electronics and Systems Div., USA, and Moog GmbH, West
Germany: the group also supplies more advanced systems with full
microprocessor control, e.g. the Moog 40-point analog parison programmer.
t Barber-Colman Co. Industrial Instruments Div., Rockford, Ill., USA.
:\: Bekum Maschinenfabriken GmbH, Berlin, West Germany.
Hunkar Laboratories Inc., Cincinnati, OH, USA.
772
W. V. Titow
1 quart
546
158
133
1 litre
435
115
96
16-220z
223
193
298
773
774
W. V. Titow
775
comparison with otherwise similar but unstretched blow mouldingsquoted as typical include, for example, weight reduction of 20-25% on
15litre mineral water bottles produced in rigid PVC on a Bekum
BMO-4D machine,14 an average material cost saving of about 10%
with typical bottle formulations through elimination of impact
modifiers,15 and possible overall production cost savings of up to 20%,
despite the somewhat higher equipment cost of stretch-blow
moulding. 16
At the same time it should not be overlooked that stretch-blow
moulding is applicable primarily to simple, symmetrical shapes (e.g.
not to containers with handles), and that stretch-blown PVC bottles
can still be no cheaper than bottles conventionally blown in, say,
high-density polyethylene which-despite their inferiority in some
properties-may be acceptable for many applications where clarity is
not a requirement.
776
w.
V. Titow
777
* Initially marketed by Gildermeister Corpoplast GmbH: now KruppCorpoplast Maschinenbau GmbH, Hamburg. UK agent: Ritter Plastics
Machinery, Bracknell, Berks. In the USA exclusive rights held by Owens
Illinois, Toledo, Ohio.
t An early discussion of this way of increasing the efficiency of radiant heating
of polymeric materials was published by Grant and Foster. 19
778
w. v.
Titow
finished bottles); waste re-processing minimised (with injectionmoulded preforms); advantages associated with stretch-blowing (improved container properties, material and process economies). However, the costs of equipment and tooling are relatively high, and licence
fees and royalties are a factor.
Apart from the version of the Corpoplast process in which the
preforms are injection-moulded, injection blow moulding as commonly
practised is a single-stage operation. It must also, of necessity, involve
at least two stations, because the preform has to be transferred to
another mould for blowing. Indeed, the first machine designs to come
into industrial use operated on a two-station system. 1 Currently the
most popular configuration is a rotary three- or four-station arrangement: in a typical version, core rods are mounted on a turret which
indexes to the stations in turn. With a three-station turret these will be
the injection station, the blowing station, and the ejection station. A
four-station system may be set up to operate in various ways; some of
the common ones are given below.
Station 4
Station 1
Station 2
Station 3
Injection ~ Pre-blowing ~ Final blowing ------+) Stripping off the
core and ejection
Injection ~ Temperature----+ Stretch-blowing ----~ Stripping off the
conditioning *
core and ejection
) Surface decoration Stripping off the
Injection ~ Blowing
(e.g. printing)
core and ejection
* This can be useful with PVC (ct. Fig. 17.2B), but not absolutely necessary
because PVC can be cooled directly to optimum orientation temperature,
unlike PET which needs a separate 'tempering' treatment of the preform
(normally at a separate station) for greatest property improvement on
stretching, or PP which must be conditioned for stretching within a narrow
temperature range.
779
780
w.
V. Titow
781
of PVC the tail waste is torn off the preforms clamped in their moulds,
by sliding grippers. Examples of systems with automatic waste
trimming are the Hoover* Uniloy 300 CE line, the Automat Speed
3000 D and Maximat machines, and the Krupp-Kautex* KEB machine
range.
Part removal (take-off) systems: These too are largely automated,
especially in modern extrusion blow-moulding equipment. Typically,
mouldings trimmed of waste material (which may be automatically
routed to a granulator and from there to the extruder) are positively
deposited, in the required orientation, on a conveyor on which they
proceed to leak-testing, decorating or labelling, and packing.
(d) Cooling Methods
The blown article must be cooled in the mould before ejection.
Cooling is effected by circulation of a heat-exchange liquid (commonly
water and glycol) through drilled channels or milled labyrinth cavities
in the mould block. Blowing pins in extrusion blow moulding, and the
core rods in injection and dip blow moulding, are also channelled for
coolant flow.
Note: Preform temperatures prior to stretch-blowing can be controlled via the mould cooling system.
As in any moulding process, rapid cooling of the blow-moulded
article is desirabie for maximum output. However, in the interest of
product quality, the cooling should also be uniform and not so fast as
to set up stresses in the moulding. The relatively low wall thickness of
blow mouldings is conducive to quick cooling, whilst stresses arise less
readily in thin than in thick sections.
The rate of cooling of uPVC is faster than that of many other
thermoplastics (including PET and PP which, as materials of
stretch-blown bottles, compete with uPVC in some applications).
Note: The principal factor in this is uPVC's comparatively high
thermal diffusivity, which is the parameter governing the rate
of transfer of heat through a plastics material in transient (i.e.
non-steady) flow conditions, such as obtain during the cooling
*Hoover Universal, Plastics Machinery Div., Manchester, Michigan, USA.
t Automa SpA, Bologna, Italy.
t Krupp-Kautex Maschinenbau GmbH, Bonn, West Germany.
w.
782
V. Titow
x density)
783
effective heat transfer the flow should be fast and turbulent. These flow
characteristics are achieved by a combination of appropriately high
pressures in pumping the coolant through, with suitable design of the
channels.
Since the shortest practicable cooling time is desirable for increased
outputs, various methods are available of supplementing the mould
cooling with internal cooling of the moulding. Reductions of cooling
time by up to 30% are claimed for some of these. The cost of the
techniques has been a restricting factor on their industrial use,
although they are of definite practical interest, particularly in the blow
moulding of large articles which normally require long cooling dwell
times in the mould. The following internal cooling methods may be
mentioned.
Liquid nitrogen or carbon dioxide cooling: In this, N2 or CO2 is
injected into the interior of the moulding directly after normal
blowing. Vaporisation and expansion of the originally liquified gas, and
its warming to the temperature of the cavity, abstract a substantial
amount of heat from the moulding.
Chilled-air cooling: With this system, a shot of air, cooled to a low
sub-zero temperature (about -50C), is injected under pressure into
the blown article through a special insulated nozzle.
Cooling with air and water mist: In the Hunkar variant of this
method (the Hunkar ILC process)* an amount of highly compressed
air and a metered quantity of water are simultaneously injected into
the interior of the moulding. The rapid expansion of the air as it leaves
the nozzle causes sharp cooling: the atomised water freezes, and
further heat is then extracted from the moulding as the ice particles
melt and the resulting water droplets evaporate.
Air flushing: There are several embodiments of this approach to
internal cooling. In the 'Interval Blowing' systemt a minimum air
pressure is maintained inside the moulding, whilst cool, compressed air
is additionally introduced and then vented out at intervals, 'flushing out'
* Hunkar Laboratories Inc. Also relevant here: the 'Frost Air' system (Ryder
Associates, Whippany, NJ, USA).
t Battenfeld-Fischer Blastformtechnik GmbH, Lohmar, West Germany.
784
W. V. Titow
785
Lucerne, Switzerland.
786
w.
V. Titow
portion of the melt will normally flow faster), and to prevent parison
curling (outward splaying) which may occur if the outside of the tube is
colder than the inside. The flow paths and lengths must also be suitably
balanced. Multi-parison heads are available on modern extrusion
blow-moulding equipment for PVC, e.g. four-parison ones on some
Bell* and Plastimact models. A production rate of 2400 I-litre bottles
per hour is claimed for the Bell two-station machine with the
multi-parison head. 6 'Universal' die heads suitable for both PVC and
polyethylene are also available, in single- or multi-parison versions.
Resistance of working surfaces to acid corrosion is as important in
blow moulding as it is in other melt-processing of PVc. Thus the
relevant points made in the chapters on extrusion and injection
moulding also apply here. With regard to the material of moulds for
blow moulding of PVC articles (including preform moulds), good heat
transfer and wear resistance are additional considerations. An
appropriate grade of stainless steel:j: would be the first choice for its
combination of very good resistance to corrosion and wear, unless cost
(high for stainless steel moulds), and/or the highest possible thermal
conductivity, and/or light weight were paramount considerations in the
particular conditions. In such cases the alternatives would be an
aluminium alloy (for light weight and fast heat transfer), or a zinc alloy
(for similar reasons) or beryllium/copper (for high heat transfer rate
with some corrosion resistance).
The following examples illustrate something of the features and
performance of some equipment in current industrial use for the blow
moulding of PVC containers.
(b) Extrusion Blow-moulding Equipment
An example of the smaller-size, continuous-extrusion machine is the
Bekum BMO 8, the smallest unit in the BMO range. Equipped with a
50-mm (2-in), 24: I LID extruder with a capacity of 40 kg (90 lb) of
PVC per hour it can produce single containers of up to I litre, or-with
a twin head-two containers up to about 113 litre. Production in a
787
typical run, with a twin head, of 230 ml (8 oz) PVC bottles (material
weight 12 g) can be at the rate of up to 2100 bottles per hour (3,4 s
cycle: dry cycle claimed 14 s). The containers are fully de-flashed in
the machine and leave in upright position for the secondary operations
of testing, surface decoration and filling and/or packing.
The single-station machines of the Battenfeld-Fischer VKl series
range from the VK1 07 model (maximum blown container size 07 litre)
to the 30 litre VK130 model. Capable of operation with a single
extrusion head or twin heads, these machines also provide complete
in-machine trimming, and delivery in upright position for secondary
operations. A typical output for the smallest unit (with twin extrusion
heads) on 12 g PVC bottles would be about 2000 per hour.
The Automa Speed 1500 SB machine, designed primarily for PVC,
can blow mould biaxially oriented containers up to 15 litre with
single-head and up to 1 litre with twin-head extrusion. Typical output
of I-litre (32 g weight) PVC bottles in a single-cavity mould would be
480 per hour. Other machines produced by Automa (in the Speed and
Maximat ranges) produce containers between 2 and 10 litres.
Some interesting features are embodied in the fully automatic
blow-moulding line produced by Sidel* (see also Table 17.1), and in
the Krupp-Kautex KEB 2-2 unit. In the former, rotary arrangements
of 24 moulds are operated to mould and temperature-condition
preforms (produced from continuously extruded parisons) and then to
blow them into bottles. The process is run under closed-loop computer
control involving automatic monitoring and adjustment of extrusion
rate, blowing pressure, temperatures, and product wall thickness. The
KEB 2-2 machine is a two-station unit equipped for both the
conventional blow moulding and stretch-blow moulding of PVC bottles
(typically about 1 litre capacity). In the former mode of operation, twin
heads are used with two two-cavity moulds: the problems of constant
parison delivery and uniform wall thickness and temperature distribution which-as has been mentioned-ean arise in multi-head extrusion
of PVC, are overcome by the use of two extruders, each feeding one
head.
(c) 1njection Blow-moulding Equipment
Two examples of commercial equipment of this kind suitable for PVC
are the Battenfeld-Fischer FiB injection stretch-blow-moulding equip-
VK1-2ESB
BM04
BM04D
KEB 2
MSFBO 3000
MSF BO 5000
Model
Battenfeld-Fischer
Bekum
Bekum
Krupp-Kautex
Sidel (SMTP)
Sidel (SMTP)
Producer
Equipment
1
2
1
1
Number
Moulds operated
500
900
1800
500
2600
10000
TABLE 17.1
Typical Performance of Some Commercial Extrusion Stretch-blow-moulding Machines in Producing 1-litre PVC Bottlesa
--.)
:::l
ClO
ClO
789
790
W. V. Titow
791
792
w.
V. Titow
793
794
w.
V. Titow
795
Corvic D50116a
Stanclere 80C
22 phr
Paraplex G62f 28 phr
a--phenyl indole 06 phr
Kane Ace Bl2g 11 phr
Estol294h
Synthetic wax
Medium impact
1 phr
2phr
100 parts
Mel/ite 831c;d
Paraplex G62
High-clarity, high-impact
MBS
lrgawax 368;
PE wax
lOphr
12 phr
005 phr
Clear bottles
(general purpose)
ICI. K value 50. Low MW polymer for blow moulding and film production. A special grade with low 'fish-eye' level
available.
b BP Chemicals. K value 57-60. A blow-moulding resin.
C AKZO. Liquid octyltin. BPF (British Plastics Federation) and BGA (Bundesgesundheitsamt-West German Federal Health
Office) approved for food contact.
d Albright and Wilson. Liquid octylin. BPF, BGA, and FDA (US Food and Drug Administration) approved.
e Ciba-Geigy. Di-n-octyltin bis(2-ethylhexyl thioglycolate) with 25% epoxidised soyabean oil.
f Rohm and Haas. Epoxidised soyabean oil (high MW grade). BPF approved.
g Kanegafuchi Chemical Industry Co.
h Joseph Crosfield and Sons Ltd, Warrington, Lancs.
; Ciba-Geigy. Composite lubricant for blow-moulding applications.
Impact modifier
Lubricants
PVC polymer
(suspension type)
Stabilisers
Formulation
components
TABLE 17.2
Examples of Basic Outline Formulations for Bottle Compounds
:::'!
0'
:0:::
-.J
797
bottles of various kinds, but wide-mouthed jars and the like are also
blow-moulded and find diverse applications in the packaging of some
foodstuffs (e.g. dried vegetables, syrup, honey), cosmetics and
toiletries (e.g. creams and ointments), small hardware items (e.g. nails,
screws) and others.
Large-scale application areas of PVC bottles comprise their use for
packaging consumable liquids (including fruit squashes, edible oils,
vinegar, cheaper varieties of table wine, mineral and natural spring
water, and carbonated drinks), liquids for household use (detergents,
bleaches, disinfectants, cleaners), cosmetics and toiletries (e.g. lotions,
oils, shampoos and other hair-care preparations, liquid soaps), and
pharmaceuticals.
In several of these outlets PVC competes with polyethylene
terephthalate (e.g. bottles for carbonated drinks, edible oil, some
cosmetics and toiletries), polyethylene (e.g. detergent and other
household liquid bottles, bottles for pharmaceuticals), polypropylene
(bottles for household liquids, some toiletries and pharmaceuticalse.g. mouthwash), and modified polyacrylonitrile (applications in which
barrier properties are of particular importance).
As an illustrative example, it may be mentioned that the consumption of uPVC for the production of blow-moulded containers in France
in 1972 and 1973 was reported 28 as, respectively, 110000 and 130000
metric tonnes. The main items making up the figure for the former
year were stated28 to be bottles for still mineral water (70000 tonnes),
for cooking oil (17000), for table wine (14000), for vinegar (3000), for
cosmetics (2000), and miscellaneous (1000).
17.4.2 Properties and Tests
798
W. V. Titow
the temperature distribution within it) during moulding, and the rate
and efficiency of cooling. The former factor can affect the dimensional
conformity and strength of the article and the surface finish; in
extrusion blow moulding it is instrumental in the strength of the nip
weld (also affected by the speed of mould closure, shape of the nipping
edges, and the blowing time and pressure). The cooling factor can also
influence the strength and dimensions.
Two properties normally monitored in the course of routine quality
control in production are the integrity (freedom from leaks) and wall
thickness of containers. Microprocessor-operated leak detectors are
available from several suppliers for on- or off-line use, in some cases as
part of the regular blow-moulding equipment (e.g. with Bekum or
Battenfeld-Fischer machines). A typical leak tester applies accurately
controlled air pressure to the interior of the container and measures
the rate of decay: this indicates the presence and size of any leaks.
Apparatus of this kind can also be used to test the dimensions of small
moulded orifices. An example of a fully automatic, computerised leak
tester is the BLT 1000 Leak Finder (South Bend Lathe Inc., USA 5 ),
capable of testing up to 50 containers per minute (test pressure about
Ollbf in- 2): the device can be programmed for automatic removal of
rejects from the line. Thickness gauges, working on the basis of
absorption of IR radiation, are available (e.g. from Oy G. W. Sohlberg
AB., Espoo, Finland): these can measure and record the wall thickness
of a blow-moulded container at 100 points within 2 s.
Service-related quality control tests widely performed on blowmoulded containers are those for impact resistance, resistance to
crushing, and permeability (barrier effect). Many manufacturers have
their own test specifications. ASTM test methods are also available in
the following standards: ASTM D 2463 (drop impact resistance),
ASTM D 2659 (column crush test), ASTM D 2684 (container permeability). Another ASTM standard (D 2911) lays down dimensional
tolerances for blow-moulded containers. Compatibility with the
intended contents is also sometimes determined, usually by relevant
mechanical property tests on containers before and after a prescribed
period of contact.
The above tests are normally carried out on samples of actual
production containers, although where the object is to compare or
evaluate moulding compounds the container specimens may be ones
specially produced in a prescribed design and size (e.g. the standard
750 cc Lesieur test bottle25 ). Compound property tests involved in such
799
In some versions of the drop test the height of the drop is fixed; in
others it is increased by prescribed increments until a stated percentage
(often 50%) of the drops results in failures, or-in some variants of the
method-until all specimens fail, the failure criterion being fracture or
defined damage. Both approaches are represented in ASTM D 2463
(together with a third procedure, known as the 'Bruceton staircase
method'). It may be noted that, as illustrated, for example, by Sisson's
data,25 whilst increasing the K value of the polymer (within the range
acceptable for processing) does raise somewhat the impact resistance in
a drop test, that rise is much less than one brought about by
incorporating in the composition an effective impact modifier in
suitable proportion. The design of the container is also a factor in drop
impact tests.
A non-destructive dynamic compression test of a few seconds'
duration may also be used to obtain a numerical index of the resistance
to flexure in the test conditions. With appropriate allowance for the
design, wall thickness distribution, and material of construction, the
index is claimed to be a reasonable measure of a bottle's relevant
mechanical properties, and to correlate well with the results of some
conventional destructive tests. 7
Bottles for carbonated drinks have to combine resistance to internal
pressure with a low enough permeability to CO2 to provide a
sufficiently long shelf life before 'carbonation loss' occurs. For a 2-litre
bottle in PET (a material somewhat superior to PVC in this
application) many soft-drink companies specify a carbonation-loss shelf
life of 16 weeks (with 8-12 weeks for a !-litre bottle). Biaxial
800
w. v.
Titow
18.
19.
20.
21.
22.
23.
24.
25.
26.
27.
28.
29.
30.
801
CHAPTER 18
Calendering of pvc
W. V. TITaw
18.1 INTRODUCTION
According to Griffin 1 the word 'calender' shares a common Greek
antecedent with 'roller', and the first recorded reference to calendering
appears to be a description, in an 18th century publication, of a
smoothing treatment for textile fabrics, carried out by means of
individually operated, weighted rolls. The multi-roll machine of the
general type still represented by the modern calender, was developed
for the processing of rubber around the mid-1800s.
Today, in the thermoplastics context, calendering is very much a
PVC-processing operation, in that relatively little in the way of other
thermoplastics is processed on calenders, although some thermoplastic
rubbers, certain polyurethane compositions, talc-filled polypropylene,
and ABS have been calendered into sheeting. 2 ,3 More recently
chlorinated polyethylene sheeting produced by calendering has been
finding application as roof-lining material. In this context, therefore,
calendering may be defined, in general terms, as a process whereby a
hot mass of a thermoplastic is fashioned into a continuous sheet by
passage through a system of heated rolls (the calender). The sheet may
then simply be cooled (possibly after embossing-see below) and
wound up, or it may be deposited, while still hot, on a continuous base
material (e.g. fabric, paper) fed through the appropriate part of the
calender, to form an adherent coating. A calender may also be used to
laminate together externally fed sheets: however, this kind of
operation is lamination by calender, not calendering proper.
The general thickness range for typical calendered PVC products is
803
804
W. V. Titow
18 Calendering of pvc
805
only used for special purposes, such as the production of some types of
thin rigid sheeting where the extra nip can substantially improve the
surface finish. 1 ,4
Note: Three-roll (two-nip) calenders find some use in the manufacture of PVC flooring, and sequences of two-roll (single-nip)
units are used for processing certain highly filled flooring
compositions-see Section 18.4.2(a) below.
(ij)
(i)
'
Cf3
1
(iii)
"""
(iv)
Fig. 18.1 Customary roll numbering in calenders. (i) Inverted 'V type; (ii)
inclined 'z' Jype, downstack; (iii) 'V type; (iv) three-roll offset.
806
w.
V. Titow
numbers, starting from the first roll at the feed nip and ending
with the last one at the take-off (ct. Fig. 18.1).
Another roll configuration popular with manufacturers of PVC
sheeting is the inclined Z type (cf. Fig. 18.1(ii)): this too offers a
relatively wide range of the degree of lap, as well as easy aCCtSS for
fabric coating.
Note: In principle, the 'L', inverted 'L', and 'Z' configurations are
18 Calendering of pvc
807
of thin rigid sheeting: 15 MN over the roll face of a 168-m (i.e. 66-in)
calender has been quoted as not unusual in such conditions. 1 ,2 With a
typical plasticised composition a representative range would be about
O 2-05 MN m -1. These forces actually deflect the rolls, so that-if the
deflection is not corrected or compensated for-the sheet produced can
be substantially thicker at the centre than at the edges. The rolls can be
suitably contoured (crowned) to counteract this effect on the product,
where the deflecting forces are known and remain reasonably constant.
In practice this means that roll crowning can be sufficiently effective
only over a rather limited range of compositions and processing
conditions. Outside this range the crowning will either undercom}.lensate (i.e. with deflecting forces significantly higher than those for which
the crowning was designed, the sheet will again be thicker in the
middle) or overcompensate (i. e. with deflecting forces significantly
lower than those allowed for, the sheet will get thicker towards the
edges). Systems are also available in which-to cope with a wider
range of deflecting force values-roll crowning is associated with
special arrangements for nip adjustment by a combination of lateral
and vertical movements of some of the rolls in the stack. * However,
the means of counteracting the effects of roll distortion that are the
most operationally flexible and widely used in current industrial
practice are the techniques known as roll bending and roll crossing
(sometimes also referred to as roll skewing or cross-axis roll
adjustment). A modern calender is normally equipped with facilities
for both these procedures.
Roll bending is effected by applying a hydraulic load to the roll
journal ends (extended for this purpose beyond the regular bearings);
this exerts leverage on the roll (against the bearings) which makes it
slightly concave or convex at the nip, the direction of the imparted
curvature depending on that of load application. The maximum extent
of effective compensatory crown increase or decrease with this method
is limited (typically to about 0075 mm 1 ) by the extra load that may be
safely exerted on the bearings.
Roll crossing is an angular shift of one or both rolls of a nip-forming
pair so that their axes, whilst remaining in their original horizontal
planes, are no longer parallel, but form a slight angle: this increases
the end clearance between the rolls and hence the amount of material
* e.g. the ES Profit Steering calender, developed by Wiik and Hoeglund,
Finland. s
808
w.
V. Titow
18 Calendering of pvc
809
W. V. Titow
810
Plasticiser
storage
Other additives
storage
111
1
1
Cooling mixer
......
....
Internal mixer
BussKneader
Two-roll mill
Metering
extruder/strainer
Two-roll mill
.)
feed conveyor
(with metal detector)
CALENDER
Fig. 18.2 An arrangement of the compounding and feed section of a calender
line providing two alternative material routes. A, Plasticised compound
processing route; B, rigid and semi-rigid compound processing route.
18 Calendering of pvc
811
812
W. V. Titow
18 Calendering of pvc
813
814
W. V. Titaw
Plate K Calender train (AECI Ltd Vinyl Products Division Midland Factory,
RSA-eourtesy Mr. W. B. Duncker). (1) Part of the compounding and feed
section.
18 Calendering of pvc
Plate K-contd.
815
816
W. V. Titow
Plate L Calender train: part of the cooling-roll and take-off section (AECI
Ltd Vinyl Products Division Midland Factory, RSA-eourtesy Mr W. B.
Duncker).
(b) Calendering
Several features of the calender and its operation have already been
discussed in Sections 18.2 and 18.3 above. A few further important
points should be mentioned.
As the PVC composition fed to the calender is normally already
gelled and molten, the machine's main task is to form it into a uniform
sheet of the required thickness (although the material also receives a
certain amount of mechanical working-see below). The forming is
carried out gradually, in the course of passage through the consecutive
18 Calendering of pvc
817
roll nips. Two factors actuate the passage, their operation also
governing the route the material follows through the machine (referred
to as the 'sheet path') in that they determine whether the sheet
is or is not transferred from one roll of a nip-forming pair to the other.
These factors are the material's adhesion to the roll surfaces, and the
ratio of the roll speeds at a nip, usually called the friction ratio. Unless
it is grossly over-lubricated, a hot PVC calendering compound will
adhere to a hot roll surface: the adhesion is always stronger to a matt
than to a polished surface; it also usually increases with the roll
temperature, although some compositions may be formulated to
minimise or even reverse this effect by suitable selection of the
lubricant system. Where the speeds of the nip-forming rolls are
different, the material will run on the faster roll, if both have the same
surface finish. Otherwise the effect of the finish is strongly dominant,
that is to say if one of the nip-forming rolls is polished and the other
matt, the hot sheet will tend to remain on, or transfer to, the matt roll
irrespective of differences in speed and/or temperature.
In practice the sheet path is conveniently established-and changed
where necessary-by suitable settings of roll temperatures and friction
ratios. Save in the special case of the so-called low-temperature mode
of operation (see Section 13.4.2(b) of Chapter 13) it is usual to have
the roll temperatures (as well as the speeds) going up with roll
numbers.
Note: If the sheet does not lap the last roll (e.g. roll No.4 in the
TABLE 18.1
Flexible
(opaque)
Basic formulation
PVC homopolymer resin
Stabilisers
Lubricants
Plasticiser
Processing aid
Impact modifier
Filler
Pigment
Processing conditions
High-speed mixer
Tool tip speed
Mix temperature on
discharge
Cooler mixer
Tool tip speed
Mix temperature on
discharge
Buss-Kneader
Compound temperature at
die head
Internal mixer
Discharge temperature
Two-roll mill
Roll 1 temperature
Roll 2 temperature
Calender
Roll 1 temperature
Roll 2 temperature
Roll 3 temperature
Roll 4 temperature
Stripping device
Cieneral temperature
Embossing roll
Temperature
Cooling train
Temperature
5pbw
8pbw
5 pbw (coated CaC0 3)
8pbw
TABLE 18.1-eontd.
Composition type
Rigid
(crystal clear)
Flexible
(opaque)
Sheet properties
49-60MPa
22-29MPa
206-273%
45--69 kgfmm- 1
6(}-84 kgf mm- 1
a Dumbbell
b
TABLE 18.2
Some Wustrative Features of a Laboratory Preparation of Flexible PVC
Sheeting on an Inverted 'L' Type, 61-cm (24-in) Calender Producing at
3mmin- 1
Formulation
100 phr
2 phr
3 phr
47phr
0'5phr
For 0125 mm
sheeting
For 0500 mm
sheeting
155
155
160
165
158
164
168
170
0125mm
sheeting
0500 mm
sheeting
162
164
205
194
225
250
305
300
63
63
67
68
A high molecular weight VCNA copolymer containing 2% VA; porous, easyprocessing particles; recommended for extrusion and calendering of thick sheet.
820
W. V. Titow
The hot sheet is removed from the calender bowl on which it runs after
the final nip by a stripper (pick-off) roll. Whereas formerly the use of a
single pick-off roll was quite common, in modern practice a set of rolls
is employed, in which the first stripper roll is backed by a large number
of similar rolls (see Fig. 18.3), temperature-controlled in groups of two
or more: this makes for good control over sheet thickness and for
uniform, gradual cooling, or close maintenance of temperature (with
provision for an extra heat boost by an IR heater as shown in Fig. 18.3,
or by passage over a hot drum) if the sheet is to be embossed in-line.
The fact that each side of the sheet is in contact with alternate rollers
(see Fig. 18.4) is a factor in the uniformity of temperature control. In
the common arrangement where the first pick-off roll counter-rotates
with respect to the calender roll, the stripping action takes place by
virtue of the greater peripheral speed of the stripper and the lapping of
the sheet round it (and the other rolls of the set-see Fig. 18.4).
18 Calendering of pvc
821
The running of the stripper rolls may be so regulated that the sheet
coming off the calender is stretched to a predetermined extent whilst it
is still at a temperature significantly higher than any that will be
reached in subsequent processing or in service (in conditions where
retraction of the stretch with consequent undesirable distortion is
possible). This procedure offers the following advantages. Greater
operational flexibility, in that a calender profiled, roll-loaded and set to
produce one thickness of sheet can also be used for a range of lower
thicknesses: furthermore, the lowest thickness limit is effectively
brought down below that for which the machine can be set.
Note: For example, sheet of thickness about 75 J.lIIl (a typical lower
thickness limit for calendered sheeting) would normally be
produced by stretching down a sheet calendered at a higher
thickness, say about 100 11m.
A setting of the final calender nip (the gauging nip) wider than
would be required for direct production of the sheet thickness that is
ultimately achieved by stretching, means lower distorting forces on the
rolls and somewhat less drastic working (and heating) of the material.
Calendering at greater thickness can also reduce the overall power
requirements.
Stretching of the sheet should not be allowed to cause a substantial
reduction in width, or be carried to the point of excessive uniaxial
orientation of the ultimate product: uniformity of thickness should also
be maintained. These considerations are factors which-together with
the composition of the sheet and the actual calendered thickness-limit
the extent of sensible stretch in a given situation. For suitably
formulated sheet, calendered at a thickness reasonably above the
minimum for which the machine can be set, stretching (and the
corresponding thickness reduction) by a factor of about 2 would not be
uncommon: say a sheet calendered at a nominal 280l1m might be
stretched down to 14(}-120l1m.
EMBOSSING
822
W. V. Titow
18 Calendering of pvc
T'''''
823
,....-,--------,
824
W. V. Titow
tion in the running of the train. The presence of lowtemperature strain impairs the dimensional stability of the
sheeting in any subsequent heat processing (e.g. heat
lamination) and in service. A typical example4 of a problem
that may be caused by such strain is the wrinkling or
puckering of interior car door trim produced from calendered
PVC sheeting: during its manufacture, or in subsequent use,
the temperature inside a car can reach about 80a C (or even
higher in hot countries), giving rise to these unsightly faults as
a result of the reversion of any substantial strains originally
introduced at or below such temperatures.
COOLING
18 Calendering of pvc
825
example, in the cooling section shown in Fig. 18.3, drums 1-3 might be
kept at 50C, drums 4-6 at 40C, drums 7-9 at 25C, and drums 10-12
at a temperature about 5-lOoC below ambient. As indicated in the
figure, the sheet is lapped around the drums in such a way that each of
its surfaces is alternately in contact with consecutive drum surfaces:
this promotes even, uniform cooling.
SHEET THICKNESS MEASUREMENT AND CONTROL
Note: The nature of the measurement also means that the thickness
obtained is gravimetric thickness. * For a plain sheet this is the
same as the directly measurable 'geometrical' thickness. For
an embossed sheet-where the geometrical thickness cannot
be measured because of the surface contouring produced by
the emboss-the gravimetric thickness is the appropriate one,
and it is thus particularly useful that this is what is measured
by the ~gauge.
More recently, the scanning ~gauge has been integrated into a
complete, computerised on-line control system incorporating feedback
control loops: the thickness data from the gauge are utilised by
microprocessor-based controls which automatically make continuous
adjustments to the roll-crossing and roll-bending devices to keep the
* The notional average thickness (t) which, for a given piece or section of
uniform sheet is determined by the area (A), mass (m) and density (p), in
accordance with the relationships:
m/At = p;
t = m/Ap
826
w.
V. Titow
18 Calendering of pvc
827
828
W. V. Titow
18 Calendering of pvc
829
830
W. V. Titow
Fig. 18.5 Lamination or web coating with PVC film on an inverted 'L'
calender. Schematic representation. A, Nip lamination; B, lamination, with a
squeeze roller, against calender bowl; C, in-line lamination.
18 Calendering of pvc
831
Much calendered sheeting is surface printed, whilst some largeoutlet applications (e.g. as reservoir lining, upholstery material,
luggage covering) involve welding of the sheeting (ct. Chapter 20).
Print adhesion and bond formation in welding can both be impaired by
excessive external lubrication (as can the fusion in press laminationsee Section 18.7.2 below).
The intensive working and relatively high temperatures experienced
by calendering compositions in modern high-rate production entail the
need for good heat stabilisation. This is especially important with rigid
compounds, and most particularly those used in the production of
high-clarity transparent colourless foil and sheeting for packaging
applications. For these reasons clear, rigid PVC calendering compositions (as well as some pigmented ones) are commonly stabilised with
organotin stabilisers (where relevant, ones permitted for food contact
applications) .
Barium/cadmium systems, with or without zinc, are the stabilisers
most widely used in flexible calendering compositions. The liquid
versions are of particular interest for ease of metering for compounding, and good dispersibility. However, in highly plasticised compositions a solid system may be preferable to avoid lowering the melt
viscosity. This is the current position, although the question of toxic
hazards associated with the use of cadmium compounds has been
receiving increasing attention and development effort, which has
already produced some viable (albeit still not really fully operationally
equivalent) alternative stabiliser systems (see Chapter 9, Section
9.4.3(b)).
Lead stabilisers, historically the first to be used in calendering
formulations, are no longer employed on any scale because of their
toxicity, somewhat inferior effectivity in high-speed processing, and
generally limited suitability for clear formulations.
The PVC resins used in calendering compositions are grades of
suspension or mass polymers (the latter favoured for some high-clarity
sheeting), of particle size, size distribution, porosity, and bulk density
appropriate to the requisite high-rate processing suitability, inter alia,
with regard to such features as ease and uniformity of dry flow in
metering and dispensing, ready blending with other formulation
components in high-speed mixing (including fast, uniform plasticiser
absorption), and ease of fluxing and gelation. Flexible compositions
are normally based on high K value resins (see, for example, Tables
18.1 and 18.2). This promotes good physical properties important in
832
W. V. Titow
18 Calendering of pvc
833
These are rare with good modern equipment and correct operation.
However, the following may be mentioned for the sake of completeness.
834
W. V. Titow
18 Calendering of pvc
835
836
W. V. Titow
18 Calendering of pvc
837
838
w. v.
Titow
than the top limit for direct calendering. The process is similar to
press finishing, except that only two metal plates are used, on the top
and bottom of the stack, so that the sheets forming the stack are
laminated together and the surfaces of the resulting thick sheet acquire
the desired high-quality finish. The sheets to be combined, including
the outermost ones, need not be of particularly good quality except for
uniformity of thickness, necessary for straight, parallel-faced product.
Moreover, the pressed sheet may be matt on one side and glossy on
the other-a surface finish combination not obtainable directly by
calendering. This combination can also be obtained on individual thin
sheets by press finishing.
18.7.3 Surface Treatments
(a) Printing
Much calendered sheeting is printed with decorative designs, e.g. in
the production of vinyl wall coverings, self-adhesive decorative
surface-facing sheets (including imitation veneers), vinyl shower
curtaining, etc. The methods used are mentioned in Section 20.3.5(a)
of Chapter 20. Of these, rotogravure printing (with solvent-based inks)
is the most widely used, especially for plasticised sheeting.
(b) Coating
18 Calendering of pvc
839
840
W. V. Titow
15
50
8
50
21
9 (plain-surfaced
sheet)
11 (other surfaces, or
laminated sheet)
160
250-900
14
180
21
8
Up to 400 (inclusive)
13
11 (laminated sheeting)
21
9 (single sheeting)
160
Up to 900 (inclusive)
13
35
75-250
145-159
150
Each numerical property value quoted relates to the determination method appropriate to the standard specification concerned.
Medium stiffness general-purpose single or laminated thick sheeting with plain or embossed surface (one of the eight types of sheeting
covered by the specification).
c PVC sheeting for hospital-use; production method not specified.
d The calendered sheeting covered by this specification, which also covers extruded sheeting (Type II) and cast sheeting (Type III).
Low-temperature extensibility
(%, minimum)
Extensibility after heat ageing
(%, minimum)
Thickness (JlIIl)
Tensile strength (MPa, minimum)
Elongation at break (%, minimum)
Tear strength (N mm- 1 , minimum)
Dimensional stability: change in a
linear dimension (%, maximum)
BS 3878:1982 c
(Type 1
sheetingd )
sheetin!/,)
(Type 103
BS 1763:1975
ASTM D 1593-81
BS 2739:1975
TABLE 18.3
Some Standard Property Requirements for Calendered Flexible PVC Sheeting
00
.f>.
"1:l
.....
00
MPa
MPa
Number of
failures
in test
C
Units
--
60
15
38
2000
0
45
2500
Negotiable'
70
15
Type C3
Type Cl
50
Negotiable'
38
2000
Negotiable'
Type D
BS 3757:1978"
Ibf in- 2
Ibf in- 2
Ibf in- 2
ft-Ib per in.
of notch
(Izod)
Units
70
110
7000
11 000
400000
05
Type I
66
100
5000
8500
300000
30
Type Il
Numerical value
for sheet
type b
CS201-55"
C
R scale units
TABLE 18.4
Some Standard Property Requirements for Rigid PVC Sheeting
%
%
%
%
%
%
%
%
increase
decrease
increase
decrease
increase
decrease
increase}
decrease
0
0
55
10
15
5
5
20
0
0
80
25
15
0
No delamination or disintegration in
the acetone immersion test prescribed
a Both standards are directed to rigid sheeting generally, but Types Cl, C3 and 0 of BS 3757 are specified as calendered or extruded sheets. CS 201 is a US
commercial standard.
b BS 3757: Type Cl-general-purpose sheet suitable for most applications and fabricating techniques.
Type C3--similar to Cl but with specific impact strength and possibly lower chemical resistance.
Type D-particularly suitable for deep vacuum forming.
CS 201: Type I-1:hemical resistant, normal impact resistance.
Type II-1:hemical resistant, high impact resistance.
C In BS 3757 applicable to sheet of minimum nominal thickness of 05 mm.
dIn BS 3757 applicable to sheet of minimum nominal thickness of 10 mm.
e Between supplier and purchaser.
Property retention
After immersion in 80% sulphuric acid
Change in weight (maximum)
Resistance to delamination
Property"
Standard
75
685
110
480
760
Grade V
110
685
795
Grade X
Type 2
(with PVC coating incorporating an expanded layer)
590
Type 1
(with solid PVC
coating
BS 5790:Part 1:1979
(for PVC-coated knitted fabrics)
TABLE 18.5
Some Standard Property Requirements for PVC-coated Upholstery Fabrics
40
40
300
550
Grade A
29
29
240
420
Grade B
BS 5790:Part 2:
1979 (for PVC-coated
woven fabrics)
127
114
700
109
097
700
33
400000
30
5
10
40
26
690
33
400000
30
5
26
380
33
400000
30
5
15
50
26
690
10
40
04
400000
30
5
580
26
04
300000
30
5
450
26
a Properties tested by the relevant methods of BS 3424, except for print wear, for which modified test methods are specified in both parts
of BS 5790.
b Requirements applicable to both lengthways and transverse strengths.
COn a Martindale-type abrasion apparatus, under prescribed test conditions.
w.
