Bladder Technology

ExxonTM butyl rubber curing bladder technology
manual
ExxonTM butyl rubber curing bladder technology manual Ref. B1011-598E98
Page 1 of 43
Abstract
A curing bladder is an important component of the tire vulcanizing
press and the tire curing process. The proper selection of butyl polymers and
compounding materials for the bladder formulation is essential in ensuring
durability, required service life, and efficient curing bladder operation in a tire
factory. This is due to the superior heat and steam resistance of resin cured
butyl rubber which has resulted in its wide use for high heat resistant
applications. Additionally, butyl rubber has very low permeability to gases and
water vapor that further enhances the performance of butyl rubber tire curing
bladders.
This manual reviews aspects of curing bladder technology and
presents some basic guidelines on compounding, processing, applications
technology, and trouble shooting of common curing bladder failure modes.
Model bladder compounds with selected properties are also reviewed. These
compounds provide starting points for additional development work depending
on the specific properties that are needed or that allow use in different types
of tire curing presses and factory operating conditions.
Page 2 of 43
Table of Contents
Introduction
Curing Bladder Performance Requirements....
Compounding of Tire Curing Bladders...

7
..
Processing of Tire Curing Bladder Compounds....
16
Types of Tire Curing Presses and Operation Sequence of Tire

Curing Bladders..
23
Curing Bladder Design ..
27
Guidelines for Bladder Maintenance..
30
Special Test for Curing Bladder Compounds. .
32
New Technology and Curing Bladder Market Trends
33
Appendices
Appendix 1. Typical bladder failures and corrective guidelines..
Appendix 2. Check list of failures and corrective guidelines
36
41
References..
42
Page 3 of 43
Introduction
Resin cured butyl rubber has carbon-carbon crosslinks which yield heat
stable vulcanizates. The superior heat and steam resistance of resin cured
butyl rubber has resulted in its wide use for high heat service temperature
applications such as tire curing bladders. Additionally, butyl rubber has very
low permeability to gases and water vapor providing the required properties
for butyl tire curing bladders. A curing bladder is an important and essential
part of the tire vulcanizing press. Some examples of curing bladders are
shown in Figure 1.
Tire producers are always working to improve the performance of
curing bladders, in order to maximize (i) tire curing efficiency, (ii) factory
productivity, and (iii) durability of bladders. This manual reviews current curing
bladder technology and gives some basic guidelines on compounding,
processing, technology, and trouble shooting for common tire press curing
bladder failure modes.
Figure 1
Tire Curing Bladders
Page 4 of 43
Figure 1
Tire Curing Bladders cont
Page 5 of 43
Curing Bladder Performance Requirements

Functions of a Curing Bladder.
The curing bladder is a cylindrical bag of specially compounded butyl
rubber containing a poly-methylolphenol resin cure system. This collapsible
bladder is mounted in the lower section of the tire curing press and forms a
part of the press and mold assembly. The "green" unvulcanized tire is
positioned over the bladder in the bottom half the mold. When the mold is