846
V. Titow
Specific gravity
Tensile properties:
Tensile strength
Elongation at break
Modulus at 100% elongation
Tear resistance
Brittleness temperature
Dimensional stability
Q
Test method
Volatile loss
Water extraction
ASTM D 3083
Numerical value
120
17MPa
300%
9MPa
50Nmm- 1
-30C
Linear dimensional
change Q not to
exceed 5%
Not to exceed
05% by weight
Weight loss not to
exceed 035%
690 kPa
95%
80%
90%
18 Calendering of pvc
847
REFERENCES
1. Elden, R. A. and Swan, A. D. (1971). Calendering of Plastics, Iliffe Books
and The Plastics Institute, London.
2. Stackhouse, N. (1978). 'Calendering and paste processing,' paper
presented at the PRI International Conference on PVC Processing, Egham
Hill, Surrey, England, 6-7 April, 1978.
3. Anon. (1977). Mod. Plast. Int., 7(7), 18.
4. Elden, R. A. (1977). In Developments in PVC Production and Processing-I, (Eds A. Whelan and J. A. Craft), Applied Science Publishers,
London, Ch. 10.
5. Anon. (1980). Plast. Rubb. Wkly, 13th December, p. 7 and (1981). Plast.
Rubb. Wkly, 24th January, p. 6.
6. Eighmy, G. W. (Jr) (1982). In Modern Plastics Encyclopedia 1982-1983,
pp.220-2.
7. Watkins, W. D. (1976). Plast. Engng, 32(6),23-5.
8. Private communication from Mr T. Hodgson, Storey Brothers and Co.
Ltd, Lancaster, England (1978).
9. ISO 4591-1979. Plastics-Film and sheeting-Determination of average
thickness of a sample and average thickness and yield of a roll by
gravimetric techniques (gravimetric thickness).
BS 2782: Part 6: Method 631A: 1982. Determination of gravimetric
thickness and yield of flexible sheet. (Identical with ISO 4591.)
848
10.
11.
12.
13.
14.
15.
w.
V. Titow
CHAPTER 19
LANHAM
and W. V. TITOW
19.1 INTRODUCTION
The properties, processing and applications of rigid PVC are
mentioned, in various contexts, in several parts of this book. Those
references are accessible via the Index.
In the present chapter, some salient technological and applicational
aspects of rigid PVC materials are focused more directly in a brief
review, with special reference to the most important products. The
rigid PVC compositions discussed are in fact almost exclusively
unplasticised (uPVC) materials. Although many compositions containing plasticisers in relatively low amounts might be classified as rigid
PVC on a strict, formal definition, * and could thus qualify for inclusion
here, the ways in which the presence of plasticisers affects the
properties of a PVC composition (including 'antiplasticisation' by small
proportions of plasticisers) are adequately covered in other parts of the
book (see, in particular, Chapters 5,6 and 7, and Appendix 3).
It may be noted in passing that in semi-rigid PVC compositions
(which may typically contain up to about 20-30 phr of plasticiser) the
* See Chapter 1, Section 1.1 in conjunction with ISO 472-1979 and ASTM D
883-80: both these standards define a 'rigid plastic' essentially as a plastics
material which, at a standard temperature and humidity (about 23C and 50%
RH respectively), has a modulus of elasticity (in flexure or in tension) greater
than 700 MPa (= 1Q5 Ibfin- 2). A 'semi-rigid' plastic is similarly defined as one
having a modulus of elasticity between 70 and 700 MPa (approximately
2
1Q4-1Q5 Ibfin- ). Typical modulus values for the material of main uPVC
products are given in Appendix 3.
849
850
120
DBS
11
DOA
:550
01
~40
+'
Ul
+,30
u
E
C1J
20
10
10
20
30
Fig. 19.1 Effect of some plasticisers, at low content levels, on the impact
strength of a PVC composition.
851
Powder
Pellets
Powder
Pressure pipe
Rainwater goods
Pellets
Powder
Pellets
BS 4607 Part 1}
High-impact conduit
High-impact profiles
Pellets
Powder
Form
Relevant standard
Nature
Product
--
PVC feedstock
144-146
148-152
147-149
148-152
142
148
148
146
SG
By way of non-exclusive, illustrative example. Numerous feedstock compounds available from many different sources.
Injection
moulding
Extrusion
Process
TABLE 19.1
Examples of the Uses of Some Commercial uPVC Feedstocks
'"
is
:::1
~
:0:::
;::,
l:>...
l:>
;:
l:>
;::,
;::,-
t-<
l:>
00
853
100
9
02
015
H
S or M
57
580
Injection or
blow moulding;
calendered
sheeting
995
10
05
65-67
500-550
Sb
Hb
Largediameter
pressure
pipe
100
5
02
022
He
se
66
54{)
General
extrusion
100
99
02
H
E
72
480
999
5
02
C
S
62
510
Extruded or
calendered
sheeting (for
thermoforming)
= emulsion polymer.
Battery
separators
Polymer natureD
Polymer typeD
K value (Fikentscher: DIN 53726)
Apparent density (ISO 60) (g litre-I)
Particle size (ASTM D 1705):
% below 250 /lm
% below 75 /lm
Heat IOSSd (%)
Porosity (ASTM D 2873) (cm 3 g-I)
Polymer
characteristics
Typical application
TABLE 19.2
Some Characteristics of PVC Polymers Typically Chosen for Various Applications
(Based largely on data from Ref. 2)
997
15
18
C
S
47
780
Gramophone
records;
flooring
'l:
:::1
:<::::
;:,
l:l..
l:l
l:l
::.-
;:,
l:l
t--
"""
00
U1
855
TABLE 19.3
Impact Resistance and Tensile Strength of Typical uPVC Compounds at
Different Temperatures
Temperature
Impact resistance"
(notched lzod: ft lbfin- I )
COC)
Tensile strength b
(lbfin- Z )
Normal-impact
composition
High-impact
composition
Normal-impact
composition
High-impact
composition
03
04
09
40
160
10
40
160
180
190
12200
8900
6400
4100
2300
10400
7000
5500
2900
1500
-40
25
60
82
"ASTM D 256.
b ASTM D 638.
VCNDC copolymer
(Breon CS 100/30)
VCNA copolymer
(Breon AS 70/42)
Relative
density
Specific
viscositya
K value
Impact
resistanceb
(J cm- 2 )
141
055
66
155
137
036
55
073
856
Some of these are featured in Tables 19.5 and 19.6. The following
values have also been quoted 7 for We/vic (ICI) rigid PVC moulding
material:
Specific heat at 20C: 110 J kg- 1 (oq-l
Thermal conductivity at 20C: 017Wm- 1 COq-l
Approximate total heat (moulding): 270 x 106 J m- 3
ELECfRICAL PROPERTIES
70 X 10- 5
Shore D: 85
002
5 x 10- 5
ASTM D 696
ASTM D 2240
ASTM D 570
73
77
140
6600
30
480000
11500
-
ASTM D 648
BS 2782
9500
490000
10500
139
6000
792
638
638
638
790
790
695
Injection
moulding:
general
purpose,
easY-flow b
D
D
D
D
D
D
D
Injection
moulding:
general
purposeQ
Compound type
ASTM D 256
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
Method of
determination
Relative density
Tensile strength (yield) (lbf in -Z)
Elongation at break (%)
Tensile modulus (lbfin- Z)
Flexural strength (yield) gbf in -Z)
Flexural modulus (lbf in- )
Compressive strength (lbf in-z)
Impact resistance, Izod
(notched, 1/4 in bar) (ftlbfin- 1)
Deflection temperature under
load (264lbfin- z stress) (0C)
Vicat softening point eC)
Coefficient of linear thermal
expansion (mm mm- 1 C- 1)
Hardness
Water absorption (24 h) (%)
TABLE 19.5
Some Properties of uPVC Compounds for Melt Processing
71
17
63 X 10- 5
Shore D: 75
01
134
6500
30
400000
13000
375000
Extrusion:
high-impact
(for thin-section
products)C
VI
-J
00
:::.
"'-
;:s
l::>
'"3-.
"'tl
.,
.g
j:
~
"';::
:"::.
0
~
s
~
"';::
!:;'
"
"'tl
"<:::
"'-
~:
::I:l
.....
'0
ASTM D 2863
010 (020)
38"
60
R102-R113
6G--65
R115"
ASTM D 785
40-
77-83
015"
6(}...65
017"
ASTM 696
ASTM C 177
70"
8-18
134-136
6G-70
2-30
3,2-3,9
110"
32"
188
75"
137-1-45
7G-85
2-10
35-55
135"
40"
235
ASTM D 648
792
638
638
638
790
790
High-impact
0,7-3,0
D
D
D
D
D
D
Ordinary
upvc
ASTM D 256
ASTM
ASTM
ASTM
ASTM
ASTM
ASTM
Method of
determination
Specific gravity
Tensile strength (lbfin- 2 x 10')
Elongation at break (%)
Tensile modulus (lbf in- 2 x 10")
Flexural strength (lbf in- 2 x 10')
Flexural modulus (lbf in- 2 x lOS)
Creep modulus at 1000 h" (lbf in- 2 )
005 e
50"
90
Rl18-R120
38-65
014
1OG-105
2-3
152-157
82-85
8-15
4G-55
145-160
38-43
cpvc
80
70
000 (001)
17-18
R1G-R20
11-13
033--047
43--55
3--20
0941--{)965
3G-50
2G-8oo
06--18
3G-35
1G-20
40
HDPE
12-17
O 33--0 35
32-40
no break
091--{)93
1G-20
9G--650
02--{)4
1G-20
01--{)6
-
LDPE
000 (0'01)
-18
110
R8G-R110
68-110
010--{)22
55-60
2_lOb
090--{)91
3G-50
2G--600
1G-22
5G-80
17-25
60
(copolymer)
PP
105 (140)
-20
100
R3G-R118
6G-ll0
019--034
85-105
25-120
103--107
5,5-80
5-80
2G-40
6G-120
2G-35
172
ABS
TABLE 19.6
uPVC and Other Plastics Materials with Some Overlapping Applications (Especially in Pipes and Pipe Fittings)-A
General Comparison of Some Typical Properties
(Based in part on data from Refs 3 to 6)
;E
:::-J
C
:0::::
.,.,
s:>
;::
;:l
s:>
;::
;::s:>
t-<
00
1Il
00
859
TABLE 19.7
Some Electrical Properties of Two Rigid PVC Compounds (Breon RA 124 and
RA 170")
Volume resistivity
(Qcm)
Temperature
eC)
RA 124
23
40
60
80
90
100
aA
10
10
10
10
10
15
x 1014
x 1014
X
1014
x 1014
x 1014
x 1013
RA 170
10 X
25 X
70 X
20 X
90 X
50 X
1014
1013
1012
1012
1011
1011
Power factor at
Permittivity at
800 Hz
800 Hz
RA 124
RA 170
RA 124
RA 170
002
001
012
010
010
013
002
001
007
012
014
015
30
39
85
79
79
33
30
35
51
61
75
7-8
high-impact composition.
CHEMICAL PROPERTIES
Creep: Because of their viscoelastic rheological behaviour, polymers-and the plastics materials based upon them-are subject to creep,
i.e. increase of strain (deformation) with time under continued stress.
For a given polymeric material the creep strain will normally be the
higher the greater the applied stress, and the higher the temperature.
860
80
..
c"60
o
"iii
III
'EIII
c
......~40
~
01
:J
20
o0""""'3~:--."L-,---0~''='5---0~"'="6---0~.=7---='0'-=8
WavlZllZngth.l!m
o~
I&l
>C
o
iii 30
c
Fig. 19.3
0'1
100
Time in Hours
'000
0'1
10
At 51C
100
10
50
5.0
60
60
1000
g;
i;
5"
'<:5
l:l.
;:s
l:l
~.
.g
j:s
g.
~~
1.:t
~
s
~
l:l.
~:
'0
......
862
300kglcm 2
(42661bl i,;2)
100kglcm 2
1
10- L....,--...&.....,---'-:,..-----'-:----.J..,,---.....L..::,..----J
10- 2
10- 1
100
101
10 2
Timt und..r load, h
10 3
10 4
Fig. 19.4 Creep curves for a uPVC pipe composition at different loads.
Reproduced with permission from Ref. 8.
Creep strain: 'The strain at any given time produced by the applied
stress during a creep test'. 10
'The total strain, which is time-dependent, resulting
from an applied stress or system of stresses'. 12
'The total strain, at any given time, produced by the
applied stress during a creep test'. 13
Two further definitions are particularly relevant to data most
frequently quoted and used in connection with creep of thermoplastics.
Creep modulus: 'The ratio of initial stress to creep strain. It is given
by the equation Eo = alet, where a is the initial
stress in megapascals, and et is the creep strain at
time t,.10
'The ratio of applied stress to creep strain' .12
Creep rupture strength (sometimes called 'stress rupture strength'):
'(FL -2)-the stress that will cause fracture in a
creep test at a given time, in a specified constant
environment' .11
Early work by Turner 14 provided useful information on the creep of
rigid PVC at small levels of strain. The results showed, inter alia, that
the time at which the creep rate starts to increase sharply is dependent
863
en
~~ 10F======::f~=""'---+. . . ==:;;;;::;;~~D===d
ell
ell
..,~
VJ
10
10
Time,h
864
TABLE 19.8
Typical Values of Applied Stress to Produce Given Average Rates of Tensile
Creep in Some Plastics Materials
Material
1157
441
108
549
461 Q
343Q
304
177
90
865
866
typically lie would be, respectively, about 10-60 MPa and 10-106
cycles. It is usual to present fatigue data for plastics in the form
illustrated by Fig. 19.6, i.e. as a plot of stress (or stress amplitude)
versus the number of cycles to failure. This is the form of presentation
used for results' obtained with a sinusoid loading wave form which is
widely employed in experiments. However, with a square-wave form
of loading, the data can also be represented on a stress-time basis, * for
direct comparison with creep failure ('static fatigue') curves obtained
for the same material under continuous loading. The strength of uPVC
is normally higher under the latter conditions, so that, for the same
composition, the creep failure curve will lie above the corresponding
fatigue curve, as has been shown by Gotham 21 for calendered uPVC
sheet, and by Gotham and Hitch 22 for rigid pipe material. Two further
general points (made by Gotham 21 ) may be noted:
(i) Under cyclic loading a ductile-brittle transition in the failure
mode of uPVC may be expected after relatively short times,
whereas it may not occur at all under continuous loading (any
failure being of a ductile nature).
(ii) Brittle fracture occurs under cyclic loading at stresses much
lower than the corresponding yield stress.
The role of plastic deformation in the failure of PVC under stress
has been considered by Gotham and Turner;23 some data on fatigue
and creep behaviour of uPVC, and a discussion of their significance in
predicting long-term service behaviour of pipe materials, have been
published by Gotham and Hitch,22 and Moore et ai. 24
Fatigue (as well as creep) of uPVC pipes (especially those operating
under pressure) is of particular interest because of their large-scale use
in a number of important application areas. Cyclic loading arises in
service, e.g. as fluids are pumped through the pipes, or in consequence
of repeated opening and shutting of valves.
* By summing up the time under load in the fatigue experiment over the
number of cycles to failure, so that a figure for time to failure is obtained. 21
867
868
869
TABLE 19.9
Typical Ease-of-flow Characteristics of Pipes (AU Values Relate to Flow
Through a New uPVC Pipe, Taken as Unity)
Pipe material
uPVC
Cast iron
Steel
Asbestos/cement
After 30 years'
operation
1
087
093
1
093
027
029
073
% retention of
original ease of
flow
93
31
31
73
SAW
MACHINE
MARKING
OFF
HAUL
WATER
BATH
DIE AND
SIZING
DEVICE
EXTRUDER
HEATER
OlE BODY
BREAKER
PlATE
TORPEDO
BARREL
MELT FROM
- - THE EXTRUDE:R
Fig. 19.8 Typical pipe extrusion die. (Reproduced, with permission, from Ref. 8.)
APERTURE
MANDREL
OlE RING
THERMOCOUPLE
Fig. 19.7 A typical pipe extrusion line: schematic representation. (Reproduced, with permission, from Ref. 8.)
TABLE
DISCHARGE
o:E
:::j
:<:::
l::l..
l::l
So
l::l
t"'"
871
Plate M Pipe extrusion line (Superocla (Pty) Ltd, Rosslyn, Tv!., RSA). Top,
general view. Bottom, extruder (Cincinnati Milacron CM65 conical twin-screw
extruder), die, and spray cooling unit.
872
873
round the spider legs can result in the presence of weld lines in the
pipe, which may become failure sites under impact or pressure.
Note: This potential cause of weld-line formation does not present
any serious problems in good, modern pipe production
practice. In some extrusion operations even the possibility can
be eliminated by the use of a spiderless die. A commercial
example is the Cuvar* straight-flow die (with mandrel support
from the rear) originally designed for the production of
co-extruded plastics pipes. 31
Other considerations important in die design include the following.
The die 'geometry' is responsible for a substantial part of the
back-pressure generated in the extruder, and hence affects such
important process features influenced by the back-pressure as energy
consumption, extrusion rate, and the completeness (as well as the rate)
of gelation of the PVC stock. The constructional factors principally
instrumental in the generation of pressure in the die are (a) the
configuration and dimensions of the conically tapering section of the
channel, and (b) the length and cross-sectional area of the annulus: this
length is usually referred to as the land length, and its ratio to the
width of the aperture as the land length ratio. Values of 8-12 are fairly
typical for land length ratios of pipe extrusion dies. Obviously, the
smaller the cross-section and the greater the land length, the higher the
pressure developed.
The die design must promote generation of back-pressure at the
appropriate level: sufficient to secure the required throughput and
good gelation of the stock, but not so high as to result in excessive
generation of frictional heat in the material or cause abnormal wear of
screw thrust bearings. In relation to the throughput aimed at, the die
channel volume and configuration must be such that the dwell time of
the material in the die is optimised to ensure that the homogenised
melt is uniformly distributed in the parallel-sided annular gap which
imparts its shape to the emergent pipe.
The pressure that is likely to be developed in the die head can be
calculated if the melt viscosity of the compound at the extrusion
temperature, the die channel geometry and dimensions, and the output
rate are known. The calculation (especially with regard to the section
of the die channel between the spider and the annulus) is complex:
computer programs are available for use in working out the best die
874
875
sizing die is used, but in this method a vacuum is applied to the outside
of the extruded hot pipe via a number of small holes in the sizing tube.
This obviates the need for a sealing plug.
(iv) Vacuum ring and cooling tank: In this system the tubular
extrudate is passed through a vacuum ring (a short vacuum tube) which
effects the initial sizing of the pipe whilst cooling proceeds in a water
bath kept under reduced pressure. The atmospheric pressure inside the
pipe maintains its circularity during its passage through the bath.
Modern vacuum sizing tanks can handle a range of pipe sizes, up to
about 900 mm diameter. 32
As can be seen, mandrel sizing calibrates directly the bore of the
pipe, and the other systems, the external diameter (the dimension
particularly important vis-a.-vis pipe fittings and jointing requirements).
COOLING BATH
The main functions of this equipment are to pull the pipe away from
the die and through the sizing and cooling units at the required rate
and in such a way that it is kept straight during calibration and cooling;
it also feeds the cooled pipe forward to the marking and cutting
sections of the line. The haul-off is usually of the caterpillar or
pneumatic-tyre type, employing these elements to grip the pipe
securely and impart the necessary traction. The haul-off speed is
normally set slightly in excess of extrusion speed, to achieve the
requisite degree of draw-down. As is largely self-evident, the wall
thickness of the pipe will decrease with increasing draw-down
(increasing take-off speed), whilst the uniformity of take-off rate is an
important factor in wall thickness uniformity. For these reasons close
controllability and fine adjustment of haul-off speed are of cardinal
importance in the process.
876
MARKING EQUIPMENT
Pipes are usually cut by so-called flying saws. A flying saw is a circular
saw which travels along with the pipe as it makes the cut. The saw is
generally activated by a limit switch touched off by the end of the pipe
when a desired length has passed under the saw position. On large
pipes (diameter> about 150 mm) peripheral ('planetary') saws are
used, which do not cut right across the pipe but move around the
circumference, cutting through the wall: such saws may be associated
with a chamfering device.
Complete 'downstream handling' systems for pipe or profile
extrusion operations are available, comprising take-off and all
subsequent units (including on-demand cutters, transport, packaging
and automatic control equipment) for use on- or off-line. Automatic
perforating equipment may be used as part of an extrusion train for the
production of sub-soil drainage pipe. 32
For certain kinds of jointing (rubber-ring joints in common use in
some large-diameter pipe lines; solvent-cemented joints of the
spigot-and-socket type) a shaped socket is required at one end of a
length of pipe, with internal diameter equal to (or slightly greater than)
the external diameter of the pipe. Such sockets are produced by a
'belling' operation, in which the pipe end is heated to a suitable
temperature (quite commonly 160-165C), moulded on an expanding
mandrel of appropriate shape, and cooled. The operation may be
partly or fully automated. Some automatic belling equipment can
operate in-line with the extrusion train. 32
(b) Some Formulation Aspects
In very round figures, the cost of raw materials can amount to as much
as 60-70% of the total production cost of uPVC pipe. This is the main
reason behind the importance of material cost economy in pipe
compound formulation. At the same time, the fact that the fastest
practicable production rates are desirable for the process economy they
offer, imposes a need for considerable sophistication in formulation to
ensure stability, completeness of gelation and good rheological
877
lOOpbw
03 phr
100 pbw
12 phr
12 phr
0,1 phr
2-3 phr
878
Lubricant system:
External lubricants: paraffin wax (MP 71 0c)
partially oxidised polyethylene
(MP 104C)
Internalluhricant: calcium stearate
Acrylic processing aid
Pigment: Ti02
Filler: CaC0 3
12 phr
02 phr
08 phr
10 phr
15 phr
25 phr
879
The property tests commonly carried out on uPVC pipes for some
typical applications are cited in Table 19.10. Analogous or corresponding tests are also performed on the appropriate fittings. Some of the
tests are applicable only to the fittings or only to pipes (see the list of
relevant specifications in Appendix 1, Section 6.1).
As has been mentioned, resistance to creep (including creep
rupture) and fatigue are long-term properties very important in the
service performance of uPVC pipes operating under internal pressure.
Pipe design, and prediction of behaviour in service on the basis of
evaluation tests rely to a considerable degree on extrapolation-in
accordance with established procedures-of plots of relevant test data
(cf., for example, ASTM D 1598 and D 2837, and Refs 35 and 36).
Much is now also available in the way of actual results obtained in
long-term service. 35 ,37
Note: Evidence has been produced35 indicating that the bursting
strength of uPVC pipe can increase significantly after a long
period under steady internal pressure (as experienced in a
creep test or in service). It appears possible that such
improvement might be attributable to molecular orientation
effected by the prolonged stress, andlor possibly also to some
annealing effects.
19.3.4 Some Special Pipe Products
FOAMED uPVC PIPE
Rigid pipes with cellular (structural foam) walls are not produced or
used on a large scale because of the unfavourable difference in
mechanical properties in comparison with solid-walled pipes. However,
in some areas where the property requirements are less critical (e.g.
certain types of electrical conduit), or where the superior heat
insulation performance of cellular wall structure is relevant, foamed
V
V
V
V
v
v
Solvent immersion
(acetone or CH2 C12 )
Chemical resistance
Water-extractable content
Water absorption
v'
V
-
Vb
Vb
Vb
Vb
v
v
-
Rainwater
goods
Above-ground
sanitary piping
Sewerage
and drains
Industrial
uses
Cold-water
services"
Temperature cycling
Electric wire
conduit
TABLE 19.10
Tests Commonly Performed on uPVC Pipes for Various Applications
Decrease in length on
heating
Alternating hot and
cold water cycling
Test for completeness of
gelation
Weight change after
immersion in acid and
alkali, sometimes also
other reagents
In some cases checked
for Sn and Pb
Remarks
t-<
:::'1
0
:0::::
;:
l::l..
;::,
;::,
;:-
;::,
;:
00
1/
1/
1/
(tensile
impact
resistance in
some cases)
1/
1/
1/
Resistance to flattening or
crushing
Bursting strength
Tensile properties
(of pipe material)
(often only
high-impact
grades)
Impact resistance d
v'
v'
v
v
v
Usually a falling-weight
test method, but sometimes special tests
(ct. Chapter 11,
Section 11.2.2(a))
00
00
'"
;:
5"
l:l
'"'
~:::-:
;:
I:l..
l:l
'"
~.
'"'
S"
.?
'1:l
.,
.g
;::
I:l..
;j
'1:l
'C;"'
;::
I:l..
;j
'1:l
-.:::
'1:l
I:l..
~:
'0
'-
882
pipes are of interest. They can certainly offer cost advantages over the
solid-walled pipes in view of the already mentioned high share of
material cost in the total cost of pipe production. A good summary of
the main aspects of production of foamed pipes (including formulation,
extrusion conditions, and economics) and their properties has been
published by Szamborski and Marcelli. 38
'HOLLOW-WALLED' uPVC PIPE
Sewer pipes have been produced incorporating closely spaced
longitudinal channels in the wall (formed by the extrusion die of
special design used to produce the pipe):* weight reduction of up to
about 30% in comparison with a solid pipe has been claimed, with
corresponding cost reduction of around 20%, and only moderate
sacrifice of the relevant mechanical properties. 39 This last feature-also
said to make the strength superior to that of foamed-wall pipes-has
been attributed to the fact that the structure of the pipe wall (as readily
demonstrated by a cross-sectional view) resembles a circumferential
assembly of 'I-beams' joined at the edges: this beam shape is well
known for its high strength-to-weight ratio.
HIGH-STRENGTH, ORIENTED uPVC PIPE
Controlled, partially biaxial molecular orientation induced in the wall
material by modifications of the production process involving a
stretching operation, can result in substantial improvements in bursting
strength, impact resistance and fatigue resistance of the pipe in
comparison with standard pipe of similar diameter and pressure rating
but nearly double wall thickness. The first commercially available pipe
of this kind was developed and produced in the late 1970s. t
uPVC PIPE
Large-diameter pipes for culverts and sewers, having a corrugated
wall, are manufactured (in PVC and other thermoplastics) by extrusion
directly followed by air-pressure expansion against corrugated sectional
mould blocks. In a variant of the process a continuously extruded strip
is helically wound and fused together to form a continuous pipe. The
patented* production process can also be used to make double-walled
CORRUGATED
883
pipe (with a smooth inside wall and corrugated outside wall, or vice
versa), or conventional smooth-walled pipe.
RIBBED PIPE
Extruded profiles range from simple strips for use as beading or trim,
e.g. with PVC panelling, through more intricate cross-sectional shapes
(including channels and the like) for various trimming, finishing and
* Ribstruct pipe-Duropenta (Pty) Ltd, New Germany, RSA.
884
* Developed by GKN. Commercial 'Coexcel Thermal Clad' profiles manufactured by a subsidiary, Scope Aluminium Products Division of BKL
Extrusion Ltd, UK.
885
19.4.2 Production
The production process and typical extrusion line for profiles are
generally similar to those for pipes, the greatest degree of equipment
complexity and refinement being called for in the manufacture of
hollow multi-channel profiles of complex cross-section used for modern
uPVC window frames: sophisticated extrusion dies and calibrating and
cooling equipment (with the associated pumping gear) are employed in
lines for this product, which also include-as do extrusion trains for all
kinds of profiles-haul-off, marking, and cutting equipment. Whole
lines specially designed for window-frame profile are available from
manufacturers of this type of machinery, incorporating advanced
control systems and cutters. In the USA, production of window-frame
profiles from pellet stock on single-screw extruders is still common,
whilst dry blend extrusion on twin-screw machines is widely practised in
Europe. Typical production rate capabilities are in the range
15-3 m min- 1 , with pellet extrusion on single-screw machines near the
lower end. The main restricting factors on speed of production are the
sizing and cooling operations: both require elaborate arrangements and
sufficient time to ensure effective heat removal from the complex,
multi-channel profile, and its accurate dimensioning to close tolerances.
Foamed profiles are normally extruded from powder feedstocks to
avoid subjecting the blowing agent to extra heat processing at the high
temperatures involved in the melt-compounding of pellet feeds. Since
foaming takes place on emergence from the extrusion die (cf. Chapter
25, Section 25.2.1), a sizing die ('former') is used-normally positioned
in the cooling bath-to control the final size: the sizing operation also
determines the density of the finished profile. As a rough general
guide, the respective cross-sectional areas of the extrusion die orifice
and the sizing die should be in the same ratio as the product density
aimed at and the density of the solid (unexpanded) uPVC composition.
The density of the final product is also influenced by other factors, in
particular the distance the extrudate travels before entering the cooling
bath and sizing die. Torpedoes and spreaders used in the extrusion of
uPVC compositions into solid pipes and profiles are not normally
necessary with foaming compounds. A useful discussion of foamed
profile extrusion has been published by Davies,42 and one of methods
of production of structural foam in general (by extrusion and injection
moulding) by Harris. 43
886
887
888
, ...
,,
80
.
.......
II
r.
II
,,
"
60
',/"
.",.,,----..
',/
40
-/-
CPE modiflad
'../.....
20
/"
/"
/"
/"
/"
/"
/"',
'
........
- --....
..........
"
EVA modiflad
'<
Acrylata
mOdiflad
Unmodifiad
014.......==I:::::::t=::t=I:::::c::::c:c:~_==::x=6.........J...--I.......J
1965'66 '67 '68 '69 '70 '71 72 '73 '74 '75 '76 '77 '78 '79 'SO '81 '82 '83 '84 '85
Yaar
Fig. 19.9 Percentage shares of the three basic types of impact-modified PVC
window profile compositions in the West German market. (Reproduced from
Ref. 46 by courtesy of the editor of Plastics and Rubber Weekly.)
889
890
Aim
Foil
.....
075mm
(003in)
19.5.2 Production
uPVC film is usually made by the blown-film extrusion process. Some
solution-cast film is also produced, for applications where high clarity
and/or freedom from orientation are important (see Chapter 24).
Sheeting is made by calendering, or by extrusion (from a flat sheet die
into the nip of cooling and polishing rolls-sometimes referred to as
extrusion casting). Calendering of PVC is discussed in Chapter 18: in
comparison with this process, extrusion involves lower equipment cost
* It may be recalled that the relevant British nomenclature standard puts the
demarcation point between PVC film and sheet at 0003 in (76Ilm), whilst
other standards give 250 Ilm as the upper thickness limit for film for all plastics
(ct. Chapter 20). It may also be noted that in industry the thickness range
for PVC foils is sometimes quoted as, or implied to be, 01--06 mm, or
01--07 mm.
891
and is more flexible, in the sense that calendering is best suited to long
runs on the same thickness and width of product. Very thick sheets (up
to about 25 mm and even thicker in some cases) for such applications
as, for example, glazing, chemical plant, etc., are made by compression-laminating a number of thinner sheets (see Chapter 20, Section
20.1).
892
Extrusion lines for blown film and for extrusion-cast sheeting are
available from several equipment manufacturers, e.g. inter alia,
Barmag (blown film, and sheeting, including coextruded productsEurope and USA), Francis Shaw (blown film, and sheeting-UK and
Europe), Kestermann (sheeting-Europe), and Windmoler and HOlscher (blown film-Europe and USA).
Apart from conventional thickness gauges (radiation, and other
types) long established in industrial use, advanced equipment for
continuous, on-line monitoring and-in some cases-automatic control
of product quality is available for use on film and sheet extrusion
trains. Examples include the following. The 'NC-P' thickness control
* The geometry of a coat-hanger die design with uniform flow rate and
residence time across the die width is discussed in a paper by Matsubara. 5o
893
system (Windmoler and Holscher, West Germany and USA) for blown
film,51 utilising IR transmission as the property monitored, and
automatic adjustment of individual cooling sectors in the ring to effect
corrections. The Sussex pneumatic system (Sussex Instruments Ltd,
UK) for continuous monitoring of film or sheet thickness 52 with a
feedback control loop operating on the extruder or line speed controls.
The 'Intec 500' laser-based inspection system (Intec Corp., USA)53 for
detection of defects (fish-eyes, gels, wrinkles, streaks, holes, contaminants, and surface imperfections). Sheet or film profile control
systems,54,55 which-like that forming part of the 'Profitmaster 5510'
extruder control system (LFE Corp., USA)-eouple detection of
irregularities in profile with automatic correction through adjustment
of the sheet die lip. Microprocessor-based systems for web width
control are also available, e.g. the 'Sigmat 770' system (TMS Systems
Ltd, UK), originally offered for blown film of width up to about 10 m.
19.5.3 Applications and Properties
The main uses of thick uPVC sheet are mentioned in Chapter 20. The
applications as cladding may be considered to encompass both sheet
and profile, in that some cladding systems involve the use of panels
(which may be of the pressed, and/or thermoformed56 variety) and
others of extrusions narrow enough to be classed as profiles. The main
service performance requirements applicable to external cladding are
similar to those that window-frames have to meet, including good
resistance to impact and weathering. Similar formulating approaches
are used (d. Section 19.4.3 above), with acrylic and chlorinated
polyethylene impact modifiers popular in formulations.
Note: Particularly good performance has been claimed57 for a type
of modified acrylic impact modifier commercially represented
by Durastrength 200 (M & T Chemicals Inc., USA).
Some aspects of the service behaviour of external cladding are
related to the effects of processing. Apart from any detrimental effects
of incomplete gelation, shrinkage and surface distortion can take
place-in consequence of recovery of production-induced stresses-at
elevated temperatures resulting from solar heating. The surface
distortion (local rippling and bulging) is sometimes referred to as 'oil
canning'. uPVC materials with high enough heat distortion temperatures (say about 87C) tlre less prone to this effect. The stress
894
100
3phr
3phr
05 phr
BS 2782:1970-515B
BS 2782: 1970-515A
30/30
100-160
90
1
4500
40
39-58
150-200
230
Food items b
(including ones
for deep-freeze)
40/20
30/30
10/10
100-160
90
1
1700
25
54-64
150-200
100
Non-food
articlesC
10/10
40/20
30/30
100-160
90
1
4600
50
49-69
175-250
300
Heavier or
sharp-pointed
objects d
Based on data from technical and sales literature for Vinophane films (BCL Films Division, Bridgwater, UK).
b e.g. tray-borne or unsupported fruit, fish, meats (fresh or cooked), cheeses, bakery products, sandwiches.
C e.g. toys, games, cards, table mat or coaster sets, small textile items.
d e.g. cutlery, sharp-cornered toys, tools, stationery, clothing, household textiles.
e 25-llm film. f 19-1lm film. g 125-llm film.
BS 2782:1970-514A
Optical properties:
Gloss (%)
Hazeo(%)
BS 3177
ASTM D 882-67
ASTM D 882-67
BS 2782:1970-306F
Test method
Barrier properties: g
Water vapour transmission (at 25C, 75% RH)
(g m- 2 (24 h)-I)
O 2 transmission (at 21C, 44% RH)
(cm 3 m- 2 (24 h)-I atm- I)
Physical properties:
Tensile strength (MPa)'
Elongation at break (%)e
Impact resistance at OC (g(
TABLE 19.11
Some Typical Properties of Commercial Shrink-wrap PVC Films (Relative Density 13; Thickness 12-25 pm)Q
f2
U1
2
g"
a
l'>..
~
.g
...;:t.'"
l'>..
;:
"g.
:s
::p
"tl
l'>..
;:.;,
~:
.....
'0
896
100
16 phr
6phr
19 phr
08 phr
09 phr
12phr
897
898
REFERENCES
1. Jacobson, U. (1959). Brit. Plast., 32(4), 152.
2. Corvic Vinyl Chloride Polymers (1982). Technical publication of AECI
Chlor-Alkali and Plastics Ltd, Johannesburg, RSA.
3. Howie, J. A. (1971). Chem. Brit., 7(10), 428-33.
4. Mining: Why PVC Now? Technical booklet; AECI Ltd, Plastics Division,
Johannesburg, RSA.
5. Properties of Plastics (1976). Technical booklet, Shell Chemicals UK Ltd,
London, England.
6. Titow, W. V. and Lanham, B. J. (1975). Reinforced Thermoplastics,
Applied Science Publishers, London.
7. Plastics: The Principles of Injection Moulding. ICI Technical Service Note
G103 (2nd Edn), ICI Plastics Division, Welwyn Garden City, Herts,
England.
8. Press, J. B. and Trebucq, D. A. (1977). In Developments in PVC
Production and Processing-i, (Eds A. Wheelan and J. Craft), Applied
Science Publishers, London, Ch. 9.
9. Handbook of Plastics Test Methods (1981). (Ed. E. Brown), George
Godwin Ltd and The Plastics and Rubber Institute, London, 2nd Edn,
p.189.
10. ISO 899-1981. Plastics-Determination of tensile creep.
11. ASTM E 6-81. Standard definitions of terms relating to methods of
mechanical testing.
12. BS 4618. Recommendations for the presentation of plastics design data. Part
1: Mechanical properties. Section 1.1: 1970: Creep.
13. ASTM D 2990-77. Tensile, compressive, and flexural creep and creep
rupture of plastics.
14. Turner, S. (1964). Brit~ Plast., 37(6), 322-4, and (12), 682-5.
15. Ogorkiewicz, R. M. and Bowyer, M. P. (1969). Brit. Plast.. 42(9), 125-8.
16. Bucknall, c., Gotham, K. V. and Vincent, P. I. (1972). In Polymer
Science, (Ed. A. D. Jenkins), North Holland, Amsterdam, Vol. 1, Ch. 10.
899
900
46. Anon. (1982). Pfost. Rubb. Wkfy, 13th November, pp. 8-9, and 20th
November, pp. 8-11.
47. Neudell, D. H. (1982). Pfost. Techno!., 28(8), 31-5.
48. Anon. (1981). Mod. Pfost. Int., 11(9), 8 and 69.
49. Johnson, J. E. (1978). 36th ANTEC SPE Proceedings, pp. 36-40.
50. Matsubara, Y. (1979). Pofym. Engng. Sci., 19(3), 169-72.
51. Anon. (1981). Mod. Pfost. Int., 11(11), 11.
52. Anon. (1979). Pfost. Rubb. Int., 4(3), 115.
53. Anon. (1981). Pfost. Technof., 27(2), 15-17.
54. Rudd, N. E. (1978). 36th ANTEC SPE Proceedings, pp. 565-8.
55. Anon. (1981). Mod. Pfast. Int., 11(7), 10.
56. Acton, J. (1976). Pfost. Rubb. Wkfy, 23rd April, pp. 17-19.
57. Stoloff, A. (1979). Pfost. Engng, 35(7),29-31.
58. Changfoot, J., Dickson, A. G., Noel, F. and Stark, W. M. (1976). 34th
ANTEC SPE Proceedings, pp. 42-4.
59. Briston, J. (1976). Packag. Rev., 96(3),71-4.
60. Copsey, C. J. and Gooding, V. J. (1977). 'Effects of processing on the
morphology and properties of injection moulded PVC', paper presented at
the Institute of Physics Conference on Processing, Structure, Properties
and Performance of Polymers, University of Nottingham, July 1977.
CHAPTER 20
20.1 INTRODUCTION
Very few people nowadays can be unfamiliar with plastics sheet or
film. However, it may be of some interest to consider briefly the actual
meanings of these terms, and the significance of the distinction
between the products they designate.
The main English-language standards of plastics nomenclature l - 3 all
base their definitions of sheet on the obvious cardinal feature, viz. that
this laminar product is thin in relation to its length and width. Some2 ,3
also relate the term to a single piece of such product? which may have
been individually produced or cut from sheeting, the latter term being
defined as sheet in continous form (e.g. a long length supplied as a
roll 1,2). One of the standards 1 recognises synonymous use of 'sheet'
and 'sheeting'.
On the above basis a film is clearly a kind of sheet (or sheeting).
Indeed the only distinction between the two-both in standard
terminology and in common usage-is purely a matter of thickness,
and not actually precisely defined in industry. Thus whilst the general
sequence (in order of decreasing thickness) sheet~ thin sheet~ film is
universally recognised, the actual demarcatory thickness value between
thin sheet and film (or, for that matter, thin and thick sheet) is not
uniformly quantified and can vary in practice depending on the
material, the field of application and even the country concerned.
However, in an attempt at standardisation, the general thickness limit
below which a plastics sheet should be referred to as a film is set by the
three above-mentioned standards at 250.um (0010 in). The arbitrary
901
902
W. V. Titow
nature of this figure is actually pointed out in the ISO standard, l and
illustrated by a note in the BS specification to the effect that in the case
of some materials the term 'film' should be reserved for still thinner
sheet, and that specifically for unsupported rigid PVC film the upper
thickness limit should be 0003 in (about 76,um).
The term 'foil' is also sometimes applied in certain practical contexts
to plastics film and thin sheet materials, although it is not defined in
the nomenclature standards, only one of which2 mentions it as a
(discouraged) alternative to 'film'. Thus the thin films (plastics or
metal) used in the so-called hot-foil stamping method of surface
decoration (see Section 20.3.5(a) below) are commonly referred to as
foils: this is quite logical in view of the long-standing (and
standardised) relevant terminology for thin metal films* as well as
common usage in the packaging field where such films (employed e.g.
for wrapping chocolate) are known as foils. Less obviously logical (and
vis-a.-vis the accepted meanings just mentioned even somewhat
contradictory) but none the less fairly widely encountered in
commercial and industrial contexts, is the use of 'foil' for thick plastics
film or thin sheet (with PVC roughly 0003-003 in) for such packaging
applications as thermoformed insert trays, blister packs, etc. Finally,
the word foil occasionally crops up in contexts where it is clearly
employed as a loose synonym for plastics film in general.
Note: It appears possible that the use of 'foil' in English in the latter
two connotations may owe something to the influence of
relevant plastics terminology in other languages (ct. Foliethe correct German term for 'film', and French feuille for
'film' or 'sheet', in the plastics context).
903
904
W. V. Titow
* This type of laminate was specially developed for lining metal tanks for heavy
chemical duty. Bonding large areas of rigid PVC sheet to mild steel presents
serious problems. However, when the laminate is bonded (by means of a
special adhesive) with its plasticised layer to the metal surface, and inter-sheet
joints are sealed by welding with a uPVC welding rod, satisfactory adhesion is
achieved, coupled with the overall effect of an all-uPVC internal tank
surface. 10
t Currently manufactured by a subsidiary, Weston Hyde Products Ltd, formed
by the recent amalgamation of Wallington Weston and the ICI PVC sheet
product manufacturing operation at Hyde.
905
latest for these ranges,9 they provide a valid general indication of the
kind of materials concerned and their uses. The following may also be
mentioned by way of further examples.
Roofing and wall-cladding sheet: Sintaclad (ICI)-rigid corrugated
sheet for roofing applications* and for cladding of buildings exposed to
corrosive chemical atmospheres: good retention of light transmission
(several years in moderate climates) is claimed for the transparent
version (tinted in 'solar bronze' to reduce heat build-up). Both the
transparent and opaque versions have Class 1 ratings in the
spread-of-flame test of BS 476: Part 7. Biaxially oriented uPVC
sheeting (clear or translucent) developed by Solvay & Cie., Belgiumt
(based on their Bellvic emulsion resin grades claimed particularly
suitable for outdoor applications) offers improved impact resistance
imparted by the orientation, coupled with retention of this property
down to very low temperatures (-40C is claimedll). Cobex 1350
(Storey Bros,:j: UK)-sheet for interior wall cladding in food factories,
bottling plants and the like (meets the requirements of BS 3757, Part 1,
and BPFIBIBRA Code for food-contact materials).
Linings for chemical or food-storage tanks and reactors: Vybak
(Storey Bros, UK)-pressed PVC sheet (service temperatures up to
95C claimed for GRP-clad installations). Armodur (Societe la
Cellophane, France)-rigid PVC sheet made by pressing from
calendered sheeting based on a mass-polymerised resin grade. Telcovin
TL (Telcon Plastics, UK)-flexible PVC sheet.
Safety doors: Astraglass (Dynamit Nobel, West Germany and
UK)-flexible PVC sheet.
Sheet and film for thermoforming: Kydex (Rohm and Haas, USA:
European Licensee Mazzucchelli Celluloide, Italy)-acrylic-modified
PVC sheet. Fromopack (Wallington Weston, UK)-range of thermo-
05-190mm
(002o.l in)
08-254mm
(&-1 in)
16-48mm
(rl,-rl,in)
CF standard grade
Industrial grade
Unplasticised/
plasticised grade
(laminate)
Nature and/or
colour'
Various colours; two
types of surface finish
(matt or polished)
Various colours; two
types of surface finish
(matt or polished)
Thickness range
05-12,7 mm
(0020-~ in)
Darvic sheet
Standard grade
Type and/or
grade
Main applications
Tank lining
Special features
TABLE 20.1
Some Properties and Applications of 'Darvic' and 'Flovic' PV-c Sheeting
:::J
:<:::
Up to 0'76mm
(0,003 in)
075-45 mm
(0030-0180 in)
Darvicfilm
Flovic sheet
(vinyl chloride/vinyl
acetate copolymer)
10-65 mm
(0040-0260 in)
05-65mm
(0.020-0.260 in)
Clear grade
;:,
6"
l:>
F;.
0-
i;'
;:,
I:l..
l:>
'"~
v,
;:r-
."
I\,)
909
formable packaging sheeting in clear, rigid PVC, for blister packs, skin
packs, etc. Vinophane (British Cellophane, UK)-clear PVC film for
various shrink-wrap packaging applications.
(i)
910
W. V. Titow
(i) The current edition of Modern Plastics Encyclopedia, McGrawHill, New York.
(ii) Films, Sheets and Laminates: Desk-top Data Bank, International
Plastics Selector Inc., San Diego, California.
20.3.1 VVelding
The international standard for plastics nomenclature l defines welding
as 'the process of uniting softened surfaces of materials, generally with
the aid of heat', and points out that in some countries the term
'sealing' (rather than 'welding') tends to be applied to processes in
which the surfaces of films are united by the application of heat and
pressure.
All the main techniques employed in the welding (as distinct from
bonding or cementing-see Section 20.3.2) of PVC involve the
application of heat to, or its generation in, the material at the site of
the joint. Hence the main factors instrumental in weld formation are
the welding temperature, amount of heat, duration of heating, and the
pressure applied. As in all processing of PVC, it is important to
minimise the risk of direct thermal degradation (which in this case
would be largely localised in the area of the welded joint) and
generally to ensure the minimum practicable increase of the heat
history of the material in this area. The recommended general
temperature ranges for welding rigid and flexible PVC are, respectively, 180-210C13 and 250-300c. l4 Below the lower limits of the two
ranges incomplete or faulty welds are likely, whilst exceeding the
upper limits can cause unacceptable degradation of the polymer.
911
912
W. V. Titow
913
914
W. V. Titow
techniques (thermal-impulse, heated-tool, ultrasonic, and highfrequency welding) for the production of welded seams in coated
fabrics has been published by Koehler. 20
Analyses of some welding processes for thermoplastics in terms of
their principal parameters are given in papers by Frankel and Wang21
(ultrasonic welding), and Potente and Reinke 22 (heated-tool, ultrasonic, and friction welding).
Some of the welding methods and their applications in the
fabrication of PVC products are discussed further in the following
sections.
915
WELDING TORCHES
916
W. V. Titow
and/or a gas flow meter. The gas should be free from oil, water and
other contaminants.
WELDING TECHNIQUE
917
INDUSTRIAL WELDING
For plastics films and thin sheets, where the material is too thin for
grooving, overlap welding is used. This operation can be considerably
mechanised for many applications (e.g. production of tarpaulins, in situ
joining of films used as seepage barriers, etc.) and the mechanisation
adapted to so-called 'tape welding' in which the film edges to be joined
are butted together and sealed with special thermoplastic tape which
overlaps the joint on both sides.
The lining of a metal tank with PVC sheeting (which may be the
uPVClpPVC laminate previously mentioned) can be examplified by the
following sequence of operations.
(i)
918
W. V. Titow
This is carried out in premises with PVC tiled floors, especially where
considerations of hygiene make a continuous surface particularly
desirable, e.g. in hospitals. In essence, the operation consists in
grooving the joint lines between the tiles and sealing by welding in the
normal way. In manual operation the welding rod (welding cable) may
be fed and laid in with the aid of a feed roller, with the handle
hollowed out to take the cable, and a grooved wheel to apply it to the
groove. However, here too the process can be considerably speeded up
by the use of a speed-welding nozzle (suitable for the cable diameter
employed). A still faster rate of working is made possible by floor
seam-welding machines, which run automatically, following a groove,
919
laying a weld, and shutting off upon reaching a wall, so that the
operator's function is reduced to moving the equipment over into
consecutive grooves, and general supervision. Welding rates of
30 it min- 1 are possible with this kind of automatic operation, if the
grooves are properly made, preferably by a mechanised chamfering
tool.
Felt- or foam-backed PVC flooring was originally welded from the
back, after chamfering away the backing layer. The modern method
permits the welding of such flooring in position, i.e. when stuck down
in the normal way. Exact chamfering with a motorised tool engaging in
the gap between the sheets enables a groove to be produced which is
accurately centred and of a depth so pre-adjusted that the felt or foam
layer remains virtually undisturbed. The welding can then be carried
out manually or with an automatic machine.
In all floor welding, the seam (original welding cable) will remain
protruding above the tile or sheet surface on completion of the welding
operation. These protrusions must be removed, to make the floor
surface flat and even. This can be done with a sharp knife ('spatula') or
another hand tool (e.g. a spatula fitted with a cable-cutting slide), but
is best accomplished with a trimming plane whose knives can be set to
cut no deeper than is necessary to ensure that the seam does not 'sink
in' afterwards.
(b) Extrusion Welding
This modification of the hot-gas welding method was developed in
Germany. The main general features of the extruder component of a
typical extrusion welder have already been mentioned. The second
main component of this tool is a heavy-duty hot-air gun (usually
mounted on the side of the extruder): this pre-heats the material in the
area of the joint to be formed as the tool is moved along the groove
and just before the nozzle of the extruder head lays-in a line of melt.
In comparison with conventional hot-gas welding, extrusion welding
enables welds to be produced in one operation where otherwise the
sheet thickness and width of groove would necessitate the consecutive
laying-in of several welding rods, and can give much higher weld
strengths. Heat degradation of the material can also be reduced with
this technique.
920
w.
V. Titow
its features and applications are reviewed in Ref. 16. The appropriate
sections of the parts to be joined are subjected to an alternating
high-frequency field by positioning them suitably between two
electrodes. The induced internal molecular vibration generates heat
within the material which becomes softened to the point where it can
be welded under pressure. The electrodes may be flat or threedimensionally shaped, depending on the configuration of joint
required, and should be temperature-controlled so that they do not
become overheated (by heat transfer from the material) during
welding. In commercial equipment they also serve as the means of
applying pressure to the joint. Various arrangements and electrode
designs are used. For more efficient material heating (through
reduction of heat loss to the comparatively cooler metal of the
electrodes) thermal barriers are normally interposed between the
921
electrodes and the work. Originally the material commonly used for
this purpose was a hard paper known as 'Pertinax', but a variety of
others have proved more successful, e.g. silicone-impregnated glass
fabric, PTFE sheet, etc.
The internationally recognised standard operating frequency for the
welding equipment is 2712 MHz, with a tolerance limit of only
06%. The narrow margin this leaves for variation necessitates a high
degree of built-in frequency control (which is reflected in equipment
cost), inter alia, to ensure (commonly through the use of auto-tuners)
that any change in capacity caused by reduction in the thickness of
material between the electrodes as fusion takes place in the course of
welding, does not result in frequency drift beyond the prescribed
limits. Purely from the technical standpoint, production may in fact be
improved by operating at frequencies higher than the standard (cf., for
example, the 50 MHz machines originally available from StanelcoThermatron Ltd*). The optimum power for welding depends very
much on the sheet thickness. In general, the thinner the material the
higher the power required to compensate for the proportionately
greater heat loss from the plastic to the metal of the electrodes (which
are colder than the plastic heated up in the course of welding). It is
because of this that at very low material thicknesses welding may not
be possible at all. The already mentioned use of thermal barriers is
aimed at reducing the heat loss and thus redressing the balance to
some extent. As an example, for film 0003 in thick, tOO MHz is
necessary, and the length of heating time makes little difference,
although it does, of course, above 0010 in. As a general, approximate
guide, 1 s may be regarded as about right for the heating time of films
up to 0005 in. For sheets about 0020 in thick (for example) a time of
6 s should be aimed at, although less would be preferable if the power
is available. The best seam is obtained by using a short time cycle
(excess will cause plasticiser loss and embrittlement), a light pressure,
a reasonable heat dosage, and electrodes with suitably radiused edges.
Sharp edges will cause a field concentration and overheating.
The nature of the compound influences the weld obtained. Metallic
particles and furnace blacks can give conducting paths and serious
troubles on thin sheets. Really first-class dispersion should, therefore,
be obtained if these types of fillers are to be employed. Generally, the
lower the filler content (including pigment) the better the result.
* Member of the International Group Wilcox and Gibbs Inc.
922
w. v.
Titow
Excess material can make welding more difficult and weak seams may
result. Highly filled cheap products should therefore be used with
caution, particularly with inflatable goods where good seams are vital.
Note: Arcing-a potential source of serious damage to the electrodes and danger to the operator-was a real possibility with
early versions of welding equipment, especially when processing thin films. In modern machines the hazard has been
virtually eliminated by the incorporation of arc-sensing units.
High-frequency welding machines are available from a number of
manufacturers. Stanelco-Thermatron (with its parent group) and
Radyne Ltd are among those whose equipment represents wide ranges
of size and power rating, and includes complete production lines, in
many cases incorporating also printing and other operations.
The products welded on the equipment typically include the
following: Blood-transfusion and other PVC medical equipment; liquid
packaging; clothing (including protective garments and rainwear);
footwear; stationery covers, folders and binders; book covers; fancy
goods; handbags; luggage; garden and other furniture covers; upholstery; inflatables; baby wear; pram covers; quilted goods; tarpaulins;
large welded sheets; car trim.
The welding press platen sizes range from, say, about 25 x 3 mm
(for welding blood-transfusion equipment) to 3 x 2 m (for inflatable
rafts), with generator power ratings of the order of 100 W at the lower
end of the range up to 100 kW at the higher end.
(d) Heated-tool Welding
As has been mentioned, in this method the surfaces to be welded are
heated by direct contact with an electrically heated element which may
be quite intricately shaped to give the type of weld required. In
practice the surfaces are actually pressed against the element
(pre-heated to the appropriate temperature), allowed to remain in
contact for the appropriate time, the heating element is withdrawn and
the surfaces are brought together under the appropriate pressure to
form a weld. It is claimed25 that heated-tool welding is one of the
quickest and most economical methods of heat-welding thermoplastics.
Apart from the properties of the material itself, the following points
are of crucial importance to the quality of the weld: the tool
temperature and surface condition, pressure during pre-heating, time
923
20.3.2 Bonding
924
w.
V. Titow
method is not normally used for butt joints where these are likely to
experience significant stresses (especially bending stresses) in service.
The essential features of bond formation in this method are the
interdiffusion of polymer molecules across the original interface
between the two components of the joint, and the promotion and
acceleration of this process by the swelling (increase of the free volume
content) of the polymer of the joint components at the interface,
caused by sorption of the solvent. The solvent concentration in the
polymer, originally high, is ultimately reduced to a low constant value,
mainly by further penetration inwards (away from the joint line),
and-to a minor extent-also by evaporation from the 'edges' of the
bond zone. 6
As normally practised, the solvent bonding operation involves the
following main stages:
(i)
925
926
W. V. Titow
TABLE 20.2
Strength Development in Joints Between Rigid
PVC Parts Bonded with Solvent Cement"
Time from
assembling
(h)
05
1
4
8
16
32
48
96
113 (0503)
120
220
290
400
495
505
580
(0534)
(0979)
(1290)
(1779)
(2202)
(2246)
(2580)
a PVC
equipment or power and heat sources, and the good ultimate bond
strengths obtainable. It is for these reasons that the method has been
widely used in the bonding of rigid PVC pipes and fittings. However, it
should be noted that the quality of joints depends critically on the skill
and conscientious working of the operator, as well as on good fit
(absence of gaps) between the surfaces to be joined. Other limitations
are the volatility, somewhat toxic nature, and flammability of the
solvents used (which may become particularly significant when
operating in confined spaces and/or near potential sources of ignition).
The already mentioned fact that a solvent-bonded joint cannot be
subjected to normal service stresses for some time after assembly is
also a consideration.
In general, solvent bonding may be regarded as more suitable for
rigid than for flexible PVC parts, because of the possibility of local
effects of the solvent(s) on the plasticiser content and distribution in
the area of the joint, which may lead to hardening and other
undesirable consequences. However, where this possibility has been
properly taken into account (and-preferably-the level of any adverse
effects shown to be acceptably low by suitable tests) flexible PVC
products may be successfully joined by the solvent method. An
interesting, if minor, example is the solvent bonding of flexible PVC
tubing and fittings, stitched into certain types of high-altitude flying
suits to serve as conduit for a liquid heat-exchange medium.
927
General
applicability
Type
Loctite IS 414}
CyanolitC 811
Eastmand 910
Bostik PA 779
Bostik 3250
Adhesive
Footwear (especially
soles to uppers)
Film laminates
Some typical
uses
TABLE 20.3
Main Types of Adhesives for PVC
Remarks
tv
\0
'"
:::J
:-::::
00
Nitrile
rubber
Hot-melt
(several polyesterbased)
InstawelcV
Selected members of
the Permabond e C
and F ranges
Bostik 4141 and 4142
(water-based: emulsion types)
Bostik M890 (a modified'two-part acrylic
system)
Bonding pPVC to
polyurethane foam
(e.g. in motor car
upholstery), Flooring adhesives
Mainly uPVC
Bonding uPVC
(various products) to
itself and certain
substrates
Some suppliers:
a Bostik companies in most Western countries. Hager & Kassner-West Germany.
b Loctite-USA and UK.
C Industrial Science Ltd-UK.
d Eastman Kodak, and associated companies in most Western countries.
e Permabond Adhesives-UK, and associate companies.
f National Adhesives and Resins Ltd-UK.
Predominantly uPVC
Acrylic
(acrylate
copolymers)
Acrylic adhesives are
used in some PVC
pressure-sensitive
products (e.g. tapes)
\0
tv
\0
"
""<
~.
l'>..
;l
~
"l:I
930
W. V. Titow
20.3.3 Machining
Although ordinary engineering workshop equipment can be successfully used for machining plastics, including PVC, certain tool characteristics, speeds and settings may be used to advantage. A useful review of
the subject has been made by Korani. 30 Special tools, including
portable equipment, are available for machining plastics sheet, etc. In
the UK a range of such equipment is supplied, for example, by
Interwood Ltd. This includes, inter alia, routers, trimmers, edgeclipping trimmers, and shears. Some general pointers concerning the
most common operations are briefly summarised below: most of these
relate primarily to typical rigid PVC sheet. Wherever possible,
asbestos-filled uPVC sheeting should be cut to the required size(s) by
the suppliers, most of whom offer such service.
CUTTING
For drilling the included point angle should be 140 and a quick spiral
should be employed. Without lubricant a peripheral speed of
100 ft min -1 is satisfactory but this can be increased to 200 ft min- 1
with lubricants. For holes over 05 in the drills and feeds used with
steel can be employed.
ENGRAVING
Spindle speeds of about 5000 r min -1 with a low rate of feed should be
employed. The included angle of the cutter should be 45-60 tending
towards the higher figure. A clearance angle of about 40 or larger is to
be preferred and the material should be chilled before work begins.
Apart from soluble oil, a suitable silicone emulsion may be employed.
If a coolant is not used the swarf may be prevented from sticking to the
sheet (by static) by wiping with an antistatic agent.
931
The simplest turning tool is a profile cutter, and increasing the front
rake angle reduces the amount of heat generated. With a straight
turning tool a 10 top rake and 20 front clearance give good results.
The following are general rules: the included cutting angle should be
about 60; the tool tip must have a radius of 0025 in for a side cutter
and more for a rou,nd-nosed cutter; the tool faces must have a high
polish; the tool must be sha~ilicon carbide can be used to
advantage; the speed of the work should be about 500 ft min -1.
If troubles are experienced, it is because the correct conditions are
not being used. For example, chipping and shattering are chiefly
932
w.
V. Titow
933
934
W. V. Titow
HOT-FOIL STAMPING
S
R
C
Fig. 20.2 Two basic structural variants of hot-foil stamping tape: schematic
representation. C, carrier base; R, release layer (e.g. wax, silicone); S,
protective surface layer for image (polymeric); F, metal foil; A, hot-melt
adhesive; P, coloured polymer composition layer.
935
possible in the image, and that the article's wall thickness (at least in
the image area) must be uniform and not too low, to withstand the
heat and pressure of the transfer operation. The main advantages of
hot-foil stamping are that it is the only method of true metallic printing
on plastics, that suitably embossed dies can produce inlay-emboss
print effects (on smooth or irregular surfaces) and that high quality
prints are obtainable without any after-treatment.
EMBOSSING
936
W. V. Titow
REFERENCES
1. ISO 472-1979. Plastics-Vocabulary.
2. BS 1755. Glossary of terms Used in the plastics industry. Part 1: 1967.
Polymerization and plastics materials.
937
938
w.
V. Titow
CHAPTER 21
TITOW
21.1 INTRODUCTION
The processing of PVC in paste form constitutes an important,
long-established area of the technology of this versatile polymer.
Pastes are made with emulsion-type PVC resins (although suspension
resins are sometimes added for special effects-see Sections 21.2.2 and
21.3.1 below). In the early days such resins were selected for the
purpose from among the standard grades: subsequent availability of
special paste-making emulsion polymers did much to further the
advance of the technology and applications of PVC pastes.
In the PVC context, the word 'paste' may be regarded-and is used
in this book-as the broadest generic term for a suspension comprising
particulate vinyl chloride polymer or copolymer as the principal, or the
only suspensoid, and liquid plasticiser(s) as the main, or the sole
constituent of the suspending medium. The suspension will normally
contain stabiliser(s), and may also incorporate various other relatively
minor constituents (e.g. colourants, fillers, etc.). *
A PVC paste is also often called a plastisol, the two terms being
treated as completely synonymous. * In view of this very common
usage, the question whether they are properly interchangeable is
largely academic, although it should be noted that pastes incorporating
* Although the term 'paste' is quite common in the UK, it is not included in
the main relevant English-language nomenclature standards (ISO 472-1979;
BS 1755: Part 1: 1967; ASTM D 883-80) all of which define 'plastisol' and
'organosol' .
939
940
W. V. Titow
21
941
942
W. V. Titow
substantially monodisperse suspensions in which there is no appreciable interaction between the suspensoid and the medium, those are
indeed the two governing factors, and such systems closely obey
Einstein's expression:
'TJs
'TJo
= 1 +2.5cp
(1)
where 115 and 110 are, respectively, the viscosities of the suspension and
the suspending liquid and cp is the volume fraction of the suspensoid.
The ratio 1151110 is the relative viscosity (11r).
At suspensoid volume fractions higher than about 0025 the relative
viscosity predicted by the above relationship rapidly becomes much
lower than that actually observed. Other more complicated expressions
of a similar nature, e.g. the modified Einstein equation:
'TJs - 'TJo
'TJo
= 2.5cp + 14.1cp2
(2)
(l+05cp)1/2
125cp
1
exp - -cp
1 -cp
(3)
have been shown by Johnston and Brower'! to give a better fit with
actual experimental results, but even with those the viscosity values
predicted for suspensoid volume fractions over about 02 decreased
sharply and progressively in comparison with actual experimental
figures. 3
21.2.2 Main Compositional Factors Influencing the Apparent
Viscosityt of PVC Pastes
At this point it will be useful to list the important compositional
characteristics of PVC pastes which distinguish them from the simple
suspension system so far considered, and complicate their theoretical
treatment as well as the rheological properties in practice.
(i) In PVC pastes the suspensoid volume fraction can be quite high
(considerably in excess of 02); it will also be particularly high in
rigisols, and in plastisols to which 'extender' polymers have
been added. The latter are non-paste-making PVC polymers of
* Originally derived for the viscosity of rubber latices.
t i.e.
21
943
w.
944
V. Titow
=A
;WJ
B
exp [1_
(4)
(1-33-0-84!t)(~)
<Pc
<Pc
<P
(5)
where ({Jc is the critical volume fraction, and other symbols are as
defined above.
21
945
~A
dV/-A-7----='
1
Fig. 21.1
946
w. V. Titow
(7)
This is indeed so for many liquids; such liquids are called 'Newtonian'.
Their behaviour conforms to eqn (7) in which the proportionality
constant (usually given the symbol 'YJ) is called the Newtonian viscosity;
Le. for Newtonian liquids:
T
-=7j
"Y
(7a)
and the graph of r versus y is a straight line of slope 'YJ, passing through
the origin (Fig. 21.2).
Liquids for which the shear rate is not directly proportional to shear
stress (Le. the ratio r/y is not a constant) are called non-Newtonian. In
such liquids the ratio of the shear stress to shear rate varies in some
21
947
Shear
stress
(T)
Shear rate
("y)
- == "'('Y)
'Y
(8)
or with time at constant shear rate, i.e. r:ly == 1jJ(t). PVC pastes belong
to this group.
It is worth noting in passing that the value of the ratio determined
for single, specified values of r: and y is called 'apparent viscosity' and
this is the sense in which this term was used in the preceding section.
Unlike Newtonian viscosity which is a constant, apparent viscosity
values will depend on the shear rate. In practical terms this means
that a PVC paste will flow (or spread, or drain) differently in
processing according to the amount of shear it is experiencing.
The relationship between r:lyand yor time (i.e. the nature of 1jJ(y)
and 1jJ(t) , or the manner of variation of apparent viscosity with shear
rate and time) in non-Newtonian fluids can assume various more or
less complex forms, corresponding to certain known types of
rheological behaviour. Those most important or common in PVC
pastes will now be briefly mentioned.
'BINGHAM BODY' BEHAVIOUR
(9)
948
W. V. Titow
Shear
stres/s
(T)
Yield
value
Shear rate
(1')
Where the apparent viscosity rJa( = -r/y) changes with the rate of shear,
the function (-r/y) = 'ljJ( y) (cf. eqn (8) above) is a power function which
may be written in the form: 9
rJa = Kyn-l
(10)
where the value of n in the power index reflects the nature of the
rheological behaviour. As can be seen, if n = 1 the apparent viscosity
will be constant and therefore the behaviour Newtonian. With n > 1
the shear stress and the apparent viscosity will increase with increasing
shear rate (see Fig. 21.4(a) and (b), respectively). Such behaviour is
known as shear thickening or dilatancy.
With 1 > n > 0 the shear stress and the apparent viscosity will
decrease with increasing shear rate (see Fig. 21.5(a) and (b),
respectively). This behaviour, which is the opposite of dilatancy, is
known as shear thinning or pseudoplasticity. Pastes with high polymer:
plasticiser ratios tend to be dilatant, especially in process conditions
involving high rates of shear. This may, for example, make them
difficult to spread in a coating process, but will also counteract
21
949
Apparent
viscosity
Shear
stress
(77 8 )
(T)
Shear
stress
Apparent
viscosity
(T)
(77a)
Shear rate
("y)
Shear rate
("y)
W. V. Titow
950
Shear
stress
(T)
or
Apparent
viscosity
(71a)
Time
Fig. 21.6 Thixotropic behaviour: the shear stress and apparent viscosity
decrease with time.
as thixotropy and rheopexy (also sometimes termed negative thixotropy
or antithixotropy): they are illustrated in Figs 21.6 and 21.7.
An example of thixotropic behaviour is 'non-drip' paint which will
spread and flow on stirring and/or brushing, although it is gel-like when
not worked. The viscosity of thixotropic PVC pastes (which may
appear to thicken excessively on storage) may similarly be reduced by
stirring. Pastes thickened as a result of true ageing cannot, of course,
be restored in this way.
Rheopectic behaviour is also sometimes observed in PVC pastes.
Figures 21.3 to 21.7 are schematic illustrations of the main general
types of behaviour mentioned here. Explanations and discussions of
these phenomena (which are not of course exclusively associated with
PVC pastes) abound in the literature, textbooks and reference books;
see, for example, accounts by Mendelson,11 Lodge,12 Reiner 13 and
Shear
stress
(T)
or
Apparent
viscosity
Time
Fig. 21.7 Rheopectic behaviour: shear stress and apparent viscosity increase
with time.
21
951
952
W. V. Titow
polymer particles which swell and merge, first loosely and then
progressively more fully, until-if the temperature is sufficiently high
and the time adequate-the process culminates in complete mutual
solution of polymer and plasticiser with the formation of a
homogeneous plasticised PVC melt: on cooling this solidifies into the
familiar plasticised PVC material. Overall, the transformation may be
regarded as a phase inversion: a change from a suspension of
particulate polymer in the continuous phase of liquid plasticiser, to a
dispersion (solution) of plasticiser in a continuous polymer matrix,
solid at room temperature.
.
It is usual to distinguish two main, consecutive stages in the
transformation-gelation and fusion of the paste.
Note: Either of the two terms (and particularly 'gelation'), has
sometimes been used to denote the whole transformation
process. However, with better understanding of the phenomena concerned, usage has progressively tended to conform with definitions which may be formulated on the
following lines.
Gelation (or gelling) of a PVC paste is the process whereby
absorption of the plasticiser(s) by the polymer particles, which is the
first major consequence of heat treatment (or sometimes the result of
drastic ageing), brings about the formation of a relatively weak gel. The
state attained by the material with the formation of the gel is also
sometimes referred to as 'gelation'. This state may be considered to
exist until further heating results in fusion.
Note: ASTM D 833-80 defines 'gel' in this context as 'a state
between liquid and solid that occurs in the initial stages of
heating, or upon prolonged storage'.
Fusion is the process whereby (or the state attained when), as a
result of heating, the polymer particles of a PVC paste, permeated by
the plasticiser(s) which they have entirely absorbed, become fully
merged to form a physically homogeneous plasticised PVC material
with mechanical and other properties developed to the full.
Thus the gelation and fusion of a PVC paste are marked by
morphological changes, which are paralleled by changes in properties.
From the practical standpoint of industrial processing and use of pastes
and their products, the properties are of more immediate significance
than the morphology. Even for the purposes of more fundamental
21
953
954
W. V. Titow
containing between 50 and 100 phr DOP are shown in Fig. 21.8 by way
of general illustration. The same investigators also used a balance
rheometer (the Contraves instrument) to follow changes in the
viscosity, shear modulus and loss angle of their plastisols. The viscosity
effects are illustrated in Fig. 21.8 and shear modulus changes in Fig.
21.9: the fusion points as indicated by the curve peaks for each of the
two properties are fairly close for one and the same plastisol. The
authors noted that the temperature position of the fusion peaks did not
appear to be dependent on the nature of stabilisers or other additives
in the plastisols. Other equipment used to investigate changes in
viscosity of pastes undergoing gelation/fusion on heating included the
Brookfield viscometer, 26-28 and the Bendix Ultra Viscoson
viscometer. 29 An oscillatory, parallel-plate rheometer (Rheometrics
..'"
Q.
1'0
";e
Ui
..-
.o
u
.;
::>
CI'
'"
o 3
.J
05
50
100
T~mp~ratur~
150
, 'C
21
955
'l'e
u
'"
"
::I
"Eo
01
...J
50
100
150
Tqmpqraturq. C
200
Fig. 21.9 Shear modulus versus temperature for the three plastisols of Fig.
21.8 during gelation and fusion in a Contraves balance rheometer. Conditions
and coding as for Fig. 21.8. One sample (PE 709) cooled to 120C after fusion
and then reheated. (Reproduced from Ref. 25 by courtesy of the editor of
Polymer Engineering and Science.)
Mechanical Spectrometer)* was employed by Nakajima et al. 30 to
follow the effects of heating not only on the viscosity but also on the
elastic and loss moduli of a plastisol, in the temperature range
55-195C. Some of their results are shown in Fig. 21.10.
The rate of the morphological transformations involved in the
gelation and fusion of a PVC paste, as well as the actual temperatures
at which distinguishable phases of the overall process will occur in a
particular case, depend principally on the nature of the PVC polymer
and plasticiser(s) and the resultant compatibility between them (often
simply referred to as plasticiser compatibility). A general outline of
plasticiser/polymer interactions in processing is given in Chapter 5
* As is pointed out in the second paper of Ref. 30, viscoelastic
measurements carried out with this apparatus on gelling and fusing paste do
not suffer from two shortcomings to which torque rheometer measurements
are subject. Thus, although the torque rheometer provides a good 'fingerprint'
of the gelation/fusion process, it subjects the material to mechanical working
(not experienced in most cases of industrial processing), whilst the torque
values alone give no indication whether the material is in a rubbery or a more
fluid state.
W. V. Titow
956
W : 0628 rad
sl
...
Q.
;,
"..c
G'
10
12
TimG,min
14
16
18
20
21
957
=
I:
:0
to-
958
w.
V. Titow
lowering the gelation and fusion temperatures for the same duration of
heat treatment, or reducing treatment times at the same temperatures,
by substituting some or all of the plasticiser in the formulation with one
of higher compatibility (e.g. a general-purpose phthalate with a triaryl
phosphate) if other processing requirements (e.g. paste rheology,
which is also affected by plasticiser compatibility-see Section 21.3.2),
cost considerations, and ultimate service performance requirements do
not preclude such substitution.
The end of the steep rise of the viscosity, torque and modulus curves
of Figs 21.8 and 21.9, marked by a small peak in most of these plots, is
regarded by some authors25 as corresponding to the 'dry point' in the
gelation process, at which all the plasticiser is assumed to have been
absorbed by the polymer but the strength of the resulting solid material
is still very low. However, some comparative curves published by
Greenhoe,26 who has distinguished and named a number of sub-stages
in the gelation/fusion process, suggest that it is more likely to be the
'gel point', or even possibly the 'haze point' or 'elastomeric point' (in
Greenhoe's nomenclature-cf. Refs 26 and 32, and Chapter 5, Section
5.5)-states reached consecutively at temperatures progressively higher
than the dry-point temperature (but still considerably lower than the
fusion-point temperature).
The next point of interest-and major importance-in the progress
of the gelation/fusion process is the fusion temperature. As already
mentioned, this is the temperature corresponding to the main, final
peaks of the curves of Figs 21.8 and 21.9. The drop in the curves at the
still higher temperatures to the right of this peak has been attributed to
the disruption (melting) of centres of ordered structure (microcrystallites) believed to form in the plasticised PVC polymer (d. Chapter 5,
Section 5.4), and thought-when present-to act in the same way as
microcrystalline regions in naturally crystalline polymers, i.e. as quasi
cross-linking points stiffening the structure. However, as has also been
mentioned, the fusion point indicated by the main peaks of the
viscosity or modulus versus temperature curves does not necessarily
correspond to the development of the highest room-temperature
tensile strength appropriate to the composition. * In many cases that
21
959
960
W. V. Titow
However, some solvent immersion tests for paste products can also
give an indication of the extent to which the state of the material falls
short of complete fusion (as reflected in the time of onset and severity
of solvent attack).34 The clear point test-discussed in Chapter 5,
Section 5.6.1-gives a relative index of the compatibility of a plasticiser
with the PVC polymer: this can be used as an indication of the relative
ease (and to some extent, especially in the light of relevant experience
and background data, the likely temperature) of gelation and fusion of
a paste based on the particular polymer/plasticiser system.
The results of appropriate tests, carried out and interpreted in the
right context, can provide guidance relevant in the formulation and
processing of pastes, but no laboratory test can be a full substitute for
practical production trials.
21.2.6 The Measurement of Viscosity of PVC Pastes
Reference has already been made in the preceding section to the role
of viscosity measurement as an important technique in the study of the
gelation and fusion of PVC pastes, and to the equipment employed for
this purpose.
Another important application of viscometry in PVC paste technology is its use in the determination of rheological properties relevant to
such aspects of industrial production as paste formulation and quality
control (including evaluation of ageing characteristics), applicational
suitability, and trouble-shooting. Two types of viscometer are of
particular interest in this connection-the Brookfield rotational
viscometer (for determination of the apparent viscosity of pastes at
relatively low rates of shear) and the Castor-Severs viscometer (an
extrusion rheometer used for apparent-viscosity determinations at high
shear rates).
The Brookfield instrument measures viscosity in terms of the
arresting torque on a spindle rotating in the composition under test.
The models used with PVC pastes (RV and LV) are available in a
number of variants (e.g. RVF, RVT, RVT-lOO, LVF)35,36 offering
different (though overlapping) spindle speed ranges: those recommended by the relevant ASTM standard36 are models RVF and LVF.
The combination of spindle size (designated by a number) and spindle
speed-which should be chosen in accordance with the viscosity
characteristics of the material and the desired precision of measurement-should be stated when quoting the 'Brookfield viscosity' of a
21
961
y = 4WI!r?pt
962
W. V. Titow
21
963
W. V. Titow
964
100000
Polym~r
/ plasticisar
80000
Q.
,., 40000
'iii
..
o
':>
20000
10
20
30
./.
40
50
60
70
60
90
100
...
A.
>-
'w
..
o
10000
.!!
>
5000
Ag. of
10
IIlStl,
15
days
21
965
21.3.2 Plasticisers
In addition to the properties important from the point of view of
end-use, which are discussed in Chapter 7, the choice of plasticiser for
pastes is governed by the paste viscosity and general rheological
characteristics which the plasticisers will impart; this includes also the
gelation and fusion properties, as has been illustrated in Section 21.2.5.
In addition to the studies of these effects already mentioned in that
section, there are several earlier publications on the effect of
plasticisers on the rheology of pastes. 43--47
Other factors being equal, the initial viscosity of the paste is
significantly influenced by the bulk viscosity of the plasticiser(s), but
this may be overshadowed by the effect of plasticiser affinity (solvating
power). As would be expected in the light of the relevant considerations already discussed, highly solvating plasticisers will normally tend
to produce higher paste viscosities. In those normal pastes which are
subject to appreciable ageing effects, the main viscosity increase will
commonly take place within a few hours from the completion of
mixing; it is therefore reasonable to measure paste viscosities for
routine control purposes 12-24 h after preparation.
As has been mentioned in Chapter 7, a plasticiser mixture will
normally impart to the compound physical properties and end-use
characteristics intermediate between those imparted by its individual
components. This is so also in pastes where, moreover, the principle
extends to such properties of the liquid pastes as flow properties and
ageing characteristics. An illustration of this is provided by the
examples in Table 21.1.
The effect of some individual plasticisers on the viscosity of PVC
pastes is illustrated by Table 21.2.
Solvating power of plasticisers as a factor in paste ageing is discussed
in a paper by Bigg and Hill. 49
The following further comments may be made on the effects of
various plasticisers in pastes.
In general, the phthalate plasticisers give medium-viscosity pastes,
with low to medium setting (gelation) temperatures. Most phthalates,
and especially general-purpose Cs phthalates, impart some thixotropy
to the paste even when used alone in a relatively low concentration
(down to about 50 phr) so that the paste is very viscous. This feature is
useful where pastes are required which will not flow easily without
being worked (i.e. without shear), but which must spread readily under
w. V. Titow
966
TABLE 21.1
Viscosity of Pastesa with Mixed Plasticisers48
Plasticiser composition
DOP-l00%
DOP- 90%: Polyester (Flexol R2Hy
DOP- 80%: Polyester (Flexol R2H)
DOP- 70%: Polyester (Flexol R2H)
DOP- 90%: 1TP
DOP- 80%: 1TP
DOP- 90%: Chlorinated paraffin
(Halowax 4004Y
DOP- 80%: Chlorinated paraffin
(Halo wax 4(04)
DOP- 70%: Epoxy compound
(Paraplex G60)d
30days b
223Ibfin- 2
30days b
18h 30days~
18h
30 days
l8""h
10%
20%
30%
10%
20%
10%
100
141
246
259
123
133
158
175
196
351
351
196
186
214
175
1-40
143
136
160
137
135
100
174
344
309
217
213
173
145
281
354
398
295
301
202
145
161
103
129
136
141
117
20%
158
196
124
186
217
1-17
30%
175
205
116
149
186
125
TABLE 21.2
Effect of Plastieisers on Ageing Characteristics of Pastes (ICI 'Come'
Polymer)
Plasticiser
Viscosity
(Gardner)
1 day 28 days
DBP
DAP
DOP
Bisoflex 791 a
DNP
TIP
TXP
TOP
DAS
HexapLas PPL b
HexapLas PPA
B.P. Chemicals.
ICI.
Too viscous
72
120
80
124
68
110
69
69
410 1200
320
480
13
48
6
4
1030
300
Too viscous
21
967
968
W. V. Titow
and fusion may be required, such higher phthalates as DDP and DLDP
should be considered: their comparatively low solvating power also
confers good ageing stability on the paste.
The strong solvating ability of triaryl phosphate plasticisers accounts
for the fact that their inclusion in a paste formulation makes for
increased viscosity and, in most cases, dilatant behaviour. At the same
time they promote rapidity and ease of gelation and fusion, and their
tolerance of extenders is good.
The 'low-temperature' (aliphatic diester) plasticisers lower the paste
viscosity, very considerably in some cases (e.g. DIDA; some 'nylon
acid' esters-d. Section 21.4.2), and impart thixotropic properties
(some dialkyl sebacates and adipates are particularly effective). The
ability of several members of this group to promote a large drop in
paste viscosity with increasing temperature makes them useful in
formulations for rotational casting. Pastes containing aliphatic diesters
(normally-in view of their secondary-plasticiser character-as one
component of the plasticiser system) tend to have good ageing
resistance and relatively high setting temperatures.
Epoxy plasticiser/stabilisers are employed in pastes for the same
end-use effects as in solid compounds. Some (epoxidised soyabean
oil) will generally tend to increase paste viscosity, whilst others (epoxy
alkyl esters) normally have the opposite effect.
Polymeric plasticisers tend to give fairly high viscosity and may
promote dilatancy. However, the ageing properties imparted are good.
These plasticisers are used in pastes essentially for the permanence of
properties in end-use which they confer.
Crosslinkable and polymerisable plasticisers have a special application in some pastes, where their use permits a relatively low initial
viscosity to be combined with conversion to a semi-rigid or even fully
rigid ultimate product. However, their incorporation in paste formulations gives rise to special considerations. Unless radiation can be used
as a means of effecting polymerisation or cross-linking of the plasticiser
in the fused product (and this additional treatment, usually expensive
in any case, may not be practicable) an initiator or cross-linking agent,
commonly a peroxide, will usually be included, and this may affect
the stabiliser system or have some effect on properties. These specialist
* Proprietary product of ICI: see Chapter 6, Section 6.5.5.
21
969
21.3.3 Stabilisers
In this respect the service-suitability aspect of paste formulation is very
similar to that of solid compositions, whilst the effects of stabilisers on
paste rheology are associated largely (though not exclusively) with
their physical state: liquid stabilisers and stabiliser systems are used
where the least effect on the flow properties (minimal viscosity
increase) is desired.
A comparison of some common stabilisers in a paste compound
(Breon P13011, 100 parts; TIP, 33 phr; DOP, 33 phr; stabiliser,
167 phr) on the basis of the Congo Red test is given below.
Dibasic lead phosphite
Basic lead carbonate
Calcium stearate
Barium ricinoleate
Lead stearate
Cadmium stearate
Control (no stabiliser)
39
27
19
14
970
w.
V. Titow
21.3.4 Fillers
Fillers are included in pastes for the same end-use purposes as in solid
compounds, but their effects on paste rheology and ageing characteristics must be considered, as most can increase the viscosity and reduce
the shelf life of the paste, or modify the response to shear. Films and
coatings produced from filled pastes are usually less tacky and harder
than those made from unfilled ones, but other physical properties may
be inferior. In some cases the optical effects of a filler in the finished
product are particularly important, e.g. the achievement .of the correct
degree of translucency to impart a life-like appearance to pastemoulded PVC dolls.
Other factors being equal, paste viscosity tends to rise with
increasing filler loading and with decreasing particle size. The former
factor increases viscosity partly as a result of the increase in the
particulate phase content (and modification of its size distribution) in
the paste (cf. Section 21.2.4), and partly because more particles are
available to adsorb some plasticiser onto their surface. Particle size
reduction also increases plasticiser adsorption by the filler because the
specific surface (surface-to-volume ratio) goes up. The surface
adsorption effects can be considerably modified if the filler particles are
coated (see Chapter 8, Section 8.3.2). The amount, distribution and
chemical nature of the coating all play their role, the most common
overall effect being a reduction of plasticiser adsorption-and hence of
viscosity increase-by the presence of the coating. Some of the effects
of organic titanate coatings on fillers upon the viscosity and other
properties of filled PVC pastes are discussed in a paper by Monte and
Sugerman. 51
21
971
TABLE 21.3
on Absorption of Fillers
Filler
Barytes
Slate powder
Dolomite
Whiting
China clay (medium fine)
China clay (very fine)
Silica
Water-ground mica
35
55
42
79
None
Calcined clay
Blanc fixe
Ppted CaCO/
Ppted CaC0 3c
Barytes
Diatomaceous earth
Lithopone
0
20
31
21
20
34
18
33
10000
17000
15000
18000
40000
7000
40000
40000
2400
2050
2250
2100
2250
2220
1900
1750
1000
1125
1100
1000
1100
950
1175
1000
350
340
320
350
370
420
270
320
66
38
36
45
16
148
37
a Breon P1301l, 100 parts; DOp, 667 phr; filler as shown (each weight represents a
volume equivalent to that of 20 phr calcined clay).
b Low oil absorption grade.
c High oil absorption grade.
W. V. Titow
972
1500
Sturcal L
_ - - - - - - - - 3 3 phr
_ - - - - - - - - - - C a I O f i l A.4
33phr
ll.
>,
....
"iii
ou
III
:>
__
---------Sturcal L
8phr
~_ _- - - - - - - - - - - - C a l o f i l A.4
8phr
__------------NO filhzr
10
TimlZ, days
15
Fig. 21.14 Effects of two CaC03 fillers on viscosity of a PVC paste. Sturcal L
(John E. Sturge Ltd), medium oil absorption filler; Calofil A4 (John E. Sturge
Ltd), low oil absorption, resin-coated filler.
Paste formulation:
PVC resin (Breon P130/1)
DOP
TIP
Filler
Stabiliser (white lead paste)
lOOpbw
33 phr
33 phr
as shown
1.7 phr
21
973
974
w.
V. Titow
A
100
40
40
4
6
100
100
80
55
4
6
4
As required
25
25
4
21
975
The gelled material has the same good ageing properties as normal
PVC compounds.
21.3.6 MisceUaneous Paste Components
These include the following.
(a) Viscosity Depressants
These are used when it is essential, for end-use properties, to employ a
particular plasticiser system and plasticiser: polymer ratio which at the
same time give unduly high paste viscosities. Viscosity depressants are
usually surface-active agents of various kinds. The effect of a particular
depressant in a particular formulation cannot be entirely predicted and
therefore tests are necessary. Most viscosity depressants also retard the
ageing of the paste. These compounds are added in low quantities (of
the order of 1%) in order not to upset the formulation, and to avoid
exudation. Polyethylene glycols and Lubrol MOA (non-ionic surfaceactive agent: fatty alcohol/ethylene oxide condensate-ICI) are
examples.
(b) Diluents
These are usually organic solvents producing a thinning effect on the
paste, and are mainly used in organosols (see Section 21.4.1).
Organosols
976
W. V. Titow
21.4.2 Rigisols
As mentioned in Section 21.1, these are plastisols specially formulated
to achieve low viscosity for processing, but combining this with high
polymer content and hence rigidity of the ultimate products. The
factors which are adjusted and controlled to achieve this result are the
following.!
(i)
21
977
t Ciba-Geigy.
978
W. V. Titow
REFERENCES
1. Goodier, K. (1960). Proceedings of the International Congress on the
Technology of Plastics Processing, Amsterdam 17th-19th October, N.C.
V't Raedthuys, Amsterdam.
2. Ciba-Geigy Technical Service Bulletin PL 3.3 (1975).
3. Johnston, C. W. and Brower, C. H. (1970). SPE J., 26(9), 31-5.
4. Underdal, L., Lange, S., Palmgren, O. and Thorshaug, N. P., (1978).
'PVC paste technology and polymer characteristics', paper presented at
the PRI International Conference on PVC Processing, Egham Hill, Surrey,
England, 6-7 April, 1978.
5. Bjerke, O. (1966). 'Relation between the distribution of size of the
primary particles and the rheological properties of PVC plastisols', SCI
Monograph No. 26, pp. 370-80.
6. Ram, A. and Schneider, Z. (1970). Ind. Eng. Chem., Prod. Res.
Develop., 9(3), 286-91.
7. Mooney, M. (1951). J. Colloid Sci., 6, 162.
8. Eilers, H. (1941). Kolloid Z., 97,313.
9. Breon Pl30II Paste Resin. (1969). BP Chemicals International Ltd.,
Technical Manual No.2, pp. 5-10.
10. Cawthra, c., Pearson, G. P. and Moore, W. R. (1965). J. Plast. Inst., 33,
39-44.
11. Mendelson, R. A. (1968). Encyclopedia of Polymer Science and
Technology, Vol. 8, (Eds H. F. Mark et al.), Interscience, New York, pp.
588-90.
12. Lodge, A. S. (1964). Elastic Liquids, Academic Press, New York, pp. 228,
246-8.
13. Reiner, M. (1960). Lectures on Theoretical Rheology, North Holland
Publishing Co., Amsterdam.
14. Fredrickson, A. G. (1964). Principles and Applications of Rheology,
Prentice-Hall Inc., New York, pp. 27, 142-4.
15. Gillespie, T. (1966). J. Colloid Interface Sci., 22,554-9.
16. Hoffman, R. L. (1974). J. Colloid Interface Sci., 46,491-7.
17. Strivens, T. A. (1976). J. Colloid Interface Sci., 57,476-80.
18. Rangnes, P. and Palmgren, O. (1971). J. Polym. Sci.-Part C, 33, 181-7.
19. Thinius, K., Reicherdt, W. and Hosselbarth, B. (1963). Plaste u. Kaut.,
10,339-41.
20. Goodrich, J. E. and Porter, R. S. (1967). Polym. Engng. Sci., 7, 45-8.
21. Lee, G. C. N. and Purdom, J. R. (1969). Polym. Engng. Sci., 9, 360-;;.
22. Schreiber, H. P. (1970). Polym. Engng. Sci., 10, 13-15.
23. Shah, P. L. and Allen, V. R. (1970). SPE J., 26,56-60.
24. Buckley, C. D. (1971). J. Cell. Plast., 7,23.
25. Cayrol, B., Klason, C. and Kubat, J. (1974). Polym. Engng. Sci., 14(12),
868-72.
26. Greenhoe, J. A. (1961). Plast. Technol., 7(2), 35-8.
27. Hoy, K. L. (1966). J. Appl. Polymer Sci., 10(12), 1871-93.
28. Johnston, C. W. and Brower, C. H. (1966). SPE J, 22(11),45-52.
29. Alter, H. (1959).1. Appl. Polym. Sci., 2(6),312-17.
21
979
CHAPTER 22
22.1 INTRODUCTION
22.1.1 Preparation
In the early days, with old-type resins,. grinding was essential to
produce satisfactory pastes. With modern paste polymers 'stir-in'
techniques in good mixing equipment are effective. The method and
equipment used in the industry for paste preparation are discussed in
considerable detail in Chapter 13 (Sections 13.4.3 and 13.4.4(f)).
The use of an effective mixer and proper technique should ensure
that the paste is free from lumps, with all constituents uniformly
distributed, and not excessively aerated (to facilitate the postpreparative de-aeration which will usually be carried out). Of the two
possible general modes of operation, continuous mixing is in practice
confined to industrial processes: batch mixing is practised on both
industrial and laboratory scale. Modern equipment (e.g. a planetary
mixer) makes it possible to prepare a satisfactory paste batch in a
one-step operation, and versions of this kind of technique are laid
down in standard specifications (ISO 4612-1979; DIN 54800-1979) for
the preparation of standard pastes to be used in the control and
evaluation of formulation factors (especially the nature of the PVC
resin) and the rheological properties of pastes. However, this does not
detract from the practical value of a good two-stage method of paste
preparation, especially for low-viscosity pastes, both in the laboratory
and for production purposes. The following is a brief, general outline
of one such method.
981
982
w.
V. Titow
22
983
984
W. V. Titow
985
n3
35
...
30
..
25
.!
20
15
'j
-..
10
5
o ---- \
)(
x
4-5
25
26
x
HI
1"4
160
170
180
190
x
2-3
)(
22
200
OVln tllllperltlill
)(
33
32
I
210
220
230
240
(C l
fusion. The curve constituting the boundary between the two regions is
thus the locus of the minimum time/temperature conditions for
complete fusion in the particular process. The steeply rising portion of
this curve may be regarded as asymptotic to the 172C temperature
line: this indicates that 172C is the minimum temperature for
complete fusion of the paste (and in the conditions) used.
Figure 22.1 also demonstrates that the test is sensitive enough to
distinguish between degrees of fusion where fusion had not been
complete. This is shown by the fact that the times to flaking increase
with increasing oven temperature and with increasing oven time.
986
W. V. Titow
22.2 APPLICATIONS
22.2.1 Rotational Casting
This is the main process for producing hollow moulded articles (dolls'
heads and body parts, hollow 'squeaky' toys, playing balls, etc.) from
PVC paste, offering several advantages over slush moulding which is
the alternative method (see the next section). The development of
rotational casting began around 1950, and the first descriptions of
machinery4-6 are of that vintage. The principles and early practice of
this process were described by Meazey.7
Modern rotational casting equipment, of various sizes, numbers of
moulds and capacities, is available from several manufacturers in the
UK, USA and Europe, most of whom will be found in the current
editions of the relevant directories. 8
Rotational casting (also known as rotary casting, roto-casting, or
rotational moulding) has gained popularity for the following reasons,
most of which represent advantages over slush moulding. Rotationally
moulded hollow articles can be produced with uniform wall thickness
and fine surface detail, from a pre-metered amount of paste. Virtual
absence of flash minimises trimming operations, and the amount of
material waste is also minimal. The equipment and operation are
automated to a large extent, whilst the capital expenditure on
machinery and moulds is moderate by present-day standards.
The principle and basic process of rotational casting are simple,
although in their modern embodiments the equipment and technique
have attained considerable sophistication and versatility. Typically,
multiple moulds-earried on one or more arms indexed to move
between operational stations-are each charged with the appropriate,
metered amount of paste at the filling station, and closed. Transfer to
the heating/cooling station follows, the moulds being spun in one plane
and simultaneously rotated at right angles to the spin direction at the
outset and throughout the heating period. The heat treatment takes
place in an oven powered by electricity, gas or oil, employing hot air or
IR radiation as the heating medium. The complex two-directional
rotation of the moulds spreads the paste evenly over their interior
surfaces, where it is gelled and fused by the heat. The rotary
movement is continued during cooling (by an air stream and/or water
spray) in a cooling chamber, after which the moulds are returned to
the filling station where they are unloaded prior to the commencement
987
of the filling step of the next cycle. A typical cycle time may be about
15 min. Spinning rates of 5-16 r min- 1 are fairly representative, with
the ratio of these to the rotation rates between about 1: 1 and 1 :4. For
a given product, the best rates and their combinations are established
on the basis of trials. Simple moulds can be quite satisfactory, made by
the electrodeposition technique (e.g. nickel on copper for good release
properties and thermal conductivity), or cast or machined in
aluminium.
Some rotational mouldings (e.g. playing balls) are inflated after
manufacture with air introduced through a hypodermic needle, the
resulting hole being heat-sealed. Rotationally cast products may also
be filled with foam generated from a polyurethane composition poured
in through a hole foamed in situ whilst the hollow moulding is
supported in a retaining mould. This method has been widely used in
the production of car arm-rests with outer 'skins' rotationally moulded
from PVC paste. However, in that particular application, it is being
strongly challenged by essentially one-step moulding of the arm-rests in
structural polyurethane foam. The following basic formulations
illustrate the kind of pastes used for some rotationally cast products.
Rotational casting formulation for soft dolls or playing balls (paste
viscosity about 12P):
l00pbw
40phr
50phr
3phr
50pbw
50pbw
25 phr
3phr
2phr
t Suspension resin
988
W. V. Titow
70pbw
30pbw
50phr
lOphr
2phr
15 phr
2phr
22
989
990
W. V. Titow
Plasticisers: DIOP
Pliabrac 810
Stabiliser:
Colourant:
70pbw
30pbw
55phr
15phr
3phr
075 phr
Blue Masterbatch C
PVC resin:
Plasticiser:
Stabiliser:
Colourants:
Corvic P65/54
DNP
Calcium stearate
Reckitt's:
ultramarine blue M 6925
blue 8651
100pbw
60phr
4phr
1 phr
2phr
991
992
W. V. Titow
993
result-ideally the rate should be the same as that at which the paste
drains off. Not much heat should be left in the object: the final fusion
is effected in a separate step. 'Dip marks' (paste drips) usually formed
at the bottom of the article may be brushed off before the heat
treatment for fusion. This will be appropriate to the paste composition,
coating thickness and other relevant process factors. An under-fused
coating which may appear matt and be weak or even crumbly, may be
returned to the oven for further treatment, providing that the fault is
not due to the oven temperature being generally below the minimum
necessary for complete fusion.
Articles PVC-coated by the hot-dip process include fence posts and
fittings, handles, thick wire baskets and trays, mounting brackets and
the like.
(b) Hot-dip Moulding
This process is closely similar to hot-dip coating, except that the object
being dipped is a suitably shaped metal former (which may be treated
with a release agent), and the coating becomes a hollow moulding
when it is stripped from the former after fusion and cooling.
Two procedural variants are in use. In one, the formers are
pre-heated in an oven and dipped into the paste in the dipping tank at
a controlled rate: this is usually quite fast (say about 10 s to submerge
the former to the required depth) to avoid differential cooling with
consequent uneven paste layer build-up. The immersed formers are
left for the time necessary for the coating layer thickness required: this
residence period may be quite short. They are then withdrawn at a
uniform rate (normally slower than the dipping rate) so regulated as to
avoid excess paste being dragged out of the bath through viscosity
effects. Once out of the bath, the formers are inverted to let any drips
merge back into the coating layers, and transferred to a second oven to
fuse the coatings. This treatment is followed by cooling (which may be
forced), stripping, and any trimming operations that may be necessary.
The second variant involves the same dipping and withdrawal
procedures, but the pre-heating of the formers and gelation/fusion of
the paste coatings picked up are both done by immersing the formers
in a tank of a liquid heating medium. More effective heating for
shorter periods (e.g. completion of gelation and fusion about 2-3 min
in many cases) are claimed as the main advantages over the method
involving oven heating, with consequent faster cycles and reduced
994
W. V. Titow
22
995
between the two, are household clothes lines and some types of cords
and ropes.
Cold-dip coating of metal objects-where there is no surface
anchorage effect of the kind afforded by a fibrous substrate-is
generally more difficult to operate and control than the hot-dip
process. A low-viscosity, non-dilatant paste may be used to build up
the required coating thickness, by multiple dipping, from a number of
thin layers, each pre-gelled before the application of the next one. In
this kind of procedure enough heat must be applied at each gelling step
to soften the previous coat sufficiently to ensure good merging with the
one undergoing gelation. The combined layer is ultimately fused as a
whole in a final heat treatment. In some cases a one-dip coat may be
given with a viscous paste formulated to be strongly thixotropic at the
relatively low shear rates involved in the dipping process: such a paste
will 'set-up' in the form of a fairly thick coating, with very little
draining, directly after withdrawal from the tank.
996
W. V. Titow
100pbw
65phr
16phr
2phr
22
997
2000 lbf in- z, to force the paste through a small spray orifice (typically
OOB-in bore) and thereby obtain the right atomisation.
Electrostatic spraying of PVC paste may be carried out by either of
the above two general methods, with appropriate arrangements for
charge generation. This mode of operation, which is particularly useful
with metal objects, can offer economies in paste consumption and
coating time: uniformity of coating of intricately shaped surfaces is
another advantage of a properly run electrostatic spray-coating
process.
Problems which may be experienced in spray coating with pastes are
generally similar to those encountered in paint spraying. Some of the
more common ones are: a 'pebble' finish caused by excessively high
line pressure or the gun being held too far from the work; runs which
may form if the gun is too close or the paste too fluid; wrinkles or sags
on vertical surfaces where the coating has been applied too thickly.
After spraying, the coating is gelled and fused by a heat treatment.
This may be preceded by drying if an organosol has been used. The
drying temperature should be kept to a reasonable minimum to
prevent bubbling by the departing solvent, and to keep down the
polymer's heat history. The gelation/fusion of coatings on metal
substrates may take about 5-10 min at an oven temperature of around
180aC. Higher temperatures may be used to shorten the time, but
caution is necessary, as hot spots can develop (especially in a large
oven) which can lead to local overheating.
The following are two examples of basic formulations for spraycoating pastes:
Plastisol
PVC resin:
Plasticisers:
Stabiliser:
Corvic P 65/54A
DAP
DNP
Paraplex G62
Stanclere80(AKZO, Chemie, Sarl, France)
100pbw
40phr
50phr
2phr
075 phr
Breon P 130/1
DOA
Mellite131 (Albright and Wilson Ltd, UK)
MIBK
white spirit
TiO z paste (1 : 1 in DOP)
100pbw
25phr
2phr
15phr
15 phr
5phr
Organosol
PVC resin:
Plasticiser:
Stabiliser:
Solvents
(diluents) :
Pigment paste:
998
W. V. Titow
22
999
1000
w. v.
Titow
l. I
E
Fabrics: as D
Typical uses
May be angled
(up to about
4)
AsD
Vertical, or
angled up to
3
Usually vertical
Vertical
Usual knife
setting
Remarks
Fig. 22.3 Some common doctor blade profiles: schematic representation. Substrate movement from
left to right. Other factors being equal the amount of coating will increase with increasing radius of the
leading edge of the blade.
r r
$::>
--
-~
.Q.,
$::>
<"'>
:=::-:
).
s::..
;:,
~.
'"
<"'>
C3
"1:l
.r
6'"
i:l
$::>
!OO2
W. V. Titow
22
1003
1004
W. V. Titow
proportion to the chance that a pinhole in the first layer will coincide
with one in the second.
22
1005
1006
W. V. Titow
In this kind of operation, the paste formulated for the skin layer is
spread ('cast') on the surface of strong kraft paper treated with a
silicone release agent. The layer may be gelled before the next
operation, or it may be left ungelled. The next step is to cast a second
layer of suitable foamable paste composition onto the skin layer: if the
latter has been gelled in the meantime, this second step will constitute
a 'wet on dry' application; if not, then the application will be 'wet on
wet'. The second coat (or both if the application has been wet on wet)
is then usually pre-gelled at a temperature low enough not to cause
foaming or excessive hardening. The base fabric is applied to the 'free'
surface of the second coat and fixed in place by a heat treatment which
will gel and fuse the PVC and produce expansion of the intermediate
layer (by activating the blowing agent-see Chapter 25). In another
variant, gelation/fusion and blowing may be accomplished before the
application of the fabric, and a third thin bonding coat of paste
(without blowing agent) may then be applied and the fabric laminated
to this to be finally fixed by heating. In either case the material is then
22
1007
stripped from the paper (with the original first PVC/paper interface
becoming the top surface of the coated fabric).
Where only simple, single-station coating equipment is available, the
wet-on-dry procedure will be followed, each coating step being
effected in a separate passage. In modern large-scale coating practice
the whole process can be carried out on a single line with multiple
coating, heating and cooling stations, and usually incorporating the
facilities and refinements mentioned above in connection with direct
coating. The final stripping of the substrate/coating laminate from the
carrier may also be carried out in-line, or on a separate machine. In
the latter mode of operation faster coating speeds may be possible (say
up to about 500 ft min-I) as stripping is, in general, slower than
coating.
Cellular leathercloth may also be produced by a variant of transfer
coating involving a film lamination step. In this method the foamable
paste is first cast onto the carrier (release paper) and the fabric
applied to this layer (which may be pre-gelled). The laminate is passed
through an oven to foam and fuse the PVC, then through a cooling
station, and the carrier is stripped off. Next a thin layer of paste is
applied to the coating's surface; this paste is formulated (often on the
basis of a vinyl chloride copolymer) to fuse at a relatively low
temperature at which the foamed layer will not collapse. A thin
calendered film, formulated to function as the skin layer of the
composite coating, is then laminated to the assembly and fixed on by a
heat treatment which fuses the thin adhesive layer.
(e) Promotion of Adhesion between Coating and Substrate
The use for this purpose of a tie (bonding) or priming coat has already
been mentioned. Such coats may be applied to a substrate (fabric,
paper, metal) to be subsequently coated by a direct or transfer
method, or to the 'free' surface of a transfer coat deposited (if
composite, assembled) on a carrier prior to the final lamination to the
substrate, or to a film in the film-lamination coating method. In some
cases, especially with direct coating, a priming coat can serve as both a
bonding layer and a barrier restricting penetration into a porous
substrate of the material of the main coat. Such priming costs on paper
or fabric substrates may be thin latex-deposited PVC layers (see
Chapter 23.)
Certain adhesion promoters may be incorporated in the coating
paste. For instance, special liquid isocyanurates (e.g. Vulcabond
1008
W. V. Titow
VP-ICI) have been used as such additives in PVC pastes for coating
nylon and polyester fabrics in the production of tarpaulin and
protective clothing materials.
2pbw
3pbw
5pbw
40pbw
40pbw
22
1009
exposure to sunlight will occur in service, the lacquer may serve, inter
alia, as a vehicle for an extra light stabiliser interposed in this way
between the incident radiation and the PVC coating. Colourants are
also common additives. Matting agents are incorporated in lacquers for
matt finishes. The resin components of a lacquer may also be (or
include) polymers other than those already mentioned, such as
polyurethanes (e.g. Argutop LV), polyamide (e.g. Argutop LN
1060-a high gloss commercial lacquer), or cellulose acetate butyrate
(for surface slip and anti-blocking).
Keying solvents (e.g. cyclohexanone, isophorone, tetrahydrofuran)
may be included in the lacquer formulation for better ultimate
adhesion to the PVC surface, but care must be taken that their
presence does not disfigure the emboss during heat treatment.
Whilst the lacquers have traditionally been solvent-based, aqueous
polyurethane and acrylate systems (colloidal dispersions) have also
made their appearance among the commercial products. Two examples
are Neo-Rez R-900 (Polyvinyl Chemical Industries Inc., USA) and
Laqua WB 240 (Bee Chemical Co., USA).
Lacquers are usually applied by an engraved (gravure) roller or
doctor knife. Special effects may be achieved on embossed surfaces if
the colour of the lacquer is different from that of the coating. Thus,
most emboss patterns may be 'topped' by applying a coloured lacquer
by roller in light contact with the surface so that only the protruding
portions are covered and thereby made to contrast with the
depressions. The speed of passage of the coated, embossed material
under the roll, and its presentation to the roll surface, can be arranged
to deposit the lacquer predominantly on the 'slopes' to one side of the
tops of the raised portions of the emboss. This effect is known as
'shading'. With suitable heavy emboss patterns a coloured lacquer can
also be applied (usually by a doctor blade suitably profiled and set-ef.
the caption of Figure 22.3) so that it is deposited in the depressions,
whilst the tops of the raised elements of the embossed pattern are
wiped substantially clean and thus retain their original colour. This
effect, produced on some leathercloths used for decorative purposes, is
referred to as 'antiqueing' or 'antique finish'.
(g) Testing of Coated Materials
Completeness of fusion of coating may be determined by a solvent test.
In some cases a test of coating-strength properties may be practicable
(e.g. a bursting-strength test on the coated material, or a tensile
1010
W. V. Titow
strength and elongation test on the coating removed from the substrate
with the aid of a leather-splitting machine).
Most of the other tests and determinations commonly carried out on
coated materials, including conveyor belting, will be found in the
standard specifications listed in Section 7.1 of Appendix 1. The
properties of most frequent interest include weight of coating per unit
area, breaking strength (bursting strength with some coated knitted
fabrics), resistance to flexural fatigue, adhesion of coating, abrasion
resistance, tear strength, low-temperature properties of coating
(cold-crack, cold-bend, etc.-see Chapter 12, Section 12.2), water and
air permeability, volatile matter content (cf. also ISO 176-1976; BS
2782: 1970, Method 107F; AS 1441.8: 1973; Canadian Standard
4-GP-149: 1972), the effects of weathering and ageing, and various
performance tests directly relevant to end-use. An early summary of
some test techniques and equipment was published by Dalton,12 and a
useful test for soiling resistance (carried out on an abrasion tester) by
Kratschmann. 13
Note: Resistance of flooring materials to staining by contact with
rubber (shoe soles, ferrules) or shoe polish, and by other
agencies, is assessed in various ways, some used as standard
tests, e.g. by plasticiser manufacturers. 14
1011
soft PVC soles onto the uppers of certain types of cheap footwear.
Fairly typical conditions would be: injection of paste under about
50 lbf in -2 pressure into a mould pre-heated to about 170C and
thereafter maintained at that temperature for the time required to
complete the gelation/fusion of the moulding (normally a few minutes).
Soft sealing gaskets for tin box lids have also been produced by
low-pressure injection moulding. Direct injection of a paste into the
gap of a joint between metal components (inter alia, in vehicle
construction) to act as a caulking medium (after gelation/fusion by
external application of heat) is another example of the application of
this kind of process.
1012
W. V. Titow
REFERENCES
1. Kling, A. (1951). Kunststoffe, 41(8),240-2.
2. Schimke, F. (1956). Kunststoffe, 46(11), 537-9.
3. Titow, W. V. (1958). Investigation into the validity of the claims of British
Patent 624 795 (James North and Sons Ltd). Unpublished.
4. Anon. (1949). Plast. Ind., 7, 11.
5. Anon. (1951). Mod. Plast., 29,87.
6. US Patents 2629131,2629 134 and 2 681 472.
7. Meazey, A. C. (1959). Brit. Plast., 32,55.
8. European Plastics Buyer's Guide, IPC Business Press Ltd, London.
Buyers Guide for Plastics Processing Machinery and Equipment, British
Plastics Federation, (Machinery and Engineers Group), 5, Belgrave
Square, London SWIX 8PH, UK.
Plastics Manufacturing Handbook and Buyers' Guide: Plastics Technology
Magazine, Rubber/Automotive Division of Hartman Communications Inc.
(a subsidiary of Bill Communications Inc.), 633 Third Ave., NY, NY
10017, USA.
9. Meazey, A. C. (1968). Brit. Plast., 41, 133-40.
10. Schmidt, P., and Polte, A. (1967). Kunststoffe, 57(1),25.
11. Clayton, F. R. (1978). 'Printing techniques relating to the gravure
process,' paper presented at the PRI International Conference on PVC
Processing. Egham Hill, Surrey, England, 6-7, April, 1978.
12. Dalton, W. K. (1960). Plastics, 25(268), 71-81.
13. Kratschmann, F. (1960). Kunststoffe, 50(9), 534-5.
14. Ciba-Geigy Technical Service Bulletin PL 1.1.1, 1976.
15. Blumberg, H., Krummheuer, W. and Nebe, J. (1976). Kunststoffe, 66(2),
97-103.
CHAPTER 23
PVC Latices
Revised and edited by W. V. TlTaw
23.1 INTRODUCTION
In the previous edition the nature and properties of PVC latices were
discussed in this chapter principally by reference to one commercial
range of products of this type-the Breon vinyl latices. With the
permission of the suppliers, BP Chemicals International Ltd, the text
was based to a substantial extent on the appropriate part of their
relevant publication (Technical Manual No.5). This was done because
its technical scope and depth of treatment of the subject were
considered to make that part of the manual useful as a good account of
the technical and applicational aspects of PVC latices generally, even
though actual data quoted by way of illustration did relate to members
of the Breon range.
These considerations, and the relevance of the basic technical
information presented, remain valid irrespective of the changes
consequent upon the take-over of BP's PVC production operations by
ICI in the early 1980s. The chapter is, therefore, still essentially based
on the former text, although some editorial changes and additions have
been made. The original references to Breon latices have been retained
in their former role of illustrative examples: whilst other good
commercial PVC latices, e.g. those of the Geon (B. F. Goodrich) or
Lutofan 200D (BASF) ranges, would provide illustrations more
current in the purely commercial sense, it will be understood that
corresponding grades of latices from different sources, and the finished
products of their conversion, all differ among themselves, but none
fundamentally.
1013
1014
W. V. Titow
23
1015
PVC Latices
main processes (extrusion, calendering and moulding of solid compositions; paste coating). All industrially significant uses of PVC latices
involve their application to some kind of substrate, whereupon a deposit
of solid polymer is ultimately formed after the water has been removed
by evaporation (with or without some intermediate absorption into the
substrate). The general mechanism of deposit formation is virtually the
same for all polymer latices 1,2 (including PVC ones-d. also Section
23.4.2 below): it may be regarded as comprising several stages, each
characterised by the corresponding state of the latex layer on the
substrate and the associated changes in the rate of evaporation of the
aqueous phase. 2 The layer of latex as originally deposited on the
substrate (cf. Fig. 23.1(A)) loses water relatively rapidly by evaporation at a rate comparable with that for pure water. This reduces the
water content comparatively quickly to the point at which the layer
consists of polymer particles in fairly loose mutual contact, with the
interstitial spaces containing residual water (Fig. 23.1(B)). In this state
the interfacial area between the water and ambient air is substantially
B
Fig. 23.1
1016
W. V. Titow
1017
23 PVC Latices
151
Homopolymer
351
352
Unplasticised
copolymer
80
52-55
80
54-58
80
55-59
12-28
117-119
20-40
117-119
30-42
117-119
576
599
Plasticised
copolymer
80
55-59
80
54-58
35-55
30-40
112-1-14 112-114
652
Unplasticised
copolymer
70
49--53
7-12
123--125
w.
1018
V. Titow
TABLE 23.2
Physical Properties of Films from Plasticised 'Breon 352' and 'Breon 652'
Heating
temperature
(oc) for 2 min
25
90-100
150
23.2.3
1052
1673
3823
180
270
480
Breon 652
Tensile
Elongation
strength
at break (%)
(lbfin- 2 )
2445
2255
2600
760
620
750
1019
23 PVC Latices
151
351
576
352
599
652
Tensile
strength
(lbfin- 2 )
7075
8030
2140
7575
2115
1360
Elongation at
break (%)
Modulus (lbfin- 2 ) at
elongation
100%
300%
230
1825
860
380
1850
760
500%
10
15
330
20
240
570
1200
23.4 COMPOUNDING
There are two categories of compounding ingredients for vinyl latices:
(i) stabilisers, wetting agents, thickeners, anti-foaming agents and
pH modifiers affecting latex properties;
1020
w.
V. Titow
23
PVC Latices
1021
agent added, thereby increasing the wetting power of the system. This
factor can be advantageous for covering impermeable surfaces and
penetrating fibrous substrates. However, reduced surface tension gives
rise to increased foaming and the higher the level of added surfactant
the greater the sensitivity of the dried film to water. Non-ionic
surfactants, such as ethylene-oxide/fatty-alcohol condensation products, offer the greatest protection against chemical destabilisation and
a degree of mechanical stability. Protective colloids such as casein or
Lytron 820 (Monsanto Co., USA) improve the stability of the latex
under conditions where mechanical shear can cause breakdown of the
emulsion system.
Table 23.1 shows that the minimum recommended pH for Breon
vinyl latices is 7-8. It is important to maintain this level during
processing and ingredients added to the latex must be adjusted to a
minimum pH 8 before addition.
(b) Wetting Agents
Anionic and non-ionic surfactants which efficiently reduce tension
improve wetting characteristics. Those recommended include alkyl
sulphosuccinates and polyoxyethylene alkyl phenol derivatives.
(c) Thickeners
Several types of polymeric substances which form viscous solutions in
water when dissolved in relatively low concentrations, are of interest as
latex thickeners. Among those successfully used with Breon PVC
latices have been cellulose derivatives (methyl cellulose, sodium
carboxymethyl cellulose), polyacrylates (including some sodium and
ammonium polyacrylate salts), and colloidal solutions of casein and
sodium alginate. Different types of thickener, and even individual
thickeners within the same type, can differ considerably in their effects
on a given PVC latex, or on different latices: this is illustrated, by way
of examples, by the data of Figs 23.2-23.7. Some latices can be
adversely affected (destabilised) by certain thickeners. Specific advice
on thickening agents most suitable for use in a particular latex (and its
given application) is available from latex manufacturers. In general,
polyacrylates have been said4 to be particularly useful with Breon PVC
latices, and less prone to causing sedimentation than cellulose
derivatives.
100000
so 000
--_.......
-.- --
..........
I
to 000
e
-. -..
i
...... -..
5000
..
", I
_..I - ._.-..
,~
I __
iiiiiiiit_ _
7;
1-,-
1-_-1-
e-
~,
~:...-
",-.-
_.
.
I
MC (2-5)
MC (1-5)
$CMC (ZS)
MC (0'15)
SCMC '1-5)
SCMC {0'75}
1000
50 0
10 0
Fig. 23.2 Cellulose thickeners in Breon 151. Figures in brackets indicate dry
parts per 100 parts dry polymer by weight. Me, Methyl cellulose; SCMC,
sodium carboxymethyl cel!~lose.
100 000
~
50 000
...
"""Iiii
--...:.:.:
PA (z.s)
/
10000
c::::;;,;;liiii
o....
5000
--
'A (125)
PA (015)
.
u
.;
...
..!
.;
1000
I
I
-1
I
500
I
I
II I
.1
100
I
J
Mltllring lilll. (dlYs II '00
I
I
--
IIr.1pllllllr. ZJ' C)
100 000
50000
-_.-....
10000
~.:.":
.
.....
ii
5000 1---
1--
...
-;
-- - ..
~_.
~.- ~.-
--...-
~-- ~--
MC (25)
MC (15)
MC (015)
SCMC (2'5)
--
SCMC (1-5)
---
SCMC(O'15)
::0
.a
1000
500
100
Fig. 23.4 Cellulose thickeners in Breon 351. Figures in brackets indicate dry
parts per 100 parts dry polymer by weight.
100000
--
50000
"""Iii
10000
--.-...
...o
..
5000
-.r:;..
IL
.-..
- -
10"-
-- =:::
~..:: ..
~j
..-.J--
......
.;
..
APA (H)
SPA (H)
=- -
l--
PA (N)
APA (1'U)
SPA (1-25)
SPA (0'15)
PA (1'25)
APA (075)
PA (OlS)
oM
.;
1000
500
I
100
tOO 000
50000
10000
oN
5000
iii
...
u
~~
1000
--
SCMC (2'5)
SCMC (1-5)
MC (z.s~
SCMC (0 5)
MC (t 5)
.....
-. --
I
I
MC (015)
500
100
tamparatura 23'C I
Fig. 23.6 Cellulose thickeners in Breon 576. Figures in brackets indicate dry
parts per 100 parts polymer by weight.
100000
50000
~.
...
1---
I'
_-..-
-- --
e-
o
N
5000
II.
u
~
.;
o
--- --
----
r-
10000
..-
~;
~_
APA (2-5)
PA (z.s)
APA (1 25)
SPA (1-25)
~--'
PA (1-15)
APA (015)
.sPA (0 7S)
=:=.~
j
SPA US)
..
u
.;:
,,
...
D
~
::Ii
PA (015)
1000
500
i
I
I
100
1028
W. V. Titow
The basic rules for introducing a thickener into a PVC latex are the
same as for other latices. The best dispersion and maximum efficiency
are obtained when the latex is added slowly, under constant, slow
agitation, to a solution of the thickener. An alternative method is to
'masterbatch' the thickener. This involves thoroughly mixing the thickener solution for a large compound batch with a small amount of the
latex mix in an efficient small mixing vessel. This added to the main
batch will disperse when stirred to give maximum efficiency. When
very large batches of highly filled latex are prepared it is sometimes
possible to add the thickener solution directly. Effectiveness depends
here largely on the agitator efficiency.
(d) Anti-foaming Agents
Both silicone and non-silicone based anti-foams have been used
effectively with Breon vinyl latices. It is important that the most
suitable type is chosen with each latex for maximum efficiency. Silicone
Antifoam A and RD have good general-purpose efficiency. The Nopco
and Bevaloid grades most suitable for each Breon latex are given in
Table 23.4.
TABLE 23.4
Anti-foaming Agents for 'Breon' Latices
a
Breon latex
151
351
352
576
599
652
a
Bevaloid
Type
566 or
942
6250
6250
6250
60
6250
Amount (% on
latex)
03-05
02-D3
01-D2
01-D2
005-D1
01-D2
O2-D3
Nopco b
Foamaster
Type at 025% on total
latex
NDW or 8034
DNH-1 or 8034-E
NX2 or NDW
DNH-1 or 8034-E
DNH-1 or NXZ
DNH-l or NXZ
23
PVC Latices
1029
1030
W. V. Titow
1031
23 PVC Latices
Components
Mellite 39 (Albright and Wilson Ltd, UK)
Lankroflex ED3 (Lankro Chemicals
Ltd, UK)
Tween* 20 (Honeywill-Atlas Ltd, UK)
Spant 20 (Honeywill-Atlas Ltd, UK)
Dibutyltin dilaurate
Morpholine oleate
Water
System 1
System 2
(pbw, wet)
2860
(b) Plasticisers
PVC homopolymer latices dry out to hard, normally discontinuous
deposits. Softness and flexibility can be achieved only by the use of
copolymer (internally plasticised) latices, or by external plasticisation,
* Polyoxyethylene sorbitan monolaurate (emulsifier).
t A sorbitan fatty ester (emulsifier).
1032
W. V. Titaw
23 PVC Latices
1033
move together into close mutual surface contact. At this stage the
capillary forces are supplemented in their action on the particles7 by
forces arising from the polymer/water interfacial tension ('surface
tension forces'S). If the particles are sufficiently soft, they deform as
they pack tightly under the influence of these forces (as, for example,
in the case of rubber and some PVC copolymer latex particles),
achieving intimate, extensive surface contact. The quality of softness
which makes this possible is also usually associated with relative
freedom of movement of the polymer chains. The combination of good
surface contact and chain mobility plays a cardinal part in the ease of
coalescence of the particles (cf. Section 23.1) through the basic
mechanism of inter-diffusion of polymer chains across particle
boundaries. Coalescence (and the attendant development of cohesion
in the polymer layer) will-in favourable circumstances-proceed until
the layer is transformed into a homogeneous film. The term
'autohesion' has been coined for this kind of effect. 9 In the context of
the morphology of latex deposits, autohesive cohesion may be
.contrasted with the much weaker one produced in a layer of closely
packed but essentially discrete polymer particles by capillary and
surface tension forces developed on drying. With hard particles,
coalescence sufficient for the ultimate formation of a continuous film
may occur only at suitably elevated temperatures (heat fusion). The
very hard particles of a PVC homopolymer latex (e.g. Breon 151)
require the addition of plasticiser for satisfactory fusion even at high
temperatures. External pressure is also employed in some cases. The
presence of a plasticiser in the polymer deposit facilitates fusion, as its
penetration into the polymer increases the free volume and reduces the
effective Tg , thus effectively increasing chain mobility (as well as particle
softness).
The likely performance of a plasticiser in the ultimate latex film may
be estimated from a knowledge of its effects in solid PVC
compositions. However, with base polymers of the same type it may be
necessary to reduce the amount of plasticiser used in a latex
formulation, because of the greater inherent flexibility of thin films.
The main factors to be taken into account in selecting plasticisers for
latex formulations include all those relevant in the formulation of
solid compositions (cf. Chapters 4 and 7), with-additionally-ease of
emulsification for blending with the latex. Where nitrile rubber is to be
used as a plasticising modifier of high permanence in the ultimate film
(cf. Chapter 11, Section 11.2.2) this is introduced by addition to the
W. V. Titow
1034
TABLE 23.5
Physical Properties of Films from 'Breon' Vinyl Latices after the Addition of
Plasticiser
Latex
Breon 151
Breon 352
Breon 599
Tensile strength
(lbfin- 2 )
Elongation at
break (%)
DAP
TIP
Breon 1562a
Acetyl tributyl
citrate (ATBC)
DAP
TIP
Breon 1562a
ATBC
Phthalate-preplasticised grade
1800
3200
2780
150
150
150
2000
1850
2400
2700
1750
210
300
210
100
250
1700
350
PVC latex of the appropriate nitrile rubber latex (e.g. Breon 1561
high-nitrile latex, or 1562 medium-nitrile latex which imparts somewhat better low-temperature flexibility to the ultimate film).
It is essential in latex working to obtain an even, stable plasticiser/
latex mixture. Pre-emulsification is the most common method used for
ester types. Sometimes it is possible to emulsify the plasticiser directly
into the latex compound. This involves adding a carefully controlled
type and amount of emulsifier to the latex and agitating the oil in
slowly. Type and amount of emulsifier vary according to the plasticiser
and the base latex used. Optimum association of polymer and
plasticiser is not often possible by this method because of limitations
on the shear rate which can safely be applied to emulsion latex
systems. Other ingredients such as fillers and thickeners assist in
maintaining an even mixture and preventing phase separation.
The addition of pre-emulsified plasticiser to Breon vinyl latices at 35
parts per 100 parts of dry polymer affects the physical properties of the
dried, fused polymer film according to the type of plasticiser chosen.
The data in Table 23.5 were obtained on thick films cast on glass
plates, dried at 23C and fused at 160C. The higher plasticising
efficiency obtained by pre- as against post-plasticisation is demonstrated by the higher elongation and lower tensile strength of film from
Breon 599 vis-a-vis that from Breon 352 post-plasticised with 35 phr
23 PVC Latices
1035
DAP (as the nature and contents of the polymer and plasticiser of the
two latices are closely comparable).
In general, for a given base polymer, the higher the plasticiser
content the lower the tensile strength and the higher the elongation of
the resultant film. As with solid compositions, epoxidised oils are not
commonly used as primary plasticisers in PVC latices, but they may be
included for improved heat stability.
The hard PVC latices, Breon 151,351 and 352, require plasticisation
and/or pressure, in addition to heat fusion, to form films. The
minimum amount of general-purpose phthalate plasticiser which has to
be added to render Breon 151 film-forming varies, according to
processing conditions, from 15 phr to 20 phr; it is slightly less for Breon
351 and 352. Where-as is sometimes necessary-a very hard film has
to be formed of lower plasticiser content (and without use of pressure),
a temporary, 'fugitive' plasticiser may be used. An example is
polypropylene glycol, which evaporates from PVC at fusion temperatures of about 160C but assists film formation at about lOOC in the
earlier stages of processing.
(c) Fillers
Fillers are added to PVC latices for one or more of the following
effects on the final product: cost reduction; reduction ('flattening') of
gloss; increase of hardness and stiffness; reduction of tack. The fillers
most commonly used are calcium carbonate, clay, barytes, and some
types of particulate silica. Relatively small amounts of filler (up to
about 20 phr) modify latex-produced PVC films without too drastic an
effect on their physical properties. The actual amount of filler to be
used in given circumstances will depend on its type and particle size, as
well as the nature of the polymer and the plasticiser level. However,
there is a volume concentration of filler (or pigment) for a PVC latex,
as there is for a surface-coating emulsion in the paint industry, above
which a sharp drop occurs in a number of physical properties of the
ultimate film. Experimental evidence indicates that at this 'critical
pigment volume concentration' (cpvc) the filler becomes the major
structural component of the film, with the role of the polymer changing
from that of a continuous matrix to one of a binder holding the filler
particles together without enveloping them entirely. Whilst the binding
power of PVC in such a system is quite good, the resulting cohesion is
inferior to that of a continuous film. 4 The cpvc may be determined for
the latex-produced filled (or pigmented) films of most polymers by
1036
W. V. Titow
~ 300
.c
to
c:
~200
iii
I
I
'"oc:
I
I
I
I
x SG of filler x 100
x SG of film
23
PVC Latices
1037
In many applications small amounts of filler below the cpvc level are
used, to cheapen the mix, modify flow characteristics, or reduce the
gloss of the final product. The relevant points made in Chapter 8
concerning the properties and effects of fillers apply here. Thus, for
economy, whitings followed by clays are the most widely available and
attractively priced fillers in most countries. Whitings are available in
many different particle size forms according to the method of
manufacture and mineral source: the cost varies depending on particle
size and size distribution, chemical purity, and presence or absence of
surface treatment. Similar considerations apply to clays which,
however, are more expensive grade for grade. Mica fillers, also
occasionally used, are the most expensive. In general, whitings are the
softest fillers and cause the least stiffening, whilst clays impart
intermediate hardness-and micas high hardness-at the same loading
levels. Barytes is sometimes incorporated in PVC latices to increase
the density and weight per unit area of the ultimate coatings, as only
relatively small loadings of this high-density filler with good covering
power (see Chapter 8, Section 8.2.2) are needed to produce significant
increases. Where barytes is used, the latex viscosity must be adjusted
to prevent the filler settling out and forming a compact, hard-todisperse layer at the bottom of the container.
Gloss reduction may be brought about by the incorporation of small
amounts of fine-particle-size silica. The water absorption and soap
demand of these finely divided particles must be satisfied before
addition to the latex in order to prevent flocculation.
Bentonite clay may be used to modify flow characteristics of latex
mixes. This clay has a layered plate-like structure which readily
absorbs water, imparting 'body' to the compound. The yield value
developed can be usefully employed in coating mixes where restricted
flow, low penetration and good dimensional stability in the wet state
are required. Initial difficulty in wetting-out bentonite may be
overcome by treating it with a small amount of alcohol before water
dispersion.
Small amounts of filler used well below cpvc must be in fine particle
form, well dispersed in water to minimise depression in polymer
strength. Coarse aggregates or large particles form points of weakness
in the structure which start or propagate physical breakdown. It is
normal to predisperse these fillers in water with an added dispersing
agent and pass the resultant slurry through a cone or high-speed colloid
mill to de-aggregate the particles. When very small amounts of extra
1038
W. V. Titow
fine dispersions are needed, ball mills may be used to achieve fine filler
slurries but this process is too slow and uneconomic for large-scale
production.
Near to the cpvc point when the polymer becomes a binder, choice
of filler becomes more critical. Fine particles have large surface area
and therefore a greater binder demand but give increased covering
power. They may be tolerated where binding power is the prime
requirement in a surface coating, but where economy is the main
consideration coarse fillers may be added in greater amounts before
the film cracks and fails physically. China clay is normally preferred for
dense, high-hardness coatings, and coarse whitings for maximum filler
levels and economy.
(d) Pigments
Unfilled and unpigmented vinyl latices produce transparent colourless
films, and for some applications it is necessary to pigment the polymer
or improve the appearance of filled compositions with opacifying
pigments or colours. Choice of pigments is restricted as certain metallic
ions such as iron and zinc under some circumstances catalyse the
decomposition of PVC. Reaction depends on the chemical form of the
ion and service temperature. Many grades of metal oxide pigments
may be safely used with PVC but care is needed in the choice of grade.
Where there is a danger of small proportions of latent metal ions
existing in the pigment or being generated during its preparation for
addition to the latex, oxides of iron, zinc or copper are best avoided.
Titanium dioxide is the preferred pigment for a white base but
Iithopone and blanc fixe could be used. It is advisable to incorporate a
white base in filled and unfilled stocks required in pastel shades.
A wide range of colours is possible with vinyl latex base, as the
polymer itself is clear and does not discolour under normal
circumstances. Some care is needed in the use of Breon 652 which does
discolour more readily during service exposure to UV light or elevated
temperatures. The normal range of organic pigments is usually
satisfactory for coloured compositions, especially aqueous pastes
prepared for use in latex systems.
Pigments and dyes, like many compounding ingredients, are
prepared in aqueous dispersion prior to addition for the greatest
efficiency.
23
PVC Latices
1039
* This definition is closely in line with those given in relevant standards ll ,12
1040
W. V. Titow
pvc
1041
23 PVC Latices
nature and intended use of the textile, including full saturation of fibre
mat by immersion (followed by removal of excess latex by squeezing or
suction), impregnation with foamed binder latex, spraying, printing,
and others.
A review of the properties, applications, and structural effects of
vinyl chloride copolymer latices used as binders for non-woven fabrics
has been published by Schlauch and Caimi. 16
(b) For Coating or Impregnation of Fabrics
Applications of PVC latices in this field include backings for carpets
(tufted and woven), flame-retardant finishes, water-proofing finishes
(e.g. for tarpaulins and tent fabrics), priming (keying, bridging or tie)
coats on fabrics to be coated with PVC pastes and/or made into belting
or other composite structures (wherein the priming coat reduces
penetration of the main coating composition into the fabric and
improves its adhesion), and impregnation coatings for shoe-lining and
book-cover fabrics (to impart heat-bonding properties, or/and moisture
resistance, or/and stiffness). The following basic formulations are
illustrative of some of the types used (figures are pbw dry solids):
(i) High-quality, stiff backing for woven carpet
40
60
100
5
50
100
25
As required
1042
W. V. Titow
23
1043
PVC Latices
TABLE 23.6
Tensile
strength
(kgfcm- 2 )
Bursting
strength
(kgfcm- 2 )
Tear
strength
(kgcm- I )
Bending
length
(cm)
155
105
58
110
223
121
90
52
20
33
58
21
37
A. Heat-treated as under 1
B. Heat-treated and pressed
as under 2
60
Breon 352, 6 parts; Breon 2671 2, 4 parts. Solids content of impregnation bath: 40%.
Pick-up (% of dry fibre weight): 666 17.
Breon 576
Breon 151
65% Dialphanyl phthalate emulsion
Coalescing solvent (Bisol
DPS-BP Chemicals)
40% Calcium stearate
Pre-ground pigment dispersion *
Water
Formulation 1 Formulation 2
(pbw, wet)
100
65
22
07
5
5
100
100
Amount. required for a
viscosity rating of 20s with
No.4 Ford cup
46.6
02
02
30
20
1044
w.
V. Titow
135
(55)
90
10
(45)
to pH 10
10
23
PVC Latices
1045
65
30
Breon 576
Breon 151
Breon 1562
Antifoaming agent
Non-ionic stabiliser
Pigment
Thickener (ammonium polyacrylate)
10
01
05
10
05
REFERENCES
1. Blackley, D. C. (1966). High Polymer Latices, Vol. 1, Applied Science
Publishers, London, Ch. 1.
2. Vanderhoff, J. W., Bradford, E. B. and Carrington, W. K. (1973). J.
Polym. Sci., Part C (Polymer Symposia), No. 41, 155-74.
3. Titow, W. V. (1978). In Adhesion 2 (Ed. K. W. Allen), Applied Science
Publishers, London, Ch. 12.
4. Breon Latices: Technical Manual No.5. BP Chemicals (UK) Ltd, London,
1969.
5. Glasstone, S. (1948). Textbook of Physical Chemistry, 2nd Edn, Macmillan
and Co. Ltd, London, p. 1220.
6. Brown, G. L. (1956). J. Polym. Sci., 22,423.
7. Vanderhoff, J. W., Tarkowski, H. L., Jenkins, M. C. and Bradford, E. B.
(1966). J. Macromol. Chem. 1, 361.
8. Dillon, R. E., Matheson, L. A. and Bradford, E. B. (1951). J. Colloid Sci.
6, 108.
9. Voyutskii, S. S. (1963). Autohesion and Adhesion of High Polymers,
Polymer Reviews, Vol. 4, Wiley-Interscience, New York.
10. Humbert, L. and Humbert, P. (1959). Official Digest, 181,413, 736.
11. ISO 472-1979. Plastics-Vocabulary.
ASTM D 883-78a. Standard definitions of terms relating to plastics.
12. ASTM D 1893-67 (Reapproved 1978). Blocking of plastic film.
ASTM D 3354-74 (Reapproved 1979). Blocking load of plastic film by the
parallel plate method.
BS 2782: 1970: Method 31OA. Blocking offlexible PVC sheet.
1046
W. V. Titow
13. Krcma, R. (1971). Manual of Nonwovens, Textile Trade Press, Manchester, England, and W. R. C. Smith Publishing Co., Atlanta, Ga., USA.
14. Gillies, M. T. (1979). Nonwoven Materials, Noyes Data Corp., NJ, USA.
15. Whitehead, D. A. (1980). Tex. Ind. SA, February, pp. 5-11.
16. Schlauch, W. F. and Caimi, R. J. (1974). Text. Chern. Color., 6(10),
223-9.
CHAPTER 24
24.1 INTRODUCTION
The applications of vinyl chloride polymer and copolymer solutions are
less extensive than those of solid compounds or pastes. However, the
solutions-and the special resins from which most are made-are well
established in the application areas where they are utilised, and the
advantages they offer are recognised. The principal uses are in surface
coatings (including certain paints, corrosion-protective coatings, and
overlacquers for PVC), some printing inks, adhesives (solvent
cements) for PVC, the production of PVC fibres, and solution-casting
of PVC films. These applications are discussed in more detail in the
following sections.
Although standard suspension-, emulsion- and mass-polymerised
PVC resins dissolve in the appropriate solvents, they are not too well
suited for much of the solution work where special processing and
end-use requirements have to be met: the common ones include ready
solubility in mixed-solvent systems (up to high solids content levels for
some applications), tolerance for diluents (especially aromatic hydrocarbons), good compatability with other polymeric solutes, solution
viscosities suitable for particular uses, good adhesion of solutiondeposited films to substrates (especially metals), and high strength and
toughness of the films and other end products. Resins-mainly
copolymers of vinyl chloride with other monomers (especially vinyl
chloride/acetate copolymers)-are available to meet these and other
special requirements. These polymers are 'solution' resins in two
senses: they are produced for solution applications, and most are made
1047
w. v.
1048
Titow
1049
(c) Terpolymers
The terpolymers in general use as solution resins are vinyl chloride/
vinyl acetate copolymers containing either maleic acid or vinyl alcohol
residues as the third component. The maleic acid is introduced by
using maleic anhydride as the third comonomer in polymerisation; the
vinyl alcohol groups are produced in situ in the usual way, by
hydrolysis of some of the acetyls of a VCNA copolymer. Some
information on commercial representatives of both kinds of terpolymer
is given in Table 24.1. In both, useful properties result from the
presence of the additional functional groups. The hydroxyl groups
provide reactive sites through which cross-linking can be effected by
reaction with amino resins (urea- or melamine-formaldehyde) or
isocyanates. 1 The -OH groups also improve compatibility with other
polymers (e.g. nitrocellulose and alkyd resins in surface-coating
formulations l ). The carboxyl groups in acid-modified VCNA copolymers improve solubility in relatively weak solvent systems and impart
good air-dry adhesion for a number of substrates (especially metals and
paper), important in coating and adhesive applications (ct. Table 24.7).
24.2.2 Solvents and Diluents
13-16
12-13
Approx.
10
118-142 08-12
84-87
87-88
Approx.
90
85-88
VYHD
VYLF
VYNS
VMCH
maleic
acid
Other
14-15
Vinyl
acetate
85-86
Vinyl
chloride
% Composition
VYHH
Desig
nation
60
82
Medium-high
Medium
Soluble in some
ketones and esters
Soluble in some
ketones, esters,
chlorinated
hydrocarbons, alone
or in combination
with aromatic
hydrocarbons
As VYHH (higher
solids content
solutions possible)
Solubility
characteristics
16
36
57
Solution
viscosityb
(cP)
Medium-low
Medium
(lower than
VYHH)
Medium
Molecular
weight
TABLE 24.1
Ucar" Solution Resins
Good air-dry
adhesion of coatings
to metal, paper and
other substrates;
tough, durable
coatings.
Acceptable in some
food-contact
applications
Acceptable in several
food-contact
applications
Remarks
155-189
2~53
79-82
895-915
89.5-91.5
79-83
VMCA
VAGH
VAGD
VROH
Medium
Medium
(lower
than
VAGH)
Low
5.2--6.5
vinyl
alcoholc
Approx.
5 vinyl
alcohol
Similar to
VMCC
H-25
maleic
acid
52--65
vinyl
alcoholc
Medium
(lower than
VMCH)
08-11
maleic
acid
17
43
87
20
37
Acceptable in several
Similar to VMCH,
Similar to VMCH
food-contact
but higher tolerance
(but where
applications
for aromatic
toughness and
hydrocarbons and
durability
higher solids content requirements lower)
solutions possible
Good solubility in
Coating and adhesive Recommended for
ketone/aromatic
use in conjunction
applications
solvent mixtures
with cross-linking
systems (esp.
VERRd )
Soluble in some
Coatings (alone or in Acceptable in several
ketones, esters and
food-contact
combination with
applications;
chlorinated
other resins)
hydrocarbons;
crosslinkable by
virtue of hydroxyl
tolerance for
content
alcohols in the
solvent systems
Acceptable in several
Similar to VAGI:>.
Similar to VAGH,
food-contact applicabut higher solubility
tions; crosslinkable
and maximum solids
by virtue of hydroxyl
contents in solutions
content
As VAGH, but lower
Similar to VAGH
Similar to VAGD,
costs in coatings as
but still easier and
higher applied solids
greater solubility
and cheaper solvent
systems can be used
The former. Bakelite (Vinylite) range of vinyl chloride copolymer resins for solution applications (Union Carbide Corp. in the USA, and
associate companies elsewhere). Table based on data from Union Carbide technical literature.
b 15% resin in 1: 1 MEK: toluene at 25C.
C Formed by hydrolysing part of the vinyl acetate component.
d See Note on pp. 1058-9.
Approx.
12-16
2.~5.3
144-177
815-845
VMCC
w.
1052
V. Titow
Weight
(g/lOO g
solution)
Solvent
Weight
(g/lOO g
solution)
Acetone
Methyl ethyl ketone
Methyl isobutyl ketone
Cyclohexanone
Methylcyclohexanone
Mesityl oxide
25
30
25
30
27
32
Isophorone
Benzene
Toluene
Xylene
50/50 acetone/xylene
50/50 MEK/xylene
28
1
1
1
28
28
1053
TABLE 24.3
Solubility (in 10% Concentration) of a Commercial Vinyl Chloride/Acetate
Copolymer for Solution use (Vinylitea VYHH)
Solubility
Solvent
Acetone
Butyl acetate
Carbon tetrachloride
Cellosolve solvent
Cellosolve acetate
Dibutyl phthalate
Dichloroethyl ether
Dimethyl phthalate
Dioxane
Ethanol
Ethyl acetate
Ethylene dichloride
Ethylene glycol
Ethyl ether
Dioctyl phthalate
Isophorone
at
25C
at
95C
S
S
I
I
S
S
S
S
S
I
S
S
I
I
I
S
S
S
I
I
S
S
S
S
S
I
S
S
I
I
PS
S
Solvent
Solubility
at
at
25C 95C
Isopropanol (anhydrous)
Isopropyl acetate
Mesityl oxide
Methanol
Methyl acetate
Methyl ethyl ketone
Methyl cellosolve acetate
Methyl isobutyl ketone
Propylene dichloride
Propylene oxide
Tricresyl phosphate
Hydrogenated naphtha
(diluent)
Xylene (diluent)
Toluene
I
S
S
I
S-CI
S
S
S
S
S
I
SO
I
S
S
I
S-CI
S
S
S
S
S
PS
PS
SO
SW
PS
S
Key: S, soluble; I, insoluble; PS, partially soluble; CI, cloudy solution; SO,
softens.
a Materials of this range now marketed under the trade name Ucar-see
footnote to Table 24.1.
surface-coating formulations. All these points are illustrated by the
examples of compositions given in Section 24.4, which also demonstrate that the choice of solvent, or solvent/diluent, system in any given
case is determined by the nature, mode of application and end-use of
the composition. Aliphatic hydrocarbons, alcohols, and water have
precipitant action on PVC solution copolymers, but alcohol diluents
can be tolerated in moderate amounts by hydroxyl-containing polymers
(especially when dissolved in good solvent(s) in relatively low
concentrations) .
In general, the solubility of PVC solution resins tends to increase
with rising temperature. Highly concentrated solutions may become
thixotropic or gel permanently (especially when prepared at an
elevated temperature and then cooled down to room temperature).
Viscosity increases with the solute content (cf. Fig. 24.1), and-for
1054
W. V. Titow
10000
.i
0..1000
u
'iii
0
l/l
;;:
c
(f)
.
/
I .:/
:/
-:
.: / /
I
I.
I'
1/
I
:1
,. '"
.
'
"
.
!/ ,.
//
100
....Q
(5
....
::J
..
<
",,7
....-
.... ..-7
....-
10
0
10
15
20
010 Polymer
25
30
35
1055
1056
W. V. Titow
Pigment
Titanium dioxide
Carbon black
Lead chromate
Lead sulphate (white lead)
Chrome orange
Chrome green (chromic oxide)
Iron oxide brown
Phthalocyanine green
Phthalocyanine blue
Aluminium powder
1057
The viscosities of simple PVC solutions used directly (e.g. for film
casting) or in the preparation of composite surface coatings are, in
most cases, sufficiently low for paddle or impeller mixers to be
employed in their preparation, both on the laboratory and industrial
1058
W. V. Titow
* Formerly Bakelite.
1059
1060
W. V. Titow
24.4 APPLICATIONS
Solutions of vinyl chloride/acetate copolymer resins find a number of
applications as surface coatings, of which the following are typical:
overlacquers for PVC coatings on fabric and paper in such products as
leathercloth, floor-coverings and vinyl wallpapers (see also Chapter 22,
Section 22.2.6); strippable coatings (sprayed or dipped) for temporary
protection of metal surfaces and various products during transport and
storage, cocooning compositions (applied by spraying) for equipment
and article protection in similar circumstances; protective coating
(resistant to chemicals and moisture) for concrete, wood and metal in
the building industry. Some relevant starting formulations are given,
by way of example, in Table 24.4.
Solutions of the modified copolymers (whose carboxyl or hydroxyl
groups variously improve adhesion to substrates and reactivity with
1061
TABLE 24.4
Vinyl Chloride/Acetate Copolymer Solutions for Some Coating Applications:
Examples of Basic Formulations
(Based on data from the technical literature of Union Carbide Corp.)
Component
Formulation (Pbw)
Overiacquer
for vinyl
coatings
Ucar VYNS
Ucar VYHH
Methyl methacrylate resin
Cellulose acetate-butyrate resin'
Plasticiser
Aluminium powder
Methyl ethyl ketone (MEK)
Methyl isobutyl ketone (MIBK)
Toluene
50-75 a
25-50
02-04
40d
60d
Strippable Cocooning
coating
solution
solution
10
5
16b
8
6
70
27
27
27
a Toughness,
other resins) alone or in combination with one another and/or with the
unmodified copolymers, are used in a variety of coating applications
where moisture and chemical resistance, toughness and gloss are of
interest. The applications include primers and top coats for wood and
fibre or particle board (in which the copolymers-especially the
hydroxyl-modified resins-are usually combined with other resins, e.g.
alkyd, nitrocellulose, urea-formaldehyde, urethane prepolymer), and
various paper coating uses, notably coatings for food-packaging papers
in which the hydroxyl-modified copolymers (offering particularly good
adhesion) may be used alone or in blends with vinyl acetate and other
polymers. The same copolymers are also especially useful in decorative/protective coatings for paper labels in view of their excellent
adhesion to a variety of print types, and the gloss obtainable after
drying at about 105-120C (enhanced further by a short baking
treatment). 2
W. V. Titow
1062
Formulation (Pbw)
Component
Cellosolve acetate
Methyl butyl ketone
Toluene
Xylene
VM & P naphtha
Ucar resin VAGH
Ucar resin VYHH
Ucar resin YMCA
Ucar resin VYHD
Tricresyl phosphate
Didecyl phthalate
Thixotropic agent
Red lead
Rosin
Cuprous oxide
Dispersant
Titanium dioxide
Clay extender
Zinc phosphate
Red lead
primer
Shipbottom
antifouling
White anticorrosive
primer
White
topcoat
4445
635
698
444
127
1318
1315
188
207
132
038
3676
525
578
367
105
3820
546
600
382
109
249
136
227
196
2001
1-39
2190
1566
392
092
390
105
1153
027
1095
1360
975
6530
922
1063
1064
W. V. Titow
TABLE 24.6
Adhesion of Vinyl Chloride/Acetate Copolymer Resin (Breon AS 70/42) Film
Solution -deposited onto Aluminium Sheet
Q
Stoving conditions
Solution solids
Resin (20 g)
None
30 min. at 50C
15 min. at 150C
Resin (10 g)
None
}
30 min. at 50C
30 min. at 150C
None
30 min. at 50C }
30 min. at 1500C
Adhesion
TABLE 24.7
General Adhesion Characteristics of Commercial Vinyl Copolymer Resins for
Solution Use
(Based on data from Ref. 2)
Resin type
Surface
Vinyl chloride
acetate (Ucar
VYHHor
VYHD)
Carboxylated
VClVA (Ucar
YMCA, VMCC
or VMCH)
Hydroxylated
VCIVA (Ucar
VAGH or
VAGD)
P
P
P
P
P
P
E
P
P
P
E
E
P
F
F
E
G
F-E
E
F
F
F
F
F
G
G
E
E
G
G
1065
TABLE 24.7-eontd.
Surface
Resin type
Vinyl chloride
acetate (Ucar
VYHHor
VYHD)
Carboxylated
VCIVA (Ucar
VMCA, VMCC
or VMCH)
Hydroxylated
VCIVA (Ucar
VAGH or
VAGD)
P
P
F
P
F
F
F
P
P
E
F
G
G
Nitrocellulose
Alkyd resins
Chlorinated rubber
Oleoresinsa
Shellac
Concretea
Plastera
Key: E
F-E
a Adhesion
REFERENCES
1. Bakelite Vinyl Resin Solution VYNC, Union Carbide Corp. Technical
Bulletin, 1971.
2. Bakelite Hydroxylated Vinyl Resins VAGH and VAGD, Union Carbide
Corp. Technical Bulletin, 1971.
3. Bakelite Vinyl Chloride-Acetate Resin Solution VERR-40, Union Carbide
Corp. Technical leaflet, 1978.
4. High-build Vinyl Maintenance Paints, Union Carbide Corp. Technical
Bulletin, 1973.
5. Yarsley, V. E. and Flavell, W. (1956). Cellulosic Plastics: Part 1: Cellulose
Acetate, Cellulose Ethers, and Regenerated Cellulose, Plastics Monograph
No. C6, Plastics Institute, London.
6. Couzens, E. G. and Yarsley, V. E. (1968). Plastics in the Modern World,
Penguin Books Ltd, Harmondsworth, Middlesex, England.
7. ASTM D 2564-80: Specification for solvent cements for poly (vinyl chloride)
(PVC) plastic pipe and fittings.
8. Cook, J. G. (1964). Handbook of Textile Fibres, Merrow Publishing Co.,
Watford, England.
CHAPTER 25
V. TITaw
25.1 INTRODUCTION
Neither the terminology nor its usage in the field of cellular plastics is
as yet fully standardised. The principal nomenclature standards* offer
definitions of some basic terms, but these are by no means mutually
identical. Moreover, none of the definitions can be said to be fully
comprehensive, and they are not adhered to strictly in industrial usage.
For the purpose of the present chapter the most important relevant
terms are defined as follows.
Cellular PVC: A PVC material or product whose apparent density is
significantly lower than that of its parent PVC composition by virtue of
the presence of numerous cells (voids) dispersed throughout its mass.
t As
1068
W. V. Titow
been formed by a gas evolved in, or introduced into, the parent PVC
composition in the course of production or processing.
Vinyl foam = expanded vinyl: A PVC foam whose solid material is a
flexible PVC composition.
Blown PVC: A PVC foam in which the cell-producing gas has been
generated or expanded within the parent PVC composition (and not,
say, mechanically admixed at atmospheric pressure).
Blown vinyl: A blown PVC whose solid material is a flexible PVC
composition.
In both the commercial and the technical sense PVC foams form the
most important group among cellular PVC products. They are also
significant among plastics foams generally, with several applications
where their processability and/or properties offer special advantages
over alternative cellular materials including those (like, for example,
polyurethane foams) whose volume of use is much greater in many
areas. Two characteristic examples are the foam layers of composite
coatings on vinylleathercloth (d. Chapter 22), and rigid foam cores of
GRP or other sandwich panels used in the construction of vehicle
bodies (e.g. refrigerated vans, modern high-speed train cabs l ). In the
former application, processability in paste form-unique to pPVCand good bonding to the skin and anchor layers of the coating are
cardinal advantages; as are the strength of rigid PVC foam (greater
than that of polyurethane or polystyrene foam) and its low flammability in the constructional sandwich panels.
Note: The floor in the cab of the British Rail high-speed train is a
GRP/PVC foam panel. In the prototype a more complicated
sandwich was used, with a composite PVC/polyurethane foam
core layer in which the PVC foam (of density about
40 kg m-3) was the strength-imparting component.
1069
kg m-3
lb /t- 3
10-50
50-350
350-900
06-3
3-21
21-54
1070
w.
V. Titow
low temperature and high pressure (the gas usually dissolves in the
plasticiser(s) under these conditions), followed by pressure release and
heating, carefully controlled to bring about synchronised expansion and
solidification (fusion) of the composition, which is finally cooled.
The principle has been utilised in several commercial processes,
including the Elastomer process2 ,3 (originated in the USA, but also
used in Europe), the Dennis process4 (sometimes known as the 'Fay
Foamer' process) and the German Trovipor process of the Dynamit
Nobel company. 5 The PVC foam manufactured by processes of this kind
is flexible, mainly open-cell (about 90% of the cells intercommunicating), and of low to medium density (typically 60-270 kg m- 3). It is
normally produced in the form of continuous sheet (slab) several
inches thick, which is usually slit into thin layers (e.g. for use in
upholstery). The sequence of operations in the Trovipor process is
schematically shown in Fig. 25.1. Machines have been available since
the mid-1960s capable of slitting the foam slab into layers of thickness
down to 15 mm (0,050 in) with a tolerance of about 025 mm
(0,010 in).6 The layers may be bonded to textile fabrics with adhesives,
for use, for example, in the proquction of foam-backed clothing~
However, such techniques will not produce cellular PVC leathercloth,
partly because of the comparatively coarse nature of the foam, and
partly because the thickness of coating on many types of leathercloth is
only about 0040 in or even less. It is also very difficult (and costly) to
produce cellular layers of this thickness by direct deposition of 'wet'
dispersed-gas-blown foam onto a fabric. Cellular leathercloth is not,
therefore, made from this type of foam, although it is a major field of
application for foams produced by other processes, as described below.
The most important application of foams made by dispersed-gas
blowing was for many years in the automobile industry as padding and
cushioning material, especially in car seat upholstery, where the
open-cell nature (and hence 'breathability') of the foam, its good
resilience, and-perhaps most importantly-its suitability for highfrequency welding to PVC sheet materials used for seat surfacing, were
important advantages. However, over the past ten years the use of
vinyl seating and trim in motor cars has declined drastically in favour
of fabrics, now widely used for this purpose (in conjunction with
polyurethane foam cushioning). Vinylleathercloth is currently installed
in only a few per cent of European cars (the percentage is substantially
higher in cars for export to, or made in, some overseas countries,
notably in Africa). Vinyl foam produced by dispersed-gas blowing still
25
1071
(B)
____ --.l...-
~I
()
Inlrt gu
(C)
P
s
,q
()
Free
~
blowing
Calendered sheet
(produced by compounding and pro-
Sheet
blowing
Plastisol
Cavity
filling
Principal production
operations
or process
stages
Plastisol
Form of
composition
(starting
material)
Direct
expansion
Method type
Typical products
Characteristics of
foam produced
TABLE 25.1
Main Production Methods Involving Chemical Blowing
~~
:<::
-.l
IV
pounds
E"ru,;on
<om
b
Shock-absorbent material
for crash pads and helmets,
life jackets, packaging
Plastisol
Plastisol (incorpor.
ating volatile or
Pressure blowmg { cross-linking plasticiser)
l
laminate then conveyed with (could be described as mixed
positive support through
cell structure)
heating tunnel (hot air) at
the temperature necessary to
fuse the material and effect
blowing
-.J
......
0
l::>I::
~
"
;:,
'"I::>-
l:;"
;:l.
"'"
C"'l
-.:::
...
::::::
I::
;:;-
Moulding compoundsb
Form of
composition
(starting
material)
Characteristics of
foam produced
Principal production
operations
or process
stages
Typical products
In each case containing the appropriate quantity of blowing agent, properly dispersed (d. also Section 25.3 below).
These may be purchased as special blowing grades, or produced in-plant either by a complete compounding operation (from individual
formulation components) or by compounding the blowing agent(s), or blowing agent masterbatch, into an appropriate PVC
composition. In all cases the temperatures should be so controlled that the blowing agents are not activated.
In compounding dry blends the blowing agent(s) may be added either pre-dispersed (if solid, by milling) in the plasticiser(s), or in
powder form with the drying agent (flow promoter). In the latter case the addition may be made after the cooling of the mix, as a further
safeguard against activating the blowing agent prematurely; however, the resulting degree of dispersion may not be as good as when the
blowing agent is pre-milled in plasticiser.
A good solvating plasticiser (e.g. BBP) should be included in the plasticiser system of any plasticised composition for blowing.
Method type
TABLE 25.1-eontd.
o'l:
:::'1
:-::
......
25
1075
1076
W. V. Titow
1077
usually air. The foam is fused by heating. The plastisol must contain a
surface-active agent to facilitate foaming and stabilise the froth, which
is usually spread on a support (frequently a fabric, to form a laminate,
or release paper for subsequent lamination to fabric-...cf. Chapter 22).
Fusion is effected in a hot-air, IR or rf oven. The method normally
produces soft foams, with largely open-cell structure; the cells can be
very fine. A wide range of densities, roughly 300-800 kg m- 3 or even
higher, may be achieved by varying the plastisol formulation, and
adjusting the production procedure. The foam may be embossed and
surface-coated (e.g. with a lacquer). The main applications are similar
to those of PVC foam produced by the direct expansion of a plastisol
in the free-blowing technique; they include cellular leathercloth, carpet
backing and garment padding.
The Vanderbilt process3,11l and its variant developed by Scott Bader
and Co., Ltd,6 exemplify industrial processes utilising the gasentrainment method.
(d) In-situ Gas Evolution and Cross-linking
This is not a general principle on a par with, say, 'chemical' blowing or
mechanical frothing, but the cardinal feature of a process* for the
production of rigid cross-linked PVC foam (Vinylcel). The superior
thermal and dimensional stability, chemical resistance, mechanical
strength and stiffness claimed for this material in comparison with
conventional rigid PVC foams are attributable to the cross-linked
structure. Preparation of the foam is said to start with a composition
comprising a PVC resin, vinyl monomer, maleic anhydride, a
diisocyanate, and a free-radical catalyst, and to involve, as its main
phases, copolymerisation of the monomer with the anhydride,
evolution (on heating) of CO2 (with consequent blowing) concurrent
with hydrolysis of the anhydride and its reaction with the diisocyanate
which gives rise to the cross-linked structure.
Foams in the density range 32-64 kg m-3 (2-4lb ft-3) produced by
this process found applications in sandwich panels and thermal
insulation.
1078
W. V. Titow
1079
1080
w.
V. Titow
25
1081
1082
W. V. Titow
* See, for example, the British Plastics Federation's Buyers Guide for Plastics
Additives (section on antistatic, viscosity control, depression and wetting
agents), or the Plastics Technology Buyers' Guide.
25
1083
found density increases after fusion which were most pronounced for
the thinnest layers.
The relationship between the formulation and processing conditions
on one hand and properties of chemically blown flexible foam on the
other has been receiving a considerable amount of attention over the
years. A study by Renshaw et al. 27 demonstrated that increasing
concentrations of plasticiser, filler and blowing agent all reduce the
tensile strength of the foam and that the plasticiser concentration is the
principal factor determining foam elongation (the latter being directly
proportional to the former). Elongation was also found to increase
with processing temperature within the investigated limits but, as might
be expected, to decrease with the concentrations of filler and blowing
agent. Other findings were that the compression deflection is inversely
proportional to the blowing agent concentration, that the compression
set values are governed mainly by the plasticiser and filler content
(increasing with the former and decreasing with the latter), that the
foam density is a function almost exclusively of the blowing agent
concentration, and that the use of a good solvating plasticiser is
necessary for good quality foam of the type studied.
Similar work by Deanin et al. 28 indicated that for chemically blown
vinyl foams with open-cell contents in the range 0-90%, the
open: closed cell ratio correlated directly with low-temperature
flexibility and volume resistivity, and inversely with modulus, strength,
elongation, permanent set, resilience and abrasion resistance. Modulus
and strength also varied inversely with the plasticiser content, whilst
decreasing foam density produced decreasing modulus, strength and
elongation. In an extension of this work,29 the effects of plasticiser
content and foam density were found to be generally similar also in
substantially open-cell foams produced by mechanical frothing of
plastisols of a simple basic formulation. However, at comparable
densities (in the range 19-751b ft- 3 ), the mechanical properties of the
latter foams were considerably inferior to those of their chemically
blown, partly-open-cell counterparts.
In his investigation of the effect of formulation and processing on the
properties of foams blown with azodicarbonamide (Genitron A C/2
-Fisons, UK) Visnovsky30 has evaluated such parameters as the
nature of the PVC resin, the activator, plasticiser, and ambient
temperature during expansion. His results show how variations in all
these parameters can affect foam properties, and illustrate particularly
well the effect of molecular weight (K value) of the resin.
w.
1084
V. Titow
25.3.2
1085
1086
W. V. Titow
25
250
1087
200
I
en
E 150
XX
'0
....IIIto
l...
..:-'-x
x
x
I
I
~1oo
to
en
CIl
III
<!>
50
I
;" /
xX
x
xX
xx
o
250
B
200
'en
E 150
'0
to
....
'"to
~
.
f
215C
185'C
-----
l...
en
170C
..............................
100
170C
CIl
III
<!>
50
o
Fig. 25.2 Volume of gas generated by some blowing agents, as a function of
temperature (A), and time at a constant temperature (B). - - Azodicarbonamide (ADA); x x x ADA non-plate-out grade; ... ADA activated with
a liquid CdlBalZn stabiliser system; - - . - - ADA activated with a liquid Pb
stabiliser system; ------ a commercial hydrazide-based blowing agent;
- - 4, 4'-oxybis(benzene sulphonylhydrazide) (OBBS).
EF (profile,! sheeting;
EF (profile,! sheeting;
EF (profile,d wire and
165-230
165-180
165-230
From 145
160-200
AZNP130
AZ760
AZ3990
AZ754
AZRV
Modified:
Non plate-out
Non plate-out
(coml?ounding
grade)
Flow-treated
Activated
Activated
Kempore FF
Kempore 125N
Genitron (or
Ficel) EP
Kempore MC
Genitron
(or Ficel) AC
Azocel
Porofor ADC
Kempore
Materials
Fisons Industrial
Chemicals, UK
(Genitron)
Haake Inc., USA
(Ficel)
Fairmount Chemical
Co., USA (Azocel)
Bayer, West Germany
and Mobay Chemical,
USA (Porofor)
Stepan Chemical Co.,
USA (Kempore)
Sources
SF d R" p . CC
E~ (fiJm' and sheeting;
wire and cable)
ERd (profile, pipe,
sheeting); SRQ
cabl~;
165-230
AZ130
Regular
Application areas
Approximate
operational
range Cc)
Celogen
grade
General type
:::l
S
:0::::
00
TABLE 25.2
Operational Temperatures and Applications of Some Commercial Azodicarbonamide Blowing Agents, with Special .<=>
Reference to the 'Celogen' Range (Uniroyal Chemical)Q
00
1089
1090
W. V. Titow
1091
1092
W. V. Titow
1093
application of heat before the material enters the nip of the rolls. 38
Other methods include 'direct' embossing as the material emerges from
the fusion oven (this is mainly applicable to cellular leathercloth with a
woven fabric base), and the use of embossed release paper on which
the foam layer is cast (cf. Table 25.1).38 In all cases care must be taken
that heat applied to the foam, and/or roll pressure, do not cause
uncontrolled collapse of the cell structure.
1094
w.
V. Titow
25
1095
The best formulations for pastes used in the production of flexible PVC
foam by the dispersed-gas blowing method-which is the domain of big
manufacturers operating under patents and licences-are rarely
disclosed. They are in some cases the results of extensive development
work involving, inter alia, gelation/fusion and viscosity studies of the
kind mentioned in Chapter 21, Sections 21.2.5 and 21.2.6. Such pastes
normally contain fairly high proportions of plasticisers and include a
good solvating plasticiser: they are thus similar in general type to
pastes used for the production of flexible foam by chemical blowing.
Basic formulations for chemically blown foams are exemplified by
those shown in Table 25.3. Some examples relating to foams produced
by gas entrainment are given in Table 25.4.
Basic formulations for the individual layers of a composite coating of
a cellular leathercloth are included among the examples at the end of
Chapter 4.
25.6 EVALUATION AND TESTING
Formulation (Pbw)
25
25
20
5
60
100
-
Calendered
sheet (foam
layer)
Free blowing
100
65
20
-
Coated
plastisol
(foam layer)
TABLE 25.3
20
05
18
4
50
50
100
05
10
20
55
100
Blowing in
injection
moulding
05
100
Extrusion blowing
120
100
-
Pressure
blowing
100
145
100
Cavity
fillings b
:::'j
.....
Coated
fabric and
unsupported
sheet;
leathercloth;
flooring;
wall-covering
Soft
12-40 Ib ft- 3
Mixed
Laminated
and unsupported
sheet;
leathrcloth;
flooring
Medium/soft
20-40 lb ft- 3
Mixed
025
Soft toy
filling
Soft
Variable
Mixed, fine
End application
Type
Density
Cell structure
Foam characteristics
Stearic acid
Zinc oxide (active)
Epoxidised oil
Ca stearate
Pb stearate
Pb silicate
Cushioning
Soft
SIb ft- 3
Mainly
closed
Profiles
Medium/soft
37lb ft- 3
Closed
Profiles/pipe
Rigid
56lbfc 3
Closed
05
05
30
Shoe sole
mouldings
Medium/soft
43lb ft- J
Closed
20
05
12-
s::.
1:;"
~.
r:s
."
t;:
50
30
55
30
55
100
(Breon P130/I)
100
(Breon P130/l)
Dialphanyl phthalate
Butyl benzyl phthalate
Nylonate plasticiser
(Monoplas 230)
Foam promoter
(Deckor Cellset 5)
Paris whiting
20 lb [t- 3
and higher
10-30 lb [t- 3
45
40
100
30-50 lb [t- 3
(Norvinyl PlO)
10
20
30
100
(Breon PI30/I)
50 lb [t- 3
and highe~
TABLE 25.4
Specimen Formulations for Foams Produced by Gas Entrainment26
is
<:
:<::
:::1
;:e
00
......
~
25
1099
1100
W. V. Titow
gas permeability,21 the pore size (an average value may be determined
according to BS 1752 or, for air filters, BS 2577), total pore volume
1101
REFERENCES
1. Gotch, T. M. (1979). Plast. Rubb. Int., 4(3), 119-24.
2. Elastomer Chemical Corporation US Patent 2666036; British Patents
767465; 770237.
3. Ward, D. W. (1969-70). Modern Plastics Encyclopedia, pp. 256-9.
4. Dennis, I., US Patent 2763475.
5. Fuchs, 0., Heckalt, F., and Herz, A. (1965). Kunststoffe, 55(9), 717-23.
6. Anon. (1967). Brit. Plast., 40(8), 64-9.
7. Dilley, E. R. (1966). Trans. J. Plast. Inst., Feb., pp. 17-21.
8. Challenger, P. (1970). Polym. Age, 1,9-12.
9. Harris, W. D. (1976). 34th ANTEC SPE Proceedings, pp. 154-61.
10. Titow, W. V. and Lanham, B. J. (1975). Reinforced Thermoplastics,
Applied Science Publishers, London. Ch. 10.
11. Shea, F. C. (1978). 36th ANTEC SPE Proceedings, pp. 205-7.
12. Nakajima, N., Ward, D. W. and Collins, E. A. (1976). J. Appl. Polym.
Sci., 20(4), 1187-98.
13. Anon. (1976). Plast. Rubb. Wkly, 27th August, p. 10.
14. Anon. (1982). Plast. Rubb. News, October, pp. 45-7.
15. Anon. (1975). Plast. Rubb. Wkly, 22nd August, p. 12.
16. Gross, H. L. and Angell, R. G. (1976). 34th ANTEC SPE Proceedings,
pp.162-5.
17. Hartman, J. V., Kozlowski, R. R. and Podnar, T. (1966). J. Cell. Plast.,
2(4),214-17.
18. R. T. Vanderbilt Co. Inc., US Patent 3288729.
19. Bartl, H., and Wingler, F. (1970). Kunststoffe, 60(1), 19-22.
20. Titow, W. (1961). J. Plast. Inst., Dec., pp. 186-93.
21. Collins, D. H. (Ed.) (1963). Batteries, McMillan, New York, p. 16-17.
22. Greenhoe, J. A. (to Monsanto Chemical Co.), US Patent 2864777.
23. Laskowski, W. and Skowronski, T. (1969). Polim. Tworz. Wielk. 14(8),
389-94.
24. Simonik, J. (1978). 36th ANTEC SPE Proceedings, pp. 773-fJ.
25. Acton, J. and Debal, F. (1976). Plast. Rubb. Wkly, 18th June, pp. 22-3.
26. Deckor Cellset 5, Vinyl Foam Stabiliser, Scott Bader & Co. Ltd, Technical
Booklet.
27. Renshaw, J. T., Cannon, J. A. and Minchen, J. D. (1970). SPE J., 26,
47-50.
28. Deanin, R. D., Kapasi, V. C., Georgacopoulos, C. N. and Picard, R. J.
(1974). Polym. Engng. Sci., 14(3), 193.
1102
W. V. Titow
CHAPTER 26
Applications of pvc
w.
V. TlTaw
(i)
W. V. Titow
1104
26 Applications of pvc
1105
pipework (soil, waste water and ventilation pIpmg, waste traps for
basins, baths, showers and sinks); potable water supply pipes;
rainwater systems (guttering and down-pipes); electrical conduit and
trunking.
Note: Chlorinated PVC (CPVC) is among the rigid plastics pipe
materials fulfilling the main conditions for use in domestic
hot-water systems. 5 The other materials are polybutylene6 and
cross-linked polyethylene.
Water distribution systems: Pressure pipes for potable water
distribution (below and above ground), for cold-water services
(including cooling water in mines), and for irrigation systems.
Sewage and waste-water drains: uPVC pipes have been particularly
successful in underground sewage systems. Competitive pipe materials
include pitch-impregnated fibre ('pitch fibre'), glazed clay, concrete
(including asbestos-reinforced cement) and high-density polyethylene.
Drainage gullies have been moulded in uPVc. *
Aeration systems in sewage-treatment installations
Land (sub-soil) drainage
Pipes for compressed air and vacuum lines:t For example, in mines
and industrial premises. ABS is a competitor in this application, among
common non-metal pipe materials.
Gas supply pipelines: Here the use of uPVC pipes (even of the
preferred impact-resistant 'ductile' compositions) is limited to some
countries (and generally tends to be restricted to pressures not much
above 1 bar in practice, although the nominal ratings can be
considerably higher). Possibility of environmental stress-cracking is a
technical consideration (see Chapter 12, Section 12.5). Mediumdensity polyethylene is a competitive plastics material in this
application.
1106
W. V. Titow
26 Applications of pvc
1107
(a) Rigid Sheet (see also Section 19.5 of Chapter 19, and Chapter 20)
Rigid PVC sheeting is produced by extrusion or calendering: thick
sheets are made by compression laminating layers of either kind of
sheet. The following are the main application areas.
1108
W. V. Titow
26 Applications of pvc
1109
1110
W. V. Titow
Initial
stress
(MPa)
LDPE
PVC
137
74
Ih
24h
112
49
98
32
96
32
104
39
100
34
This makes LDPE a better choice for wrapping heavy loads, but the
lower initial stress of the PVC film means that it is easier to wrap (less
force required).
Apart from LDPE film (used for stretch-wrapping since about 1970),
and the recently introduced linear LDPE, PVC's other competitor in
this field is EVA: such copolymer films of low vinyl acetate content
came into use contemporaneously with PVC, and the tougher high-VA
copolymer films towards the end of the 1970s. The lower density of all
these olefinic films in comparison with PVC is a general advantage;
some also have higher elongation. The biggest suppliers of PVC films
for stretch-wrapping are the Resinite Division of Borden Chemical,
and Goodyear (Films Division) in the USA, with their subsidiaries
abroad. A useful, brief review of stretch-wrapping (with special
reference to its comparison with shrink-wrapping, and to the properties
of the films used) was published recently by Johnson and Langford. 11
26.1.4 Foam
(a) Rigid Foam
Used as the cellular layer of some sandwich and multi-layer panels for
the construction of refrigerated vans, other transport vehicles (see
Chapter 25, Section 25.1) al)d some boat hulls.
26 Applications of pvc
1111
(i)
1112
W. V. Titow
26 Applications of pvc
1113
1114
w.
V. Titow
26 Applications of pvc
1115
1116
W. V. Titow
t In the UK from
26 Applications of pvc
1117
that the latter require shampooing, on the average every 6-8 weeks,
whereas the special flooring should perform satisfactorily if cleaned
about every 20 months. 24
1118
W. V. Titow
The development and growth of this application was given impetus first
by the development of suitable uPVC moulding compositions combining stability in processing and service with good clarity, strength, and
suitability for food-contact applications (cf. Chapters 9, 10, 11 and 17),
and then by developments in processing (cf. Chapter 17).
26.4.3 Footwear (see also Chapter 11, Section 11.2.2, and
Chapter 25)
Microcellular moulded pPVC, and PVC blend soles have been in use
for a considerable time, as have pPVC uppers in some types of
footwear. The main synthetic materials competing with PVC in the
former application are polyurethane, some thermoplastic rubbers, and
EVA (as well as natural rubber), and in the latter mainly
polyurethane. 27 ,28 Complete units (boots, shoes and sandals) are
produced from PVC by injection moulding,29 including all-weather golf
shoes (from a PVC/nitrile rubber blend30).
26.4.4 Battery Separators (see Chapter 25, Section 25.2.2)
26 Applications of pvc
1119
normally used, commonly in the form of dry blends, but meltcompounded compositions-eomminuted by freeze-grinding-have
been employed: these offer the usual advantages of this type of
compound but the cost differential is even higher than between
dry blend and pellet feedstocks, because of the expense of the grinding
operation. Because of the lack of adhesion between PVC and metal
surfaces priming is necessary in powder coating as in other coating
techniques.
The main considerations in the two techniques, brought out well in
Newton's summary,31 may be listed as follows:
Electrostatic
deposition
Typical coating thickness (mm)
Pre-heating of part to be
coated
Automation
0075-02
(tends to be selflimiting)
30-80
(oversize particles
tend to accumulate
on recirculation)
Not normally necessary
(powder coating held
by electrostatic
attraction
until sintered)
Readily effected with
suitable equipment
Fluidised bed
dipping
025-075
(not self-limiting)
Over 100
(some oversize particles
acceptable)
Required
* Including ones for use in heavy weathering conditions, e.g. the safety
balustrading and fog detector hood of the Bull Point lighthouse at
Woolacoombe, Devon, UK have a PVC powder-applied protective coating. 36
w.
1120
V. Titow
plasticised composition (with a Ca/Zn stabiliser) some plasticiser was leached out, and even detected in patients' bodies
after repeated, large-scale transfusions (no adverse effects
were found attributable to its presence). 38
Special extrusion lines are available for the production of
medical-grade PVC tubing. *
Bags fabricated from clear, flexible PVC sheeting have been used for
enclosing wounded limbs to provide an environment controlled in
terms of bacteria content, humidity, temperature and pressure, to
secure suitable conditions for healing without ordinary dressing
(whilst the transparent nature of the bag allows the wound to be
observed).t
Thermoformed PVC trays, designed specially to accommodate the
* e.g. Model 116 line of Betol Machinery Ltd, Luton, Beds, UK designed for
the production of soft, radio-opaque PVC tubing for surgical use: the tubing,
with an inside diameter of 12mm and wall thickness of O'12mm, has an
internal web, off-set so that it divides the interior into two unequal
compartments. 39
t Sterishield bag, developed in the UK by the Biomedical Research and
Development Unit of the Department of Health and Social Security.40,41
26 Applications of pvc
1121
Interest has been growing on both sides of the Atlantic,42 and also
overseas (e.g. in Australia and South Africa)43 in furniture-mainly for
outdoor use-playground equipment, balustrades, and the like, made
from rigid PVC pipe specially formulated for impact and weathering
resistance. The pipe may be plain or externally patterned-in some
cases to resemble bamboo, cane, reed or wicker. t Special 'furniture
* e.g. the total PVC content (including electrical insulation) in the current
model of the VW Golf motor car is about 15 kg.
t e.g. the Ramboo tubing of Plastirama, Mexico.
1122
W. V. Titow
In fabricating the pipe into the products it is cut into lengths and
suitably shaped (after pre-heating). Shaped surface effects, e.g.
bamboo, etc., can be produced by expanding the hot pipe inside a
mould by air pressure. The products are then assembled with the aid of
solvent bonding or special couplings. Good weathering performance
with respect to appearance and strength retention over two years'
exposures in Florida and Arizona has been reported. 42
26.5 SOME SPECIAL, UNUSUAL, OR MINOR PRODUCTS
AND APPLICATIONS
Baby pants: These are made from thin pPVC sheeting (about
01 mm thick), and usually incorporate some form of foam
(polyurethane) padding, fabric-covered elastic band, and fastening
studs. The sheeting is formulated for resistance to hardening by loss of
plasticiser through washing and wear in use, tear and staining
resistance, and good weldability. Typically, DIDP is used as the
plasticiser together with Cd/Ba/Zn stabiliser systems with very low
susceptibility to sulphide staining. A tear strength (Elmendorf test, e.g.
to BS 1763) of 180 g per 01 mm of thickness is a reasonable practical
minimum value.
Fishing lures: PVC lures moulded in the shapes of sand eel,
lugworm, squid and pilchard have been reported to be highly
successful as aids to commercial fishing in Cornwall. 44 The lures are
produced from metal-pigmented compositions, in moulds made from
highly accurate carved acrylic models of the animals. Coupled with the
paint-spray finish this results in very realistic appearance. Hooks larger
than practicable with live bait can be used.
Simulated skin: A PVC composition developed by the UK Ministry
of Defence (Stores and Clothing Research and Development Establishment) has been successfully used-in the form of a sheet about
015 mm thick (produced by Storey Bros, Lancaster, UK)-as a
26 Applications of pvc
1123
TIP
Chlorinated paraffin
White pigment
Lead tartrate
Lead stearate
Calcium stearate
100
26phr
1375 phr
1250 phr
10phr
175 phr
100 phr
075 phr
1124
W. V. Titow
Rug and mat underlay: Two special PVC products are noteworthy. A
rayon mesh coated with PVC fibre flock which provides a surface grip
(Ako-Stop, developed in West Germany50), and a highly plasticised
PVC material in the form of sheet or netting for use as dust-capturing
floor mat or non-slip underlay (Protect-A-Mafl-Dycem Plastics Ltd,
Bristol, UK).
Ball valves: These have been produced in PVC (for use in food and
chemical industries)52 and PVC/polyacetal combinations (for use with
water and other non-corrosive liquids).53
PVC bricks: Several designs have been proposed in the UK,
Germany and Sweden, most with channels to take cement (so that the
brick structure ultimately becomes a framework strengthened by a
cement core). The British-developed Inca-Brick (Inca Construction
Company Ltd) aroused particular interest. Despite claims that costs
compare favourably with those of conventional brickwork, with
building times cut by a factor of 10 or more,54 the bricks have not come
into widespread use.
Protective sheath for hydrophones: Specially formulated PVC tubing
has been used as protective sheathing for lines of hydrophones (about
100 m long) towed by geological survey vessels engaged in mapping the
sea-bed by echo-sounding techniques.55 The equipment, sealed inside
the tubes, is surrounded by paraffin which acts as a protective medium:
the tube material must thus be resistant to paraffin and sea water, and
retain its properties at near-zero temperatures (for use in the North
Sea and other cold waters).
Various minor applications and products: Reflective, self-adhesive
vinyl tape for clothing, walls, etc., for use in mines and other sites and
work situations. Hazard-warning labels (self-adhesive, PVC-film backed)
bearing symbols for radio-activity, poison, inflammable material,
and other hazards.
Ear-protection pads covered with flexible PVc.56 Decoy dummy
aircraft fabricated in PVC (some equipped with radar reflectors for
correct response).57 A low-density core material in sheet form, for
decorative and some constructional applications has been made by a
novel sheet-drawing process, from various thermpolastics, including
PVC (Nor-Core, Norfield Corp., Conn., USA).58 Heat-shrinkable
26 Applications of pvc
1125
end-caps and harness clips for cables (e.g. the Heatshrink fittings
range, Thomas Ness Ltd, UK).59 Cellular PVC monofilament has been
used as the bristles in rough-duty brushes. 60 Safety goggles, moulded in
high-clarity PVC compound (We/vic X16/909-ICI). Composting bins
for garden-use, made of interlocking, perforated rigid PVC profiles. 61
Extruded, fluted PVC curtain rods covered (by an in-line operation
during production) with vacuum-metallised polyethylene terephthalate
sheet. 62
REFERENCES
1. Plastics in Building, ICI Plastics Division, Technical Publication G.25
(revised periodically).
2. Fischer, P. (1968). Kunststoffe, 58(1), 21-5.
3. Smith, P. I. (1969). Appl. Plast., 12(7), 17-19.
4. Anon. (1976). Plast. Rubb. Wkly, 2nd April, p. 10; 25th June, p. 11.
5. ASTM D 2846-81. Chlorinated poly(vinyl chloride) (CPVC) plastic hotand cold-water distribution systems.
6. ASTM D 3309-81b. Polybutylene (PB) plastic hot- and cold-water distribution systems.
7. Petzetakis, A. G. British Patent 984247, and corresponding patents in
other countries.
8. Anon. (1981). Eur. Plast. News, 8(9), 109.
9. Anon. (1976). Plast. Rubb. Wkly, 20th August, p. 7.
10. Anon. (1981). Plast. Rubb. Wkly, 29th August, p. 5.
11. Johnson, F. M. and Langford, A. J. (1982). Plast. Rubb. Int., 7(6),
217-20.
12. Anon. (1980). Plast. Rubb. Int., 5(1), 11.
13. Anon. (1976). Plast. Rubb. Wkly, 17th December, pp. 12-13.
14. Anon. (1982). Eur. Plast. News, 9(7), 29.
15. Anon. (1982). Plast. Rubb. Int., 7(6), 205.
16. Breon P. 130/1 Paste Resin: Technical Manual No.2, B.P. Chemicals (UK)
Ltd, 1969, p. 61.
17. Wingrave, J. A. (1978). 36th ANTEC SPE Proceedings, pp. 580---5.
18. Matheson, A. F. (1981). Electrical Times, 5th June.
19. Nye, H. F. (1976). Plast. Rubb., 1(2), 87-90.
20. Anon. (1976). Plast. Rubb. Wkly, 5th November, p. 26.
21. Anon. (1976). Plast. Rubb. Wkly, 10th September, p. 9.
22. Anon. (1976). Plast. Rubb. Wkly, 16th April, p. 11.
23. Kubitzki, C. and Schulz, G. (1965). Kunststoffe, 55(9), 727-8.
24. Anon. (1982). Mod. Plast. Int., 12(11), 6.
25. US Patent 2899351; Morse, E. A. (Assignor to Personal Products
Corp.).
26. Anon. (1982). Eur. Plast. News, 9(8), 6.
1126
27.
28.
29.
30.
31.
32.
33.
34.
35.
36.
37.
38.
39.
40.
41.
42.
43.
44.
45.
46.
47.
48.
49.
50.
51.
52.
53.
54.
55.
56.
57.
58.
59.
60.
61.
62.
W. V. Titow
APPENDIX 1
1128
United Kingdom
British Standards Institution (BSI),
Linford Wood,
Milton Keynes MK14 6LE.
The annual British Standards Yearbook gives a list of all British
standards with a short summary of each one, and an alphabetical
index. The BSI News is published monthly and may be used for
manual updating of the Yearbook. In addition to lists of all new and
revised standards and amendments to standards published during the
month, draft standards and 'new work started' are also given.
A comprehensive list of standards received from all parts of the
world is contained in BSl's Worldwide List of Published Standards
which is issued monthly.
A large number of standard specifications is contained in BS
2782:1970 Methods of testing plastics, which is currently (1984) under
revision. Many of the specifications in this collection have already been
published in the revised form, and some entirely new ones have been
added. Work is in progress on others. The relevant revised and new
specifications have been included in this appendix, as have those
originally published in the 1970 edition which have not yet been
revised.
Note: In the body of this appendix the degree of equivalence of a
British Standard to an ISO standard is indicated where
possible according to the coding used in the BSI Yearbook,
viz.
1129
ASTM
Volume
~::~:}
08.03
08.04
Subjects covered
Corresponding
parts in former
classification
Part 35
Part 36
Part 34
::::: }
10.03
00.01
Part 39
Part 40
Part 48
The parts and the individual standards are obtainable from the ASTM.
Note: Where an ASTM designation is followed by a number in
brackets, this indicates the year of the latest reapproval by the
committee concerned.
ANSI: The national standardising body in the United States of
1130
America is the:
American National Standards Institute (ANSI),
1430 Broadway,
New York,
New York 10018.
A great many individual standards issued by the ASTM have been
adopted by the ANSI as national standards. These adopted standards
may be purchased through a local national ISO member body.
West Germany
DIN Deutsches Institut fUr Normung,
Burggrafenstrasse 4-10,
1000 Berlin 30.
The DIN-Katalog is published annually, most of the German titles
being given in English as well. The catalogue may be kept up to date
by Ergiinzungen (Supplements) which are published monthly and are
cumulative. Further information on standards is given in DINMitteilungen (DIN-reports), which is also a monthly publication. The
latter two are in German only.
DIN standards on plastics which have been translated into English
are available in ring binders in the following collections:
Sales no. 10053 Plastics 1. Test standards for mechanical, thermal and
electrical properties
10056 Plastics. Duroplast resins and duroplast moulding
materials
10705 Plastics 2. Test standards on chemical, optical, usability and processing properties
10789 Plastics. Semi-finished products of thermoplastic
plastics
10790 Plastics. Pipes, pipeline components and pipe joints
of thermoplastic plastics
The collections of DIN standards in German are reduced in size and
bound into Taschenbiicher (Pocketbooks) in A5 size, and cover the
same classification of the collections translated into English, viz.
TAB 18 Kunststoffe 1. Prtifnormen tiber mechanische, thermische
und elektrische Eigenschaften
1131
TAB 21
Japan
Japanese Industrial Standards Committee,
c/o Standards Department,
Agency of Industrial Science and Technology,
Ministry of International Trade and Industry,
1-3-1 Kasumigaseki, Chiyodaku,
Tokyo 100.
In view of Japan's standing as a major producer and consumer of
PVC, the existence of many relevant Japanese Standards should not be
overlooked (e.g. JIS K 6720 (1977), Polyvinyl chloride resins; JIS K
6741 (1975), Unplasticised polyvinyl chloride pipes.
It has not been practicable to include them in this appendix.
However, from the technological standpoint, they do not cover any
important specifications or methods or materials not dealt with by
standards from one or more of the four sources represented here. It is
useful to remember that Japanese Standards are regularly included in
the already mentioned BSI Worldwide List of Published Standards and
that they are available (generally in English translation) from the BSI.
1132
ASTM F 17-76
Definitions of terms relating to flexible barrier materials
1133
ASTM F 141-79
Definitions of terms relating to resilient floor coverings
ASTM F 412-81
Definitions of terms relating to plastic piping systems
DIN 7732
Part 1 (1963)
Standardized terms and definitions relating to plastics; summary
(b) Common Names and Abbreviations
ISO 1043-1978
Plastics-Symbols
BS 3502
Schedule of common names and abbreviations for plastics and
rubbers
Part 1: 1978
Principal commercial plastics
Part 3: 1978
Rubber and rubber lattices
BS 4589: 1970
Abbreviations for rubber and plastics compounding materials
ASTM D 1600-83
Abbreviations of terms relating to plastics
DIN 7723 (1971)
Abbreviations for plasticizers
DIN 7728
Part 1 (1978)
Symbols for terms relating to homopolymers, copolymers and
polymer compounds
Part 2 (1980)
Symbols for reinforced plastics
(c) Equivalent Terms in Various Languages
ISO 194-1981
Plastics-List of equivalent terms
DIN 7730
Part 1 (1965)
Plastics, equivalent terms in German, English, French and
Russian following ISO/R 194-1961
1134
1135
Part 3 (1979)
Climates and their technical application; climates with regard to
technology; climatic patterns based on statistics
Supplement to Part 3 (1979)
Climates and their technical application; climates with regard to
technology, geographical survey for open-air climate patterns
based on statistics
(b) Some General Test Methods
ISO 62-1980
Plastics-Determination of water absorption
ISO 171-1980
Plastics-Determination of bulk factor of moulding materials
ISO 3451/1-1981
Plastics-Determination of ash-General methods
2 VINYL POLYMERS AND COPOLYMERS (Chapter 2)
2.1 General (Designation, Coding, Characterisation Tests)
ISO 1060/1-1982
Plastics-Homopolymer and copolymer resins of vinyl chloride.
Part 1: Designation
ISO 1060/2-1978
Plastics-Homopolymer and copolymer resins of vinyl chloride.
Part II: Determination of properties
ISO 1163/1-1980
Plastics-Unplasticized compounds of homo- and copolymers of
vinyl chloride. Part 1: Designation
ISO 6186-1980
Plastics-Determination of pourability
ASTM D 1755-81
Specification for poly(vinyl chloride) resins
Note: This specification gives test methods referred to in some of the
ASTM standards listed in the sections that follow, e.g.
Sections 2.2 to 2.9, etc.
ASTM D 2474-81
Specification for vinyl chloride copolymer resins
1136
2.2 Viscosity
ISO 174-1974
Plastics-Determination of viscosity number of PVC resins in
dilute solution
ISO/R 1628-1970
Plastics-Directives for the standardisation of methods for the
determination of the dilute solution viscosity of polymers
ISO 3219-1977
Plastics-Polymers in the liquid, emulsified or dispersed stateDetermination of viscosity with a rotational viscometer working at
defined shear rate
BS 2782
Part 7
Rheological properties
Method 730A: 1979 ( ISO/R 1628)
Determination of reduced viscosity (viscosity number) and
intrinsic viscosity of plastics in dilute solution
Method 730B: 1978 (= ISO 3219)
Determination of the viscosity of polymers in the liquid,
emulsified or dispersed state using a rotational viscometer working
at a defined shear rate
ASTM D 1243-79
Test for dilute solution viscosity of vinyl chloride polymers
1137
1138
ISO 1265-1979
Plastics-PVC resins-Determination of number of impurities and
foreign particles
ASTM D 2222-66 (1978)
Test for methanol extract of vinyl chloride resins
2.8 Bulk Density
ISO 60-1977
Plastics-Determination of apparent density of material that can
be poured from a specified funnel
ISO 61-1976
Plastics-Determination of apparent density of moulding material
that cannot be poured from a specified funnel
ISO 1068-1975
Plastics-PVC resins-Determination of compacted apparent bulk
density
BS 2782: Part 6
Method 621A: 1978 (= ISO 60)
Determination of apparent density of moulding material that can
be poured from a funnel
Method 621B : 1978 (= ISO 61)
Determination of apparent density of moulding material which
cannot be poured from a funnel
Method 621D : 1978 (= ISO 1068)
Determination of compacted apparent bulk density of PVC resins
ASTM D 1895-69 (1979)
Tests for apparent density, bulk factor, and pourability of plastic
materials
NB Method A equivalent to ISO 60
Method C equivalent to ISO 61
2.9 Particle Size
ISO 1624-1978
Plastics-Vinyl chloride homopolymer and copolymer resinsSieve analysis in water
Al
1139
ISO 4576-1978
Plastics-Aqueous dispersions of homopolymers and copolymers-Determination of gross particle content by sieve analysis
ISO 4610-1977
Plastics-Vinyl chloride homopolymer and copolymer resinsSieve analysis using air-jet sieve apparatus
BS 2782: Part 4
Method 454F: 1978 (= ISO 4610)
Sieve analysis of vinyl chloride homopolymer and copolymer
resins using air-jet sieve apparatus
ASTM D 1705-61 (1980)
Particle size analysis of powdered polymers and copolymers of
vinyl chloride
2.10 Bromine Number
ISO 3499-1976
Plastics-Aqueous dispersions of homopolymers and copolymers
of vinyl acetate-Determination of bromine number
2.11 pH of Aqueous Extract
ISO 1264-1980
Plastics-Homopolymer and copolymer resins of vinyl chlorideDetermination of pH of aqueous extract
BS 2782: Part 4
Method 454C: 1978 (= ISO 1264)
Determination of pH of aqueous extract of PVC resins
2.U Miscellaneous Properties Relevant to Processing
ASTM D 2396-79
Recommended practice for powder-mix test of poly(vinyl chloride) (PVC) resins using a torque rheometer
ASTM D 2538-79
Recommended practice for fusion test of poly(vinyl chloride)
(PVC) resins using a torque rheometer
ASTM D 2873-70 (1982)
Test for interior porosity of poly(vinyl chloride) (PVC) resins by
mercury intrusion porosimetry
1140
Ai
1141
(d) Miscellaneous
ASTM D 729-81
Specification fOr vinylidene chloride molding compounds
ASTM D 3364-74 (1979)
Test method for flow rates for poly(vinyl chloride) and rheologically unstable thermoplastics
1142
ISO 60-1977
ISO 61-1976
BS 2782: Part 6: Method 621A: 1978
BS 2782: Part 6: Method 621B: 1978
ASTM D 1895-69 (1979)
Al
1143
(ii)
CHEMICAL
ISO/R 182-1970
Plastics-Determination of the thermal stability of polyvinyl
chloride and related copolymers and their compounds by splitting
off of hydrogen chloride
ISO 305-1976
Plastics-Determination of thermal stability of polyvinyl chloride,
related chlorine-containing polymers and copolymers, and their
compounds-Discoloration method
BS 2782: Part 1
Method BOA: 1976 (=f:. ISO/R 182)
Determination of the thermal stability of polyvinyl chloride by the
Congo red method
Method BOB: 1976 (=1= ISO/R 182)
Determination of the thermal stability of polyvinyl chloride by the
pH method
ASTM D 793-49 (1976)
Test for short-time stability at elevated temperatures of plastics
containing chlorine
ASTM D 2115-67 (1980)
Recommended practice for oven heat stability of poly(vinyl
chloride) compositions
DIN 53381
Testing of plastics; determination of the thermal stability of
polyvinyl chloride and related copolymers and their compounds;
Part 1 (1971)
Congo red method
Part 2 (1975)
Discoloration method
Part 3 (1971)
pH method
(d) Mechanical Properties
BS 2782: Part 3: Method 365A: 1976
Determination of softness number of flexible plastics
1144
ISO 1385/1-1977
Phthalate esters for industrial use-Methods of test-Part 1:
General
ISO 1385/2-1977
Phthalate esters for industrial use-Methods of test-Part II:
Measurement of colour after heat treatment (Diallyl phthalate
excluded)
ISO 1385/3-1977
Phthalate esters for industrial use-Methods of test-Part III:
Determination of ash
1145
ISO 1385/4-1977
Phthalate esters for industrial use-Methods of test-Part IV:
Determination of acidity to phenolphthalein-Titrimetric method
ISO 1385/5-1977
Phthalate esters for industrial use-Methods of test-Part V:
Determination of ester content-Titrimetric method after saponification
ISO 2520-1974
Tritolyl phosphate for industrial use-List of methods of test
ISO 2521-1974
Tritolyl phosphate for industrial use-Determination of acidity to
phenol red-Volumetric method
ISO 2522-1974
Tritolyl phosphate for industrial use-Determination of apparent
free phenols content-Volumetric method
ISO 2523-1974
Adipate esters for industrial use-List of methods of test
ISO 2524-1974
Adipate esters for industrial use-Measurement of colour after
heat treatment
ISO 2525-1974
Adipate esters for industrial use-Determination of acidity to
phenolphthalein-Volumetric method
ISO 2526-1974
Adipate esters for industrial use-Determination of ash-Gravimetric method
ISO 2527-1974
Adipate esters for industrial use-Determination of ester content-Volumetric method
BS 573, 574, 1995, 1996, 2535, 2536, 3647: 1973
Plasticizer esters
Comprises: BS 573 Dibutyl phthalate
BS 574 Diethyl phthalate
BS 1995 Di-(2-ethylhexyl) phthalate
BS 1996 Dimethyl phthalate
BS 2535 Dibutyl sebacate
BS 2536 Di-(2-ethylphenyl) sebacate
BS 3647 Dimethoxyethyl phthalate
BS 1998: 1970
Triphenyl phosphate
1146
ISO 176-1976
Plastics-Determination of loss of plasticizers-Activated carbon
method
ISO 177-1976
Plastics-Determination of migration of plasticizers
BS 2782: Part 4
Method 465A and 465B: 1979 (= ISO 176)
Determination of loss of plasticizers (activated carbon method)
BS 2782: Part 5
Method 51lA: 1970
Effect of polyvinyl chloride compound on the loss tangent of
polythene
Al
1147
1148
1149
1150
BS 3501: 1962
Dinghy buoyancy equipment
ASTM D 1789-65 (1977)
Test for welding performance of poly(vinyl chloride) structures
DIN 1910
Part 3 (1977)
Welding; welding of plastics, processes
DIN 16930 (1964)
Welding of rigid PVC (rigid polyvinyl chloride); recommended
practice
DIN 16931 (1959)
Welding of nonrigid PVC (nonrigid polyvinyl chloride); recommended practice
DIN 16995 (1976)
Packaging materials; plastics films, main properties, special
properties, test methods
Note: Some properties of PVC films and sheeting are covered by
general plastics film and sheeting standards. Such standards
are mentioned in the appropriate chapters and in Appendix 3.
Some examples are water vapour permeability, gas permeability, electrical properties and flammability. BS 1133 Packaging
Code; Section 21: 1976 Regenerated cellulose film, aluminium
foil and flexible laminates is also relevant to plastics films for
packaging (cf. DIN 16995 above).
Al
1151
ISO 2035-1974
Unplasticized polyvinyl chloride (PVC) moulded fittings for elastic
sealing ring type joints for use under pressure-Pressure resistance
test
ISO 2043-1974
Unplasticized polyvinyl chloride (PVC) moulded fittings for elastic
sealing ring type joints for use under pressure-Oven test
ISO 2044-1974
Unplasticized polyvinyl chloride (PVC) injection-moulded solventwelded socket fittings for use with pressure pipe-Hydraulic
internal pressure test
ISO 2045-1973
Single sockets for unplasticized polyvinyl chloride (PVC) pressure
pipes with elastic sealing ring type joints-Minimum depths of
engagement
ISO 2048-1973
Double socket fittings for unplasticized polyvinyl chloride (PVC)
pressure pipes with elastic sealing ring type joints-Minimum
depths of engagement
ISO 2505-1981
Unplasticized polyvinyl chloride (PVC) pipes-Longitudinal reversion-Test methods and specification
ISO 2507-1982
Unplasticized polyvinyl chloride (PVC) pipes and fittings-Vicat
softening temperature-Test method and specification
ISO 2508-1981
Unplasticized polyvinyl chloride (PVC) pipes-Water absorption-Determination and specification
ISO 2536-1974
Unplasticized polyvinyl chloride (PVC) pressure pipes and fittings,
metric series-Dimensions of flanges
ISO 2703-1973
Buried unplasticized polyvinyl chloride (PVC) pipes for the supply
of gaseous fuels-Metric series-Specification
ISO 3114-1977
Unplasticized polyvinyl chloride (PVC) pipes for potable water
supply-Extractability of lead and tin-Test method
ISO 3460-1975
Unplasticized polyvinyl chloride (PVC) pressure pipes-Metric
series-Dimensions of adapter for backing flange
1152
ISO 3472-1975
Unplasticized polyvinyl chloride (PVC) pipes-Specification and
determination to resistance to acetone
ISO 3473-1977
Unplasticized polyvinyl chloride (PVC) pipes-Effect of sulphuric
acid-Requirement and test method
ISO 3474-1976
Unplasticized polyvinyl chloride (PVC) pipes-Specification and
measurement of opacity
ISO 3603-1977
Fittings for unplasticized polyvinyl chloride (PVC) pressure pipes
with elastic sealing ring type joints-Pressure test for leakproofness
ISO 3604-1976
Fittings for unplasticized polyvinyl chloride (PVC) pressure pipes
with elastic sealing ring type joints-Pressure test for leakproofness under conditions of external hydraulic pressure
ISO 3606-1976
Unplasticized polyvinyl chloride (PVC) pipes-Tolerances on
outside diameters and wall thicknesses
ISO 4434-1977
Unplasticized polyvinyl chloride (PVC) adapter fittings for
pipes under pressure-Laying length and size of threads-Metric
series
ISO 4439-1979
Unplasticized polyvinyl chloride (PVC) pipes and fittingsDetermination and specification of density
BS 3505: 1968 (1982) (oF ISO 2505, ISO 3114, ISO 3472-3, ISO
3474)
Unplasticized PVC pipe for cold water services
BS 3506: 1969
Unplasticized PVC pipe for industrial purposes
BS 3943: 1979
Plastics waste traps
BS 4346 ( ISO 2035, ISO 2043-5, ISO 2048)
Joints and fittings for use with unplasticized PVC pressure pipes
Part 1: 1969
Injection moulded PVC fittings for solvent welding for use with
pressure pipes, including potable water supply
Part 2: 1970
Mechanical joints and fittings principally of unplasticized PVC
1153
Part 3: 1982
Solvent cement
BS 4514: 1983
Unplasticized PVC soil and ventilating pipe, fittings and accessories
BS 4576
Unplasticized PVC rainwater goods
Part 1: 1982
Half-round gutters and circular pipe
BS4607
Non-metallic conduits and fittings for electrical installations
Part 1: 1970
Rigid PVC conduits and conduit fittings. Metric units
Part 2: 1970
Rigid PVC conduits and conduit fittings. Imperial units
Part 3: 1971
Pliable corrugated, plain and reinforced conduits of selfextinguishing plastics material
Part 5: 1982
Rigid conduits, fittings and components of insulating materials
BS 4660: 1973
Unplasticized PVC underground drain pipe and fittings
BS 5481 : 1977
Specification for unplasticized PVC pipe and fittings for gravity
sewers
BS CP 312
Plastics pipework (thermoplastics materials)
Part 2: 1973
Unplasticized PVC pipework for the conveyance of liquids under
pressure
ASTM D 876-71
Testing non rigid vinyl chloride polymer tubing used for electrical
insulation
ASTM D 1785-76
Specification for poly(vinyl chloride) (PVC) plastic pipe, schedules
40, 80 and 120
ASTM D 2152-80
Degree of fusion of extruded poly(vinyl chloride) (PVC) pipe and
molded fittings by acetone immersion
ASTM D 2241-80
Specification for poly(vinyl chloride) (PVC) plastic pipe (SDR-PR)
1154
ASTM D 2464-76
Specification for threaded poly(vinyl chloride) (PVC) plastic pipe
fittings, schedule 80
ASTM D 2466-78
Specification for poly(vinyl chloride) (PVC) plastic pipe fittings,
schedule 40
ASTM D 2467-76a
Specification for socket-type poly(vinyl chloride) (PVC) plastic
pipe fittings, schedule 80
ASTM D 2665-81
Specification for poly(vinyl chloride) (PVC) plastic drain, waste
and vent pipe and fittings
ASTM D 2672-80
Specification for bell-end poly(vinyl chloride) (PVC) pipe
ASTM D 2729-80
Specification for poly(vinyl chloride) (PVC) sewer pipe and fittings
ASTM D 2740-80
Specification for poly(vinyl chloride) (PVC) plastic tubing
ASTM D 2846-81
Specification for chlorinated poly(vinyl chloride) (CPVC) plastic
hot- and cold-water distribution systems
ASTM D 2949-78
Specification for 325-in outside diameter poly(vinyl chloride)
(PVC) plastic drain, waste, and vent pipe and fittings
ASTM D 3033-81
Specification for type PSP poly(vinyl chloride) (PVC) sewer pipe
and fittings
ASTM D 3034-81
Specification for type PSM poly(vinyl chloride) (PVC) sewer pipes
and fittings
DIN 1187 (1982)
Drain pipes of unplasticized polyvinyl chloride; dimensions,
general requirements, test methods
DIN 3441
Valves of unplasticized polyvinyl chloride
Part 1 (1982): requirements and tests
Part 2 (1977): ball valves, dimensions
Part 3 (1977): diaphragm valves, dimensions
Part 4 (1978): oblique pattern valves, dimensions
Al
1155
DIN 3543
Part 3 (1978)
Tapping valves for plastics pipes, dimensions
DIN 4279
Part 7 (1975)
Internal pressure test of pressure pipelines for water, pressure
pipes of unplasticized PVC
DIN 6660 (1980)
Pneumatic tube systems; conveyor tubes of rigid PVC
DIN 6661 (1979)
Pneumatic tube systems; sleeves of rigid PVC
DIN 6664 (1980)
Pneumatic tube systems, conveyor tube bends 900 of rigid PVC
DIN 8061
Part 1 (1974)
Pipes of rigid PVC; general quality requirements, test methods
Part 2 (1971)
Pipes of high impact PVC; general quality requirements, test
methods
DIN 8062 (1974)
Pipes of rigid PVC; dimensions
DIN 8063 Parts 1-11
Pipe joints and their elements for pipes of unplasticized PVC
under pressure
DIN 8079 (1974) (Preliminary Standard)
Pipes of PVC-C (chlorinated polyvinyl chloride) dimensions
DIN 8080 (1974) (Preliminary Standard)
Pipes of PVC-C; general quality requirements and test methods
DIN 16450 (1975)
Socket-fittings for pressure main lines of rigid polyvinyl chloride;
symbols
DIN 16451 Parts 1-7
Socket-fittings of cast iron with lamellar graphite for pressure main
lines of rigid polyvinyl chloride
DIN 16929 (1965)
Tubes and sheets of rigid PVC; resistance to chemicals, recommended practice
DIN 19531 (1980)
Pipes and fittings of unplasticized PVC, with rubber ring sockets,
1156
1157
ASTM D 876-80
Testing nonrigid vinyl chloride polymer tubing used for electrical
insulation
ASTM D 922-80
Specification for nonrigid vinyl chloride polymer tubing
ASTM D 3150-81
Specification for crosslinked and noncrosslinked poly(vinyl chloride) heat shrinkable tubing for electrical insulation
DIN 16940 (1964)
Extruded hoses of nonrigid PVC (nonrigid polyvinyl chloride);
permissable deviations for dimensions for which tolerances are not
indicated
DIN 16942 (1966)
Water-hoses of nonrigid PVC (nonrigid polyvinyl chloride);
dimensions
6.3
ISO 3514-1976
Chlorinated polyvinyl chloride (CPVC) pipes and fittingsSpecification and determination of density
ISO 3608-1976
Chlorinated polyvinyl chloride (CPVC) pipes-Tolerances on
outside diameters and wall thicknesses
ISO 4065-1978
Thermoplastic pipes-Universal wall thickness table
BS 4962: 1982
Pipes for use as light sub-soil drains
BS 5556: 1978 ( ISO 161/1)
Specification for general requirements for dimensions and pressure
ratings for pipe of thermoplastics materials (metric series)
BS CP 312
Plastics pipework (thermoplastics materials)
Part 1: 1973
General principles and choice of material
ASTM D 2152-80
Test for degree of fusion of extruded poly(vinyl chloride) (PVC)
pipe and molded fittings by acetone immersion
ASTM D 2564-80
Specification for solvent cements for poly(vinyl chloride) (PVC)
plastic pipe and fittings
1158
ASTM D 2855-81
Recommended practice for making solvent-cemented joints with
poly(vinyl chloride) (PVC) pipe and fittings
ASTM D 3036-73
Specification for socket-type poly(vinyl chloride) (PVC) plastic
line couplings
ASTM F 409-81
Specification for thermoplastic accessible and replaceable plastic
tube and tubular fittings
ASTM F 412-81
Definitions of terms relating to plastic piping systems
DIN 16929 (1965)
Tubes and sheets of rigid PVC (rigid polyvinyl chloride);
resistance to chemicals, recommended practice
ISO 1419-1977
Fabrics coated with rubber or plastics-Accelerated ageing and
simulated service tests
ISO 1420-1978
Rubber and plastics coated fabric-Determination of resistance to
penetration by water
ISO 1421-1977
Fabrics coated with rubber or plastics-Determination of breaking
strength and elongation at break
BS 351: 1976 (=1= ISO 22)
Specification for rubber, balata or plastics flat transmission belting
of textile construction for general use
BS 490
Conveyor and elevator belting
BSO 490
Part 1: 1972 (=f:. ISO 282, ISO 283, ISO 703, ISO 1121)
Rubber and plastics conveyor belting of textile construction for
1159
1160
1161
ISO 2796-1980
Cellular plastics-Test for dimensional stability of rigid materials
ISOrrR 2799-1978
Cellular plastics-Determination of the temperature at which fixed
permanent deformation of rigid materials occurs under compressive load
ISO 2896-1974
Rigid cellular plastics-Determination of water absorption
BS 3869: 1965
Rigid expanded polyvinyl chloride for thermal insulation purposes
and building applications
BS 4370
Methods of test for rigid cellular materials
Part 1: 1968 (=1= ISO 844, 845, 1923)
Methods 1-5
Part 2: 1973 (=1= ISO 1922; ISO 1926)
Methods 6-10
Part 3: 1974
Methods 11-13
ASTM D 1621-73 (1979)
Test for compressive properties of rigid cellular plastics
ASTM D 1622-63 (1975)
Test for apparent density of rigid cellular plastics
ASTM D 1623-78
Test for tensile properties of rigid cellular plastics
ASTM D 2126-75
Test for response of rigid cellular plastics to thermal and humid
aging
ASTM D 2842-69 (1975)
Test for water absorption of rigid cellular plastics
DIN 53421 (1971)
Testing of rigid cellular plastics; compression test
DIN 53423 (1975)
Testing of rigid cellular plastics; bending test
DIN 53424 (1978)
Testing of rigid cellular plastics; determination of dimensional
stability under heat in the case of flexural load and compression
load
DIN 53425 (1965)
Testing of rigid foams; creep-depending-on-time compression test
under heat
1162
BS 4023: 1975
Flexible cellular PVC sheeting
BS 4443 (~ ISO 485, 1794, 1798, 1856,3386)
Methods of test for flexible cellular materials
Part 1: 1979
Methods 1 to 6
Part 2: 1972 (= ISO 2439)
Method 7-Indentation hardness test
Part 3: 1975
Method 8--Determination of creep
Method 9-Determination of dynamic cushioning performance
Part 4: 1976 (;zf ISO 2440)
Methods 10-12
Part 5: 1980
Test for dynamic fatigue by constant load pounding
Part 6: 1980
Methods 14-16
ASTM D 1565-81
Specification for flexible cellular materials-vinyl chloride polymers and copolymers (open-cell foam)
ASTM D 1667-76 (1981)
Specification for flexible cellular materials-vinyl chloride polymers and copolymers (closed-cell vinyl)
DIN 53570 (1981)
Testing cellular materials; determination of linear dimensions
DIN 53571 (1978)
Testing of flexible cellular materials; test of the tensile strength
1163
1164
Al
1165
(iii) ACOUSTICAL
ASTM C 384-77 (1981)
Test for impedance and absorption of acoustical materials by the
impedance tube method
ASTM C 423-81
Test for sound absorption and sound absorption coefficient by the
reverberation room method
(g) Cushioning Materials
ASTM D 1596-78
Test for shock absorbing characteristics of package cushioning
materials
ASTM D 2221-68 (1979)
Test for creep properties of package cushioning materials
(h) Sandwich Structures
ASTM C 273-61 (1980)
Shear test in flatwise plane of flat sandwich constructions or
sandwich cores
ASTM C 393-62 (1980)
Flexure test of flat sandwich constructions
1166
Al
1167
10 PVC FLOORING
BS 3260: 1969
PVC (vinyl) asbestos floor tiles
BS 3261
Unbacked flexible PVC flooring
Part 1: 1973
Homogeneous flooring
BS 4902: 1976
Specification for sheet and tile flooring colours for building
purposes
BS 5085
Backed flexible PVC flooring
Part 2: 1976
Cellular PVC backing
DIN 16950 (1977)
Flooring materials; vinyl-asbestos-tiles, requirements, test
methods
DIN 16951 (1977)
Floor coverings; polyvinyl chloride (PVC) flooring without
backing, requirements, test methods
11.2 Miscellaneous
ISO 580-1973
Moulded fittings in unplasticized polyvinyl chloride (PVC) for use
under pressure-Oven test
1168
BS 3887: 1965
Regenerated cellulose and unplasticized PVC pressure-sensitive
closing and sealing tapes
ASTM D 2301-73 (1979)
Specification for vinyl chloride plastic pressure-sensitive electrical
insulating tape
ASTM D 3005-73 (1979)
Specification for low-temperature resistant vinyl chloride plastic
pressure-sensitive electrical insulating tape
DIN 16941 (1964)
Extruded profiles of nonrigid PVC (nonrigid polyvinyl chloride);
permissable deviations for dimensions for which tolerances are not
indicated
DIN 53419 (1977)
Extruded profiles of unplasticized polyvinyl chloride (unplasticized
PVC); test method of the behaviour against methylene chloride
APPENDIX 2
1170
W. V. Titow
ISO 1000-1973. * 'SI Units and recommendations for the use of their
multiples and of certain other units'.
BS 350. 'Conversion factors and Tables'
(Part 1 :1974, Part 2: 1962 with Supplement No.1: 1967).
BS 1991. 'Letter symbols, signs and abbreviations'
Covering general aspects (Part 1: 1976), chemical engineering,
nuclear science and applied chemistry (Part 2: 1961), fluid mechanics
(Part 3: 1961), structures, materials and soil mechanics (Part
4: 1961), applied thermodynamics (Part 5: 1961), electrical science
and engineering (Part 6: 1975) with a list of subscripts for electrical
technology (Supplement No.1: 1973 to Part 6).
BS 3763: 1976. 'The International System of Units (SI)'
ASTM Metric Practice Guide (1976). US National Bureau of
Standards.
Changing to the Metric System. (1969). Anderton, P. and Bigg, P. H.,
HMSO.
The International System of Units (1973). HMSO.
The Use of SI Units (1969). British Standards Institution.
Quantities, Units and Symbols (1975). The Royal Society.
A Dictionary of Scientific Units. (1964). lerrard, H. G. and McNeill,
D. B., Chapman and Hall.
A2
1171
Unit
Name
Common
Equivalent in
equivalent
base (and
Symbol
in Sl
supplementary)
units
Sl units
Length (L, I)
Mass (M, m)
Time (T, t)
Electric current (I)
Thermodynamic temperature
(e, T)
Luminous intensity (J, I)
Amount of substance
(N, n)
metre
kilogram
second
ampere
m
kg
s
A
kelvin
candela
cd
mole
mol
Supplementary
units
radian
steradian
Tad
sr
Derived units
with special
names
gray
farad
siemens
Gy
F
S
J kg-I
Cy-l
Ay-l
m2 s- 2
s' A 2 m- 2 kg-I
S3 A 2 m- 2 kg- 1
volt
ohm
WA- 1
YA- 1
m2 kgs- 3 A- 1
m2 kgs- 3 A- 2
joule
newton
hertz
lux
henry
lumen
weber
tesla
watt
pascal
J
N
Hz
Ix
Nm
m2 kg S-2
m kgs- 2
S-I
WbA- 1
1m
Wb
T
W
Pa
Ys
Wbm- 2
J S-l
Nm- 2
coulomb
Base units
!p,
etc.)
cd srm- 2
m2 kgs- 2 A- 2
cd sr
m2 kgs- 2 A- 1
kgs- 2 A- 1
m2 kgs- 3
kg m- I S-2
As
1172
W. V. Titow
Multiple
Prefix
Symbol
x 1018
exa
E
x 1015
pela
P
Sub-multiple
Prefix
Symbol
x 10- 1 x 10- 2
(deci) (cenli)
d
c
1012
lera
10- 3
milli
m
109
giga
G
10- 6
micro
/.l
6
X 10
mega
M
10- 9
nano
n
x 1cP
kilo
k
x lOZ
(hecla)
h
10- 12
pica
10- 15
femlo
f
xlO
(deca)
da
10- 18
atto
a
SI unit
s
1
3155 6926 x 10'
8640 x 1Q4
3600
60
a
year
3169 x
1
2738 x
1141 x
1901 X
10- 8
10- 3
10-4
10- 6
d
(solar day)b
h
(hour)
min
(minute)
1157 X 10- 5
36524
1
4167 X 10- 2
6944 X 10- 4
2778 X 10- 4
8766 x 103
24
1
1667 X 10- 2
1667 X 10- 2
5259 x lOS
1440
60
1
1000
10
1
1 X 10- 3
1 X 10- 7
9144
3048
254
100
1
01
1 X 10- 4
1 X 10- 8
9144
3048
254
1
001
1 X 10- 3
1 X 10- 6
1 X 10- 10
09144
0304 8
00254
254
X
10
1 X 106
1 X 104
1 X 103
1
1 X 10- 4
jimQ
1X
1X
1X
1X
1010
108
107
104
1
(angstrom)
mm
cm
Sf units
328084
0032808
32808 X 10- 3
3
1
0083333
1
0333333
0027778
ft
(foot)
1093610
0010 936
1093 6 X 10- 3
yd
(yard)
36
12
1
393701
0393701
0039370
in
(inch)
?3
-.I
........
'"
if
c::r-
;:;'J
;:l
'"5't::l
-<:
;:l
~.
~
too>
'"
;;l
~.
~:
K:l
1
1 X lO-4
1 X lO-6
08361
009290
6452 X lO-4
mm
1 X 1()6
100
1
8 361 27 X lOS
92903 X 10'
645-16
1 X 10"
1
001
8361 X 10'
929
64516
cm 2
SI units
1196
1196xlO- 4
1196 X 10- 6
1
01111
7716 X 10- 4
yd
10764
1076 X 10- 3
1076 X 10- 5
9
1
6944 X lO-3
it>
1550 X lO3
01550
1550 X lO-3
1296 X 10'
144
1
in 2
:0::::
......
......
cm3
UK gal
(UK gallon)
2200
2-2 X 10- 4
22 X 10-7
1
08327
0-2200
6-229
3605 X 10- 3
mm 3
1 X 109
1 X 103
1
4-546 X 106
3-785 X 106
1 X 106
2-832 X 107
16387 x 104
1 x 106
1
6
1 X 101
1 X 10-3
1 x 10- 9
4546 X 10-3 4-546 X 103
3-785 x 10-3 3-785 X 103
1 x 10- 3
1 X 103
0-02832
2832 x 104
1-6387 x 10- 5
16-39
m3
Sf units
264-2
2-642 X 10- 4
2642 X 10-7
1201
1
0264 2
7-4805
4329 X 10- 3
US gal
(US gallon)
1 x 103
1 X 10- 3
1 X 10- 6
4-546
3785
1
2832
001639
(litre)a
fr3
35-32
3-532 X 10-5
3532 X 10- 8
0-1605
01337
0-03532
1
5787 x 10- 4
6-1024 x 104
0061024
61024 x 10- 5
2774
2310
61024
1728 x 103
1
-.l
V1
........
1r
<::>-
o
;:s
~
;,..
""
'"~
~.
in 3
S
S.
:::to
to
343775 x 1cP
60
1
00166667
54
54 X 103
572958
1
00166667
277778 x 10- 4
09
90
1
00174533
2908 88 x 10- 4
484814 X 10- 6
00157080
157080
206265 x
36 X
60
1
3240 x
3240 X
10
105
10
103
"
(secondt
Other units
g
636620
111111
00185185
308642 x 10- 4
1
100
(grade)
(minuteY
(degree)ab
rad
(radian)
S1 unit
0636620
0011111
1851 85 x 10- 4
308642 x 10- 6
001
1
(right angle)
:-=:::
a-
--.I
--
123457 x 10- 4
1
1
081
4052 85 x 10
328281 x 1<>3
0079577 5
1
1
125664
3046 17 x 10- 4
246740 x 10- 4
(square grade)
OK
00
(square degree)
sp
(spat)a
Other units
sr
(steradian)
SI unit
-J
-J
--
ff
0-
;:
0"
'"C::l"
;:
~
::::
'"
;:J
S.
~
l:l
s:~
10
~
N
1 x lQ3
1
1 X 106
1
1 x 10- 3
1 x 103
101605 x 103
907185
508023
0453592
0028350
f'
1 x 10- 3
1 X 106
1
101605
0907185
005080
45359 x 10- 4
(tonne)
1102 3 x 10- 3
1102310
112
1
0056
500 X 10-4
0984207
1
0892857
005
44643 x 10- 4
US tone
9842 1 x 10- 4
UK ton b
196841
20
178571
1
89286 x 10- 3
0019684
cwt
(hundredweight)
220462
220462 x 10- 3
220462 x 103
224 x 103
2 x 103
112
1
00625
(pound)
352740
0035274
352739 x 104
3584 X 104
32 X 104
1792 x 103
16
1
oz
(ounce)
Also known as 'metric ton' or 'metric tonne'. Unit recognised for use with the International System. 1 t = 1 Mg (which is an SI unit).
The 'long' ton.
e The 'short' ton.
508023 x 10
453592
283495
g
(gram)
kg
Sf units
:::1
-..l
00
.....
.....
1179
kgm- 3
gcm- 3
kgl- 1
Ibin- 3
Ibft- 3
lb UKgal- 1
1
1 X 1<P
1 X J(}l
276799 X lO'
160185
99776
1 X 10- 3
1
1
27-6799
00160185
0099776
I X 10- 3
I
I
276799
00160185
0099776
36127 X 10- 5
0036127
0036127
I
57870 X 10-'
3-604 6 X 10- 3
0062428
62-4280
62-4280
1728XI<P
I
622884
0010022
100224
100224
277-419
0160544
I
1
2777 6 x 10- 4
0,16666
13561 x 10- 3
3600
60000
488243
16666 x 10- 3
1
81370 x 10-3
73734
020481
12289
1
kg!
(kilogram-force)"
dyn
(dyne)
UK tonf
(UK ton-force)
lbf
(pound-force)
pdl
(poundal)
I
9807
I x 10- 5
9964 x I<P
4448
01383
01020
I
1-02 X 10- 6
1016 x 1<P
04536
00141
I X lOS
1004 X 10-'
9842 x 10-'
02248
22046
2248 X 10- 6
2240 x I<P
I
00311
7233
7093
7233 X 10- 5
7207 x 10'
32174
I
1
4464 x 10-'
1390 x 10- 5
bar
1 X 10- 5
1013
1
09807
006895
2-491 X 10- 3
1333 X 10- 3
1 X 10- 6
atm
(standard
atmosphere)b
9869 x 10- 6
1
09869
096708
006805
2458 X 10- 3
1316 X 10- 3
9869 X 10- 7
1 Pa
1450 X 10- 4
1470
1450
1422
1
003613
001934
1450 X 10- 5
clbfin- z
foo atm.
1020 X 10- 5
1033b
1020
1
007031
2540 X 10- 3
1360 X 10- 3
1020 X 10- 6
kgfcm- z
= 1 N m- z ; 1 MPa = 1 MN m- z = 1 N mm- z .
1 atm = 1033228 technical atmosphere (at); 1 at = 1 kgf cm- z.
C Often denoted by 'psi'.
dOften referred to as 'inches water gauge' (in w.g.).
C 1 mm Hg = 1 torr (to within one part in seven million); 1 torr =
1013 X 105
1 X 105
9807 X 104
6895 X 103
2491
1333
0100
PaO
SI unit
4015 X 10- 3
4068
4015
3937
2768
1
05352
4015 X 10- 4
in HZO d
(inches of
water)
7501 X 10- 3
760
7501
7356
5171
1868
1
7501 X 10- 4
mmHgC
(millimetres
of mercury)
10
1013 x
1x
9807 x
6895 x
2-491 x
1333 X
1
106
106
105
104
103
103
dyn cm- z
~
:0:::
10-7
2724 X 10- 6
1163 X 10- 6
29307
2931 x 10- 4
3766 X 10-7
2778
kWh
(kilowatt
hour)
01020
3671 x 105
1
04270
10759 x 107
10759
01383
kgfm
02388
85985 x 105
23420
1
25200 x 107
25200
03238
cal
(calorieY
1 X 10- 5
1285 X 10- 8
9478
003412
9294 x 10- 8
3968 X 10- 8
X 10- 9
therm
1285
X 10- 3
Btu
(British
thermal unity
07376
26552 x 106
72330
30880
77817 x 107
77817
1
ftlbf
The
The
The
The
The
In this table these units have their International Table values, now in general use (1 cal == 41868 J; 1 Btu == 105506 J.
These values are always implied when the unit is written without a specifying subscript (i.e. simply 'cal' or 'Btu') but the
notation 'cain' and 'BtuIT' is still sometimes employed. Other values occasionally used are:
1
3600 X 106
98066
41868
1055 06 x 108
1055 06 x 103
13558
SI unit
--
:-:l
"
~
~.
'
'"
'"
~
~.
'
;:0
s:
lC
::t>.
""
W. V. Titow
1182
W
1
7355
9807
4187
7457
029307
kgfms- I
cal S-I
hpb
(horsepower)
Btuh- 1
x 10- 3
010197
7500
1
04268
7604
002988
02388
1757
2343
1
1781
006999
1341 x 10- 3
098632
001315
5613 x 10- 3
1
3929 x 10- 4
34128
2510 x 103
33-47
1429
2545 x 1Q3
1
1360
1
0013 33
5692 x 10- 3
10139
3984 x 10- 4
No symbol for this unit in English-speaking countries (in France ch or CV; in Germany
PS). Unit now regarded as obsolescent.
b Unit traditionally used in the UK and USA. Now regarded as obsolescent.
Sf unit
hertz (Hz)
reciprocal second (s-I)
Periodic frequency
Rotational frequency
(i.e. number of rotations
in unit time)
Angular frequency
Other units
cycle per second (c s-I)a
revolutions per second;
minute, etc. (i.e. r S-I,
rOlin-I; etc.)b
(kelvin)
(degrees
Celsius)
OR
(degrees
Rankine)
yKa
xOC
uOR
zOF
y
x + 27315
ul18
y - 27315
x
(ul1'8) - 27315
(z - 32)/1'8
l'8y
l'8(x + 27315)
u
z + 45967
is
Ka
(z + 45967)/18
o~
of
(degrees
Fahrenheit)
18y-45967
18x + 32
u - 45967
z
2388 X 10-3
02388
1
2778 x 10- 3
4134 x 10- 3
3445 X 10- 4
1 X 10- 2
1
4187
001163
001731
1442 x 10- 3
1
08598
8598
3600
1
1488
01240
kcal h- 1 m- 1 K- 1
05778
5778
2419
06720
1
008333
aBtu h- 1 [t- 1 F- 1
6933
6933
2903 x 103
8064
1200
1
Btu in h- 1 [t- 2 F- 1
Where they form part of the units in this table, the calorie and Btu have their international table values (see the Energy
Unit Conversion Table).
100
4187
1163
1731
01442
Wcm- 1 K- 1
Wm- 1 K- 1
51 unit
00
.....
......
......
~
~
;;l
'
.~
~
[
~
to>
'"
:::z
~.
s::...
I:>
::>.
::>.
lC
tv
W. V. Titow
1184
085984
1
36001 x 104
488240
1-16301
41868 x 104
567827
238846 x 10- 5
2 7777 x 10- 5
017611
0204 81
7372 9 x 103
1
13562 x 10- 4
a Where they form part of the units in this table, the calorie and Btu have their
international table values (see the Energy Unit Conversion Table).
Dynamic viscosity
Sf unit
01
1 x 10- 3
Sf unit
pa
(poise)
cP
m 2 s- 1
(centipoise)
10
1
001
1 X 103
100
1
1
1 X 10- 4
1 X 10- 6
sf>
cSt
(centistokes)
1 X 104
1
001
1 X 106
100
1
APPENDIX 3
TITOW
Nm- 2 (=Pa);
lbf in- 2 (psi);
kgf cm- 2 ;
For fibres: g per
denier, or g per
tex
Tensile
strength
arb
kgm- 3
gcm- 3
Ibin- 3
lb ft- 3
Common
units
Brief definition
Density
p
Property arid
usual symbol
M; S: 130145 g cm- 3
M(G): approx
15gcm- 3
F: approx 14
gcm- 3
PVC homopolymer: 14
gcm- 3
Rigid PVC
M: 110-135 g
cm- 3
Flexible PVC
ISO/R 527-1966;
ISO/R 1184-1970 (for films);
BS 2782: Part 6:
Methods 620A-D: 1980;
BS 4618: Section 5.1: 1970;
ASTM D 792-66 (1979)
(Displacement method);
ASTM D 1505-68 (1979)
(Density gradient tube);
DIN 53479-1976
ISO/R 1183-1970;
ISO 6383-1983;
BS 1763: 1975 (thin sheeting:
Elmendorf test);
BS 2739: 1975 (thick sheeting);
BS 2782: Part 3: Method 36OB:
1980 (trouser-tear test);
M: 62-100
MPa
(ASTMD
790)
M(G): approx
138MPa
(ASTMD
790)
S: 20-100 N mm- 1
M: 150-400%
S: 120-250%
M: 2-40%
M(G): 1-2%
S: 5-35%
F: 10-20%
b.d
(continued)
M = mouldings; M(G) = mouldings with 25% glass fibre; S = sheeting and/or film; F = fibre.
Symbol not in wide general use.
c Specification numbers in brackets after numerical property values indicate the source of standard test(s) by which the values were
obtained, not that the values are numerical requirements laid down in the particular specification(s).
N; kgf; lbf;
or
g; oz; lb;
or
Nmm-\ kgf
mm- 1
OF
ISO 178-1975;
BS 2782: Part 3:
Method 335A: 1978;
ASTM D 790-81;
DIN 53452-1977
Flexural
strength
Normally % of
the original
length; occasionally units of
length
Elongation at
break (or
yield)
eTd
Impact
resistance
(Impact
strength)
Tear resistance
(contd)
Property and
usual symbol
Brief definition
Nm (=J);
kgfcm;
lbfft;
per unit length of
notch (for notched specimens) or
per unit area of
the cross-section
of the unnotched
part, or (for unnotched specimens) per unit
specimen width
or crosssectional area.
Common
units
Flexible PVC
M: 05-25 lbf
With small
ft in- I
amounts of plasticiser impact
(ASTMD
strength can be
256)
M(G): approx
very low 05
llbfft in- I lbfft in-I) the
embrittlement
(ASTMD
256)
being caused by
the so-called
'antiplasticisation'
effect. Very high
at normal plasticiser contents
Rigid PVC
:::'l
0
:0:::
00
00
ASTM test essentially similar to ISO 180, but differs (in root radius of notch) from that of BS 2782.
Applicable mainly to pPVc.
Relevant to glass-reinforced plastics.
Hardness
(continued)
M (and other
compounds):
BS softness No.
15-90
Durometer
(Shore A
scale): 50-95
Rockwell (R
scale) 5-80
t;-
~c
I::l
"tl
.s;,
~
::to
~
.g
~
E:.:
I::l
v,
)..
...,
(b) in shear
G
(c) in flexure
EB
Common
units
As for tensile
strength
Brief definition
Elastic
moduli:
(a) in tension;
E
Property and
usual symbol
ISO 178-1975;
ISOITR 4137-1978 (Alternating
flexure method);
BS 2782: Part 3:
Method 332A: 1976 (stiffness
of film);
Method 335A: 1978;
ASTM D 790-81;
DIN 53457-1968
ISO/R 527-1966;
BS 2782: Part 3: Methods 320A
to F: 1976;
ASTM D 638-82;
ASTM D 882-81 (for thin sheet
and films);
DIN 53457-1968
Rigid PVC
:::l
S
>-'
>-'
:g
(ASTMC 177)
Wm-1K- 1
;:
it
l:>
<">
1;;
(continued)
f}
;:s
(ASTM C 177) ]
Wm- 1 K- 1
M (and other
compounds):
014-017
M (and other
compounds):
014-028
Thermal conductivity
k;)"
M (and other
~
compounds): ~
General-purpose It
plasticised com- ~
pound typically ~
about 40, but
i:!-.
the range is wide ~
(ASTM D 1525 .Q.,
does not recom- ~
mend the test for ~
pPVC for that
~
reason)
~
M (and other
compounds):
65-100C
(ISO 306:5
kg load)
ISO 306-1974;
BS 2782 : Part 1: Methods 120A
to E: 1976;
ASTM D 1525-76;
DIN 53460-1976
"'"
:t.
Cor OF
Low at
normal
plasticiser
contents
M: 22-35
GPa
(ASTMD
695)
ISO 604-1973;
ASTM D 695-80;
DIN 53457-1968
(d) in compression
K
(BS 2782:
Method
335A)
K- 1 ; 0C- 1 ; F- t
C; of
Percentage deformation of a
sheet specimen of prescribed dimensions by a
specified load at 70C,
under stated test conditions
Coefficient of
linear thermal
expansion
Deflection
temperature
under load
Deformation
under heat of
flexible PVC
compounds k
ISO 75-1974;
BS 2782: Methods 121A and
B: 1976;
ASTM D 648-72 (1978);
DIN 53461-1969
Common
units
Brief definition
Property and
usual symbol
M (and other
compounds) :
15-65%
(BS 2782)
M (and other
compounds) :
10 x 10- 5_
25 x
10- 5 K- 1
(ASTMD 696)
Flexible PVC
M (and other
compounds):
6O-80Ci
(ISO, BS,
ASTMor
DIN)
M(G): 7085Ci
(ISO, BS,
ASTMor
DIN)
M (and other
compounds):
5 x 10- 5_
15 x 10- 5
K- 1
(ASTMD
696)
M(G): 27 x
10- 5
(ASTMD
696)
Rigid PVC
'l:
:::'l
S
:<::;
to.>
'0
......
......
Permittivity'"
(dielectric
constant)
k'; '
Loss tangentn
(dissipation
factorO)
tan 0
None
(a ratio)
None
(a ratio)
J g-IK- 1 ;
Ical g-l 0C-\
IBtu Ib- 1 F- 1
M (and other
compounds):
45-85 at 50
Hz
35-45 at
1 MHz
(ASTMor
DIN)
M (and other
compounds):
1.0--2.0 J g-l
K- 1
~.
~
~
::t
'"
..,<;;
'"
~
3
.....
.....
\D
.,
~o
M (and other
M (and other
-s;,
comcompounds) : ."
pounds):
0OS-O15 at ~
60Hz
0007-0017
004-014 at ~
at 60Hz
0006-0019
1 MHz
at 1 MHz
(ASTM D 150)
.,."
(ASTMD
150)
~
M (and other
compounds):
33-36 at
50Hz
29-31 at
1 MHz
(ASTM or
DIN)
M (and other
compounds):
0S-O9 J
g-l K-1
At 254Ibfin- 2 .
k The temperature of heat distortion (extension or shrinkage), under tensile load, of 00025-15 mm thick, relatively stiff plastics
sheeting (room-temperature elastic modulus >69 MPa) may be determined by the method of ASTM D 1637-61 (reapproved 1976).
I Numerically identical.
m Strictly, relative permittivity (see, e.g. BS 4618 or ASTM D 150).
n Term favoured in the UK.
o Term favoured in the USA and Europe.
(continued)
Specific heat
c
Resistivity
p;s
Property and
usual symbol
Qm
Qcm
Common
units
Brief definition
M (and other
compounds) :
1012_10 15 Q
cm at 60%
RH; room
temperature
(ASTM;DIN)
Flexible PVC
M (and other
M (and other
comcompounds):
1011_10 12 Q
pounds):
1013_10 14 Q
at 60% RH;
at 60%
room
RH;
temperature
room
(DIN)
temperature
(DIN)
room
temperature
(ASTM;
DIN)
RH',
M (and other
compounds):
About
1016 Qcm
or higher
at 60%
Rigid PVC
is
:::;j
:-:::
.j:o.
\0
--
Water absorption
g; mg; mass %
(volume % for
cellular plastics)
Vm- I ; Vcm-I;
Vmm- I ; V mil-I
(1 mil = 0001 in)
(continued)
M (and other
M (and other
compounds) :
compounds):
3O-150mg
(48 h)
8-50mg
(BS 2782:
(48 h)
Method
(BS 2782:
502e)
Method
015-10%'
502e)
007-040%' (ASTMD 57024h
(ASTMD57024 h
specimen
0125 in
specimen
thick)
0125 in
thick)
M (and other
compounds:
25D-400V
mil-I
(ASTMSpecimen
125 mil thick)
M (and other
compounds):
400-500 V
mil-I
(ASTMSpecimen
125 mil
thick)
Dielectric
strength
......
......
\0
VI
1}
l::
;>
~o
!i
f2
.s;,
'"
i;.
.g
~
.:
.......
)..
Fo
/is
= FsIL
Ilo = FoIL
where Fs = the minimum force
None
(a ratio)
Coefficients of
friction
Il
No conventional units.
Measured in
terms of mass
loss by the
specimen, or
visual effects,
e.g. marring
of surface,
loss of transparency.
Common
units
Brief definition
Abrasion
resistance
Property and
usual symbol
Flexible PVC
:::J
<s
The values of friction coefficients
of PVC depend cardinally on the
formulation, and generally decrease with increasing rigidity
M (and other
M (and other
comcompounds);
pounds);
also S: about
also S:
02-20
normally
<02
Rigid PVC
particular material
None
(a ratio)
/-l;n
Refractive
index
ISO/R 489-1966;
BS 4618: Section 5.3: 1972;
ASTM D 542-50 (1977);
DIN 53 491-1955
PVC resin:
approx
155
M: 152-155
!:;-
;:s
s::
~o
f2-
."
.g
~.
INDEX 1
General
Acrylic
impact modifiers, 99,107,391,395,
396,482,887
lacquers, 1008-9, 1061
light-protective coatings, 482
processing aids, 98, 108, 372-5,
395,396,795
thickeners for PVC latices, 1021,
1023, 1025, 1027
Acrylonitrile butadiene styrene
(ABS) copolymers
blends with PVC, 99, 393,395
impact modifiers, as, 99,113,114,
390,391,393-5,482
processing aids, as, 373
sheet laminates with PVC, 745
Activators ('kickers'), see under
Blowing agents
Adhesion
promoters for PVC coatings, 62,
174, 1007-8, 1119
solution-deposited copolymer films,
of, 1047, 1049-51, 1061,
1063-5
Adhesive bonding of PVC, see under
Bonding of PVC
Ageing of pastes, 943-5, 963,964,
966
AGS acid ester plasticisers (see also
under Aliphatic diester piasticisers), 149, 165, 166,976,
977
1199
1200
Index I General
Antistatic agents-contd.
thermal stability, effect on, 106,
260,423-4
A p / Po ratio (of plasticisers), 130-1,
140-1
physical properties of PVC, effect
on, 140-1
Asbestos
filler, as, 216, 217, 242, 243
surface treatments for, 242
flooring, in, 109-10, 217, 233
hazards of, 242
heat stability of PVC, effect on,
217
properties, 243
sheet reinforced with, 217, 903,
908-9
.
thixotropic additive, as, 242
AZDN,1090-1
Azobisformamide (ABFA), see Azodicarbonamide
Azodicarbonamide (ADA), 108(r90
Baby pants, 1122
Barium
stabilisers, 91, 109, 113--15,275,
280,303-4,338,341,345,
347-54,356
sulphate, 219-20, 222-3, 282-3, 285
Barrier properties of
blown bottles, 458, 462-3, 798-800
PVC compositions, see Permeability
shrink-wrap PVC films, 895
Barytes, 219, 222
Battery separators
passim, 1069
polymer for, 854
production, 1078, 1079
property tests, 1100, 1101
PVC's competitor materials, 1118
Biaxial stretching effects on
impact resistance, 19, 27, 761,
774-5, 794
permeability, 19,29,464,774-5
'Bingham body' behaviour, 947-8,
951,996
Index I
Blow moulding-eontd.
product-eontd.
General
1201
Bonding of PVC-contd.
solvent and solvent cement-eontd.
procedures, 924-5
specifications relevant to, 927,
1063
Brittle-ductile transition, 386-8, 866
Brittle fracture, 384-5, 866, 868
Brittle point, 386, 388, 440
Brittle temperature, 386-8
Brittleness temperature, 386, 440,441
Bronzing, 405
BS softness
fillers, effect of, 218
measurement, 65, 184-5
number scale, 184, 186
plasticisers, effect of, 162, 172, 185,
187
rubber hardness, and, 184, 186
Shore hardness, and, 184,186
temperature, effect of, 189,450
values of pPVC, 72-7, 1189
Bulk (mass)
polymer particle characteristics, 46,
47,690-1
polymerisation, 40
Burning (see also Flammability)
plastics, of, 424, 426-7, 428, 501-2,
508-9
PVC, of
effect of plasticisers, 161,204-6,
503,508
products of 499-500
role of chlorine in, 161,427,429,
502-3,508
Cable and wire insulation and coverings (see also under Compounding)
application (by extrusion), 717-19
compounds, 72-3,111,346,581
cable design, and, 602
cross-linkable, 72, 449-50, 1114
formulation, 111, 202, 346
production, see under Compounding
PVC/nitrile rubber, 400,1166
reclaimed PVC in, 601-2
1202
Index 1 General
Calender---eontd.
roll (bowl)---eontd.
crossing, 807-8
crowning, 807
deflection, 806-7
number in stack, 804-5, 828
numbering, 805-6
stripper rolls, 820-1, 822
suppliers, 804
Calendered sheet
applications, 847, 1107-9
defects and faults in, 809, 823-4,
833-7
flooring, for, 828
lamination of, 829-30, 837-8, 839-
40
Index I
Calendering-eontd.
General
1203
Chlorinated compounds
paraffins
degradation of, 255-6
flame retardants, as, see under
Flame retardants
plasticiser extenders, as, 171-3
polyethylene (CPE)
calendering of, 803
chemical structure of, 396
degradation of, 255
impact modifier, as, 396-7, 887,
888
plasticiser, as 397, 832
polyvinyl chloride (CPVC), 24-9
applications, 5, 25, 28, 851,868,
1105
chemical structure of, 25-7
commercial compounds of, 25,
27,28,832
fibres from, 5,25
production of, 5, 24-5
properties of, 26-9, 858, 868
solvent cements for, 1063
thermoformability of, 745, 761
Chromium pigments, 409, 415,418,
1056
Citrate plasticisers, 174
Cladding, 452, 893-4
Clay
filler, as, 100, 101,216,217-19,
220,223,971,1037
oil absorption of, 971
thickener for pastes, as, 973-4
Clear point temperature, 127-9,959
commercial plasticisers, of, 129
Coated fabrics
applications and products, 1111-12,
1113--14
production, 829, 998-1009, 1072,
1077,1094
properties and tests, 844-5, 100910
Coating, see under Lacquers, Pastes,
and Surface
Coextrusion, 482, 685, 765, 884, 892
Cold bend temperature, 193,442
Cold crack temperature offilm, 193,
441
1204
Index 1 General
Compounding~ontd.
in-line
calendering, for, 589-97, 81014
extrusion, for, 549, 867
latex compositions, of, 1019-38
masterbatches, of, 587
melt, 577-603
equipment for, 609-51
pellet production and handling
in, 526, 530, 557, 582-6,
587,588
mixing aspects of, 549-51
operations, general nature and
objectives of, 79, 513-14
pastes, of, 603-9, 981-2
continuous, 605, 657-9
equipment for, 652-9
laboratory-scale, 981-2
standards for, 981
powder blends, of, 547-77
cold,548
continuous, 549, 867
effects of fillers, 519
hot, 548-9,551,574-6
mixers used, 554
high-speed (intensive), 557-62,
564-71,576-7
hot/cold combination, 562--4,
572-3,577
re-cycled material, of, 599-603
schematic outline, 514, 515
solution compositions, of, 105760
typical line, 516-17
'upstream' equipment associated
with, 513, 515, 519--47
Compounds (see also PVC compositions)
commercial,59-77
costing of, 83-5
definitions, 1--4, 79
injection moulding, 726-7
pellet (granulate), melt compounded
designation of, 64
feedstocks, as, 518, 686-7,7367, 789-90, 851-2
Index I
Compounds-contd.
pellet (granulate), melt compounded-contd.
production of, see Compounding,
.
Melt
physical forms, 80, 514
powder, see Powder compounds
production of, see Compounding
Compression moulding
gramophone records, of, 896-7
pastes, of, 1011
thick sheets, of, 837-8, 891, 902-3
Congo Red test, 320, 322, 1143
Conveyor belting, 421-2, 1112
Cooling of PVC mouldings, 781-4
Copolymers
abbreviations for, 4
ABS
blends with PVC, in, 375
impact modifiers, as, 99, 367,
373,390,39>'-5
processing aids, as, 373
butadiene/acrylic ester, 20
butadiene/acrylonitrile, see Nitrile
rubber, and under Impact
modifiers
butadiene/fumaric ester, 391
butadiene/methylisopropenyl
ketone, 391
butadiene/2-vinyl pyridine, 391
copolyester elastomer (Hytrel
3495), 391
EVA, 96, 99,390,395
MBS, 99, 367, 390, 394-5
SAN, 373, 374
styrene/maleic anhydride, 24
vinyl chloride, of, 19-21,22-3,832,
855
commercial, 5, 41
emulsions (latices) of, 1016-18
graft, 20, 41, 887
morphology of, 21
properties of (general), 20
solution type, 1048-9, 1050-1,
1052, 1053, 1054
VC/acrylic ester, 23, 887
VC/acrylonitrile (fibres), 20, 22
VC/ethylene, 22, 41
1205
General
Copolymers-contd.
vinyl chloride, of,-eontd.
VCIEVAt 20,23, 99, 367,392,
394-~,887
VClfumaric ester, 23
VC/itaconic ester, 23
VC/maleic ester, 23
VClmaleinimide (N-substituted),
20
VClpropylene, 22, 41, 795,851,
896
VCltrifluorochloroethylene
(TFCE), 23, 1049
VC/vinyl acetate, 5, 19,22,39,
41,42,50,832,851,894,
897,904,907,1008,1048-9,
1050-1, 1052, 1053, 1060-2
1064-5
VC/vinyl alkyl ether, 23,795
VClvinylidene chloride, 19,20,
21, 22, 41, 832, 851, 896,
964
Co-precipitates, 266, 286, 340
nature, 286
Sr/Zn laurate, 286
Co-stabilisers
epoxy compounds, see under Epoxy
stabilisers
organic, 278, 283, 285, 292
phosphites, 282-3, 290-2, 304-5
polyols, 305
CPVC (chlorinated polyvinyl chloride) see under full name
cpvc (critical pigment volume concentration), 1035-6
Crack initiation (see also Fracture)
nibs and impurities, by, 381
notches, by, 381,387,390
role in impact resistance, 380-1
Creep, 859-63
coated fabrics, resistance to, 1010
data for uPVC, 451, 861-3, 864
definitions, 860, 862
modulus, 862
PVC pipe, of, 863, 866, 879
rate, 860
rupture, 862
strain, 859, 862
1206
Index I
Creep-contd.
temperature, effect of, 450, 451,
759
tests on thermoforming sheet, 75960
Cricket pitch surface, 1123
'Critical solution temperature' (in
plate-out), 688
Cross-staining, see under Sulphide
staining
Crystallinity
plasticised PVC, in, 12~1, 139, 142
PVC polymers, in, see under
Polyvinyl chloride
VCIVDC copolymers, in, 21
Degradation of PVC, see under
Photochemical degradation
and Thermal degradation
Dilatancy, 948-9, 951, 967
Dip coating, 992-6
Dry blends (see also Powder compounds, and powder blends
under Compounding)
commercial, 61, 64, 70, 795
conveyance of, 562, 564
feeds, as, 518
blow moulding, in, 789-90, 795
extrusion, in, 686, 691,867
foamed product production, in,
1074,1076
nature,79,80,548-9,564,574-6
passim, 1,513,514
production of, 372, 547-53
standard designation of, 63, 64,65
uPVC processing, in, 851, 852, 867
Dry colours, 405
Dry point, 122, 123
Duckboard, 1123
Electrical insulation, see Cable and
wire insulation
Electrical properties of PVC, 73,
90, 101, 107, 206, 207,
859,1114-15,1165-6,
1193-5
General
Index I
Extruders-contd.
cascade, 583, 598, 599, 600,610,
621,623,628-30,706
commercial, 609-51, 698, 703-10
compounding, 609-51
heating and cooling, 579-80, 612,
623,627,634,642,676,677,
678,681-2
LID ratio, 673, 677
main components of, 674-82
manufacturers of, 704-5
output
factors affecting, 680
PVC compositions, 599, 630,
632-3,635,637,639,645,
682-3, 707, 708
planetary 610, 639-42, 644-5, 813
single screw, 673, 677, 698-9
energy efficiency with PVC,
683
screw configurations, 698-9
twin screw, 675, 699-703, 706-8
mode of operation: differences
from single-screw, 700-1
screw arrangements, 675, 702
venting of, 677, 683-4
Extrusion, 673-721
ancillary equipment, 710, 713,
718-19,870-1,874-6,885-6,
891,892
blow moulding, 766-72, 784-7
compounding, see under Compounding and Extruders
(compounding)
computers, use of, 686, 698
dies, 680-1
blown film, 712, 891
cross-head, 717, 785
pipe, 870-1, 872-4
sheet, 892
variable-thickness (for blow
moulding), 769, 771
feedstocks for, 514, 518,686-7,
789-90,851-2
feedstocks pre-heating, for, 682,
687
formulation aspects, 274, 687, 853,
876-8,886-9,894,896
General
1207
Extrusion-contd.
fusion and gelation in
completeness, 688, 694-8, 878
phenomenology, 692-4
general nature of process, 673
high-speed, 714-7
historical development, 6, 7, 673,
699
lines, 704-5, 706
cable and wire coating, 718
pipe, 869-76
PVC hose (braid-reinforced), 719
sheet, 598, 600,892
window frame profiles, 706, 708,
885
normal, of pPVC, 713-14
pastes, of, 1011
pipes, of, 869-78
products, common faults in, 688-9
profile, of, 884-9
sheet, of (see also under Extruded
sheet)
advantages over calendering,
890-1
equipment, 598, 600, 892
melt temperature profiles, 597
Fatigue, 863-6
data for uPVC, 865-6
definition, 863, 864
dynamic, 863
life, 864
resistance of uPVC, 864-866
temperature, effect of, 450
Feedstocks for PVC processing, see
under Compounds and Powder compounds
Fillers (see also under individual
names and types), 99-102,
215-54
conductive, 248-50
cost considerations, 100,215,216,
221,231-2
definition, 215
effects in PVC, on
BS softness No., 218
density, 100, 220, 233
1208
Index I
Fillers---contd.
effects in PVC, on-eontd.
paste rheology, 228, 229, 237,
251,970-3
tensile properties, 219, 247
fibrous, 217,240,242-6
flame retardant (see also under
Flame retardants), 842-3
functional, 215, 240-51
glass, 243, 245, 246
latices, in, 1035-8
loading, effects of, 220
microfibre, 242-4
mineral, 216-23
oil (plasticiser) absorption by, 104,
221,222-3,226,230-1,971-2
pastes, in, 970-3
properties (general), 222-3
reinforcing, 240-6
silicaceous, 216-19, 251
smoke suppressant, see under
Smoke
starch, 250-1
suppliers, 251-3
surface treated, 104, 225, 228, 242,
833, 970, 971, 972
trade names, 221, 222-3, 226,227,
252,253
wood flour, 250
Film (see also under uPVC)
applications of, 893-6, 1109-10
conversion and manipulation of
(for packaging), 932
definition, 890, 901-2
extruded, see Extruded film
latex, from, 1015-16, 1018, 1019,
1034
properties, 860, 893-6, 1064, 11867, 1190, 1197
shrink-wrap, 894-5
solvent-cast, 890, 1058, 1063
stretch-wrap, 199, 1109--10
thickness
measurement and control, 892-3
normal range, 890,901-2
'Fish-eyes'
count, specification for, 89, 1140,
1144
General
'Fish-eyes'-eontd.
melt-processed compositions, in,
49, 689, 793, 835
nature, 49, 89
passim, 51
standard tests for, 89, 1140, 1144
Fishing lures, 1122
Flame retardants, 83, 424-34, 508
chlorinated paraffins as, 204-6, 432
fillers, as, 206, 242-3, 247-8,431,
433
modes of action, 429--31, 433-4
phosphate plasticisers, as, 160-3,
204-6,430-2
special additives, as, 427, 429--34
Flammability (see also Burning)
definition, 502
PVC, of (see also under Burning),
161,204-6,427,429,502-3
terminology, 424, 426, 501-2
test specifications, 426, 434, 502,
505-7, 509
Flooring (see also under Asbestos and
Calendered sheet)
antistatic, 422
asbestos-filled, stabilisers for, 10910,349,352
calendered,828-9
coated, 1005, 1006, 1010, 1084,
1094
dust-capturing, 1116
embossed, 1092, 1094
expanded, 1084, 1092
fillers in, 109-10, 217,232-4
formulations, 109--10
linoleum, advantages of PVC over,
1116
stain resistance of, 210, 1010
unsupported, 1084, 1116-17
Flow moulding, 737-8
Flow promoters
dry (powders), 251
melt, definition, 373
Foams (see also Cellular PVC, and
under Pastes), 1069-78,
1080-92
cross-linked, 1077
definition, 1067-8
Index I
Foams---eontd.
density
general ranges, 1069
values for PVC, 1068, 1069,
1070, 1076, 1077,1083,
1097, 1098
evaluation and test methods, see
under Cellular PVC
formulations for
chemically blown, 1097
mechanically frothed, 1098
microcellular, 1069, 1075
production methods
'chemical' blowing, 1071-6, 1080,
1085-92
dispersed-gas blowing, 1069-71
mechanical frothing (gas entrainment), 1076-7, 1081-2
products, 1068-77, 1079, 1084,
1088, 1094, 1096-7, 1099,
1100,1110-11
properties of
blowing agent, effect of. 1083
cell stabilisers, effect of, 10812
factors affecting, 1080-4
plasticisers, effect of, 1081, 1083,
1084
PVC polymer, effect of, 1083-4
structural, 1075
'Fogging', 157, 202-4, 446
leatherc!oth, role in, 202
tests, 202-4
Foil
applications, 894, 1109
definition, 890, 902
stamping, see Hot-foil stamping
thermoforming, for, 894
Footwear,76-7,89, 401, 581,586,
1011, 1069, 1074, 1096-7,
1118
Formulation, 79-115
components
kinds, 81-3
mutual effects, 103-6,265,3347,339
nature and functions (general),
86-103
General
1209
Formulation---eontd.
components---eontd.
side effects, 105-6,296-7,305-7,
308-9,364-7
costing, 83-5
examples
blow mouldings, 112-13,355,
374, 796
flooring, 109-10
foam compositions, 115, 1096-8
gramophone records, 112
injection mouldings, 113,346
miscellaneous, 348, 351, 1008,
1123
pastes, 114-15,972,974,977,
987, 988, 990, 996, 997
pipes and tubing, 110,345,355,
877
profiles, 114, 346, 354
sheet and film, 107-9, 199, 203,
348,355,818-9,894-6
solutions, 1061-2
wire and cable coverings, 111, 346
general considerations, 80-81
Fracture
impact, on, 375, 376, 377, 380, 384
modes of, 380, 384-6
uPVC, of, 387, 388-90, 866
Fusion point (pastes), 853, 854
'Gassing'
calcium sulphate, by, 221
lead stabilisers, by, 266
Gear pumps, 684-5
'Gel block', 122, 959,1011,1099
Gelation/fusion
melt processing, in, 132, 688,
689-98
pastes, of, 122,694, 951-60,982-5,
1095
stages in, 951-2, 956-9
solvent tests for degree of, 696,
697,878-9
foams, in, 1100
paste products, in, 959-60, 983-5
pipes and profiles, in, 697,878-9,
889
1210
Index 1 General
Heat stabilisers-eontd.
complexes, 275, 337
composite metal, 91-3, 281-6, 335,
337-8,345,347-56
cross-staining by, 272, 278, 309
detection and analysis of, 330
evaluation of, 311-28
hazard and hygiene considerations,
265-6,280,341-2
latices, in, 1030-1
lubricants, and or as, 95-8, 104-5,
265,269,274,278,281,282,
283,286,306,339-40,364-6
metal soaps and salts as, 275, 337-8
mode of action, 291, 299-305
non-metallic, 93, 286-92, 348
non-toxic, 92, 106,272,278,279,
281,283-4,287,291,348
one-pack systems, in, 335, 340-1,
348,351
organic, 286-92
pastes, in, 969-70
physical forms, 266, 273,275,
282-3,340-1,343,345,347,
348-51,353-4,356
polymeric, 271
selection criteria, 262-3, 335, 337
single-metal compounds as, 275-81,
343,348,349
types, 89-93, 264
window-frame formulations, in, 887
Hose, see Tubing
'Hot bench', see Gel block
Hot-dip coating and moulding, 992-4
Hot-foil stamping, 934-5
Hydrocarbons, plasticiser extenders
as, 174
Impact modifiers (see also under
371,390-401,793-4
evaluation of effects, 381
fillers as, 226, 236, 241, 246, 391,
419
mode of action, 391
polymeric, 99,105,390-401,853-4
side effects of, 392-3
Index I
Impact modifers-eontd.
window-frame compositions, in, 20,
482,88~
General
1211
1212
Latices-eontd.
vinyl (PVC)-contd.
Index I
General
Lubricants-eontd.
mutual effects with-eontd.
plasticisers, 366
polymeric modifiers, 366-7
stabilisers, 95, 104, 364-5
one-pack systems, in, 98, 339, 340,
370
stabilising effects of, 95, 105,339,
364-5
Lubrication
effects of
plasticisers, 82, 360, 363, 366
polymeric modifiers, 367
stabilisers, 269, 274, 278, 281,
282,283,284,286,366
evaluation of effects, 361-2, 367-70
external, 82, 95, 359-63
internal, 82, 95
rheological effects of, 360-2, 368,
369
Machining of rigid PVC, 930-2
Magnesium carbonate, 247, 433
Mass polymerisation and polymers,
see under Bulk
Masterbatches
colour, 406
compounding of, 587
Maximum swelling temperature, 123
Maximum torque temperature, 132
MBS impact modifiers, 99, 390, 391,
392,394,395
Microbiological attack, 208-9, 483-6
definition, 48~
manifestations and mechanism, 483
protective additives, 208, 484-5
resistance to
plasticisers, of, 208-9, 483-4
PVC, of, 208, 483, 484
vinyl chloride polymers, of, 483
testing of resistance, 208, 485
Migration of
colourants, 404, 411
plasticisers, 135, 175, 199-200,
1146-7
Mills
ball, 652, 654
roll, 656
Index I
General
1213
1214
Index I
General
Permeability, 452-66
biaxial orientation, effect of, 19,
27, 761, 774, 799
blow mouldings, of, 774, 798,799
coefficient
definitions, 453, 455, 461
units, 459
definition, 452, 453, 455, 460
determination
containers, on, 462, 798
plastics, on, 462
standard methods, 456-8
porous materials, of, 460-2
PVC, data for, 451, 463-6
units, 453-4, 456-9, 460
Phosphate plasticisers, 94, 96-7, 15963
flammability, effect on, 160-3,
204-6,430-1,432,503
halogenated alkyl phosphates, 163,
431
mixed alkyl aryl phosphates 161
PVC compounds, performance in,
160, 162
thermal degradation, effect on, 260
trialkyl phosphates, 160
triaryl phosphates, 159, 160
Phosphite stabilisers, see under Costabilisers
Photochemical degradation, 260-1
impurities, effect of, 261, 482
mechanism, 261
protective additives, see UV stabilisers, Antioxodants, Carbon
black, and Titanium dioxide
relevant tests, 328-30, 476-80
weathering, in, 472, 474-5
Phthalate plasticisers, 93-7,152-9
flammability, effect on, 161,205,
508
general-purpose, 153
higher, 156-8
linear, 153, 156
lower, 152-3
miscellaneous, 158-9
modified, 158-9
possible health hazard, 210
PVC compounds, performance in,
154-5
Index I
General
1215
1216
Index I
Plasticisers-contd.
health and safety aspects, 211-12
history of, 5-6
interaction,
parameter (Flory-J{uggins), 128,
130
PVC polymer, with, 122-32
'low temperature' , see aliphatic
diester plasticisers
migration, 135, 199-200
tests for, 200
miscellaneous, 170--5
monoester, 173
monomeric, definition, 119
names and abbreviations, 148-51
pastes, in, 153, 159, 265-9,976-7
permanence, 195-204
polymeric, 96-7,165-70
compositions, in, 199
definition, 119-20
nature, 165-70
solid, 169-70, 197,394-401
polymerisable, 174,968-9,1073
primary, definition of, 118
producers of, 177-9
properties in PVC, 118, 140-1,
154-5, 158, 160-2, 164, 166,
169, 173
rapid fusing, see solvating (below)
resistance to
insect and rodent attack, 209,
486
microbiological attack, 208-9,
483-6
secondary, definition of, 118
selection of, 96-7,124-5
solubility parameters of, 127
solvating, 94, 97,115,158,174,
1074,1081
synonyms, 148-52
types, 119, 149
usage features (general), 96-7
vinyl latices, in, 1031-5
viscosity-temperature relationship,
176
volatilisation, 135, 157,200-2, 212,
446-8
Plastigels, 973-5
General
Index I
Powder---eontd.
compounds---eontd.
production of (see also under
General
PVC---eontd.
1217
1218
Index I
General
PVC-contd.
solutions-contd.
Re-cycling
compounding, and, 599-603
general problems, 9, 10
sulphide staining in, 310
'Red mud' (as reinforcing filler), 1123
Relative melting temperature, 123
Rheometers
balance (Contraves), 954, 955
capillary, 327-8, 369, 580,581
oscillatory (parallel plate), 954-5
plastometers
Macklow-Smith, 65
piston (ASTM), 369, 727
review (passim), 790
torque
evaluation of lubricants, use for,
362,368-9
extrusion characteristics, determination in, 369
fusion time and rate, determination in, 362, 368, 790-1, 954
Plasti-Corder, see under
Brabender in Index 3
Plastograph, see under
Brabender in Index 3
RAPRA, see Index 3
stability tests, use for, 316, 319,
326-8
Rheometry, reference to review of,
790
Rheopexy, 949-50
Rigid PVC (see also uPVC)
chemical.resistance of, 487,488-9,
491-4
definition, 2, 3, 849
feedstocks, 851-2
typical property value ranges,
1185-97
Rigisols, 940, 976-7
Rodent attack, resistance of PVC to,
209,486
Index I
Smoke-contd.
evolution-contd.
plastics, by, 427, 502
tests for, 434, 505-7, 509
nature, 427
PVC, from burning, 499, 502, 509
suppressants, 83, 242, 247-8, 42934
Softness (see also BS softness)
measurement, 184-5
plasticisers, effects of, 185,187-9,
450,1189
Solid-gel transition temperature, 123,
127,131
Solubility parameter, 125-7
plasticisers, of, 126, 127
PVC polymer, of, 127
Solution polymerisation, 39, 42, 1048
Solution polymers, 1048-9, 1050-1
Solutions, see PVC solutions
Solvation point, 123
Solvent cements, see under Bonding
of PVC, Chlorinated polyvinyl chloride, and PVC
(solutions)
Stabilisation (see also Heat stabilisers,
UV stabilisers and Antioxidants)
blow moulding compositions, of,
793 (see also Non-toxic stabilisers)
calendering compositions, of, 831
effects, evaluation of, 312-30
external,264
'in kettle', 264
internal, 264
mechanisms, 264, 291, 299-305
Stabilisers, see under functional types
(e.g. Heat stabilisers, UV
stabilisers, Antioxidants)
Stability
heat, to
adverse effects of formulation
components, 260
concept, 311-15
induction time, and, 312
polymer nature, effect of, 259-60
stability time, and, 259, 312-15
General
1219
Stability-contd.
heat, to-contd.
testing, 315-28
light, to
testing, 328-30
Stain resistance of pPVC, 209-10,
1010
Standards
institutions, 29, 1127-31
test specifications, 29-30, 1134-68,
1185-95
Static electricity charges, 420-2
electrical resistivity, and, 420-2
measurement, 421-2
Stress
concentrating features, 377, 381,
386,695
cracking, see Environmental stress
cracking
rupture strength, 862
whitening
filled compositions, in, 102, 106,
230
impact-modified compositions,
in, 392, 794
mechanism, 392
Strontium stabilisers, 249, 281
Sulphide staining
cross-staining, 91, 105,272,278,
309,310
occurrence, 91, 106,276,308-11
tests for, 310-11
Surface decoration of PVC, 838-9,
932-5, 1005, 1008-9, 1092-5
Surface marking of PVC, 935-6
Surface processing of PVC, 936
Surface treatment of
fillers, see under Fillers and Calcium carbonate fillers
PVC
cellular coatings, 1092-5
paste coatings, 1005, 1008-9
sheeting, 838-9, 932-6
Suspension
polymer particle characteristics, 46,
47,690-1
polymerisation, 39-40, 41
Syndiotactic PVC polymer, 18, 121
1220
Index 1 General
Synergism
co-stabilisation, in, 91, 104,276,
283,340
lubricant/stabiliser, 104,274,364-5
calcium stearate/antimony mercaptide, 276, 364
glycerol esters/thiotins, 364
Tg
Thermoforming of sheet--eontd.
creep tests relevant to, 757, 75960
equipment for
integrated lines, 757
suppliers, 757, 758
materials used
assessment of, 757, 759--60
nature of, 745
products
distortion of, 756-7
finishing of, 754-~
quenching stresses in, 744
related processes, and, 746
techniques
matched-mould and related, 755-
pressure, 756
vacuum, 745-54
temperature
draw ratio, and--effects on product quality, 759--60
role in process, 751-2, 756-7, 760
Thickening agents
latices, in, 1021-8
pastes, in, 251, 973--5
Thixotropy, 949-50, 973, 976
Time/temperature effects in melt
processing, see under Thermal degradation
Tin stabilisers, see Organotin stabilisers
Titanium dioxide
clay, in, 218
light stabiliser, as, 108,297,419,
482,1056
types, 418
white pigment, as, 102,418--19,
1062
Toners, 411
Torque rheometer, see under Rheometers
Toughness, 376, 399, 440
Transfers (surface decoration), 933
Trialkyl phosphate plasticisers, 149,
160, 161, 162
Triaryl phosphate plasticisers, 149,
159-60, 161, 162
Index I
66,68,71,463-4,466,
469,489-94,849,850,85566,878-9,899,893-5118595
sheet, see under Calendering,
Calendered sheet, Extruded
sheet, Extrusion, and Sheet
UV stabilisers, 255, 292-9
1221
General
(passim),960-1
1222
Index I
Viscosity-eontd.
stability index (pastes), 966, 973
standards and definitions, 14,44-5,
50,52,1136-7
Volatile loss, 200-2, 447-8
General
Welding of PVC-eontd.
recommended temperature ranges,
910
specifications relevant to, 913, 918
techniques
dielectric welding, 912
extrusion welding, 911, 919
friction welding, 912
heated tool welding, 911, 922-3
high frequency welding, 912,
919-22
hot gas welding, 911, 914-19
indirect heated element welding,
911
radio-frequency (RF) welding,
912
spin welding, 912
thermal impulse welding, 912
ultrasonic welding, 913
vibration welding, 912
White lead, 266-7
Whiting, see Calcium carbonate fillers
(types)
Zinc-containing stabilisers, 91, 93,
106, 109-10, 112, 113, 115,
283-4,286,302-3,309,325,
338,345,347-53,355,356,
364,793,831,969,1086,
1087,1096
INDEX 2
Acryloid modifiers
equivalence to Paraloid, 375,396
formulations, in, 108, 395, 887
Adimoll plasticisers, 178
Admex plasticisers, 179
Aerosil, 252, 973
Airco PVC resins, 22, 56
Ako-Stop, 1124
Alaiftex plasticisers, 177
Alfol alcohols, 151, 156, 164
Alphanol 79 alcohols, 150, 156, 164
Amaplast Yellow RRT, 404
Amoco Resin 18, 373
Antifoam A, 1028
Antistat A, 424, 425
Araclor plasticiser extenders, 179
Arbeftex plasticisers, 177
Argutop lacquers, 1008, 1009
Armodur, 905
Artevyl PVC resins, 56
Astraglass, 905
Atmer 152, 1082
Azocel blowing agents, 1088
1224
Index 2
Cab-o-Sil, 973
Cadmium colourants, 414, 415
Calgon, 1029, 1043
Calibrite, 233, 234, 237, 252
Calmote, 252
Calofil, 252, 972
Calofort, 252, 972
Calopake,252
Carina PVC resins, 56
Carstab 700, 295
Celanese (Courtaulds) plasticisers,
163,177
Celcon, 735
Cellosolve, 1052, 1053, 1062
Celogen blowing agents, 1088, 1090
Cereclor plasticiser extenders, 127,
128, 130, 171, 172, 173, 177, 178,
432
Ceroxin lubricants, 371
Chemigum N8, 203
ChemPurge, 685
Chlorafin plasticiser extenders, 179
Chlorez plasticiser extenders, 178
Chlorowax plasticiser extenders, 178
Chrome Green DC 3593, 409
Cinquasia Violet RT 795 D, 407
Citroflex plasticisers, 174, 179
Clarechem CLA-1500, 430
Clorafin, 179
Cobex 1350, 905
Conductex 975, 424
Conoco
PVC compounds, 63, 1122
PVC resins, 56
Contrastat, 178
Corvic PVC resins, 34, 35, 52, 54, 56,
410,796,819,854,897,966,974,
987,988,990,997
Crestapol plasticisers, 129, 177
Cromophtal colourants, 408, 413
Cyanolit 811, 928
Cyasorb UV stabilisers, 294, 1055
Dacovin PVC resins, 57
Darvic,451,904,906-7,909
Dawsonite, 242, 243, 244, 248, 433
Day/Cal, 234
1225
1226
Microcarb,252
Microdol, 252
Microlith colour concentrates, 406
Microspin colour concentrates, 406
Mikro-Chek 12, 484
Millicarb, 234, 235, 236,252
Mirvyl PVC resins, 57
Mobisol plasticiser extenders, 174
Modifier PIM 101, 397
Mollan plasticisers, 177
Moly flame and smoke retardants,
430
Monastral Fast Blue BGS, 414
Monolite Fast Black LS, 414
Monolube lubricants, 371
Monoplas 230, 1098
Monoplex plasticisers, 171, 179
Morden R, 236
Morflex plasticisers, 129, 179
Movil fibre, 1117
Mural Mousse Somvyl Decor wall
coverings, 1113-14
Neo-Rez R900, 1009
Neosyl, 973, 974
Neralit PVC resins, 56
Nipolit PVC resins, 56
Nitropore blowing agents, 1090
Nitrosan, 1091
Nopco Foamaster Defoaming agents,
1028
Nopcowax lubricants, 371
Nor-Core 1124
Nordxyl, 250
Norvinyl PVC resins, 56, 1098
Nuoplaz plasticisers, 175, 179,210
Nuostabe stabilisers, 286, 348, 350,
351
Nycoflex plasticisers, 177
Omya, 100,227,234,237,238,252
Omyalite, 227, 235, 236, 252, 345,
346,354,355
Oncor flame retardants, 430
Ongard flame retardants, 430, 432,
434
Oriex, 905
1227
1228
Timonox, 253
Tinuvin light stabilisers, 108, 109,
295,347,351
Tioxide Ti0 2 , 346, 354, 355, 1043
Trihyde, 222, 252
Trocal Colour profile, 884
Trovidur HT, 25
Trovipor PVC resins, 57
TV-2 biostat, 484
Tween 20, 1031
Vacupiast, 482
Varian PVC resins, 56
Vestinol plasticisers, 178
Vestolit PVC resins, 23, 56,887
Vinamold hot-melt compounds, 63
Vinaprint GV inks, 933
Vinatex Adhesive MP 7A, 992
Vinco stabilisers, 356
Vinidur PVC resins, 56
Vinnol PVC resins, 23, 56, 203, 877
Vinoflex PVC resins, 56
Vinophane, 895,909
Vinychlon PVC resins, 56
Vinylcel, 1077
Vinylite PVC resins, 1051, 1053
Vinyon HH, 22
Vipla, Viplavil, PVC resins, 56
Viton, 175
Vixir PVC resins, 57
VS-103 (foam cell stabiliser), 1075
Vulcabond VP, 1007
Vulcafor colourants, 412, 414
Vybak,905
Winnofil, 252
Witaclor plasticisers, 178
Witamol plasticisers, 178
Wolflex plasticisers, 177, 200
1229
INDEX 3
1232
determination, 1100
Intec 500 inspection system, 893
'Interval blowing' cooling system for
blow mouldings, 783
Jungfer (sintering) process, 1079
1233
Statigun, 421
Stork system, 1094
Sussex thickness control system, 893
Taber Abraser, 1196
TCM foam moulding system, 1076
Technoform PPZ process, 875
Therimage process, 933
Thermassive window frame system,
1107
Thermorex gear pumps, 684
Topformer process, 743
TQ-150 mercury lamp, 329
Tri-Delta blow-moulding machines,
789
Trovipor process, 1070, 1071
Turbosphere mixer, 559, 560
Ultra Viscoson viscometer, see Bendix Ultra Viscoson
Underwriters tunnel furnace test, 506
Uniloy 300 blow-moulding line, 781
Urban AKS 3313 welding equipment,
923
Vanderbilt process, 1077
Vibrochrom FFR 2 colorimeter, 408
Weather-Ometer, 207, 475, 478
Werner Pfleiderer ZSK extruder, 623,
626, 632, 677
Xenotest apparatus, 207, 330, 478
XP-2 smoke chamber, 505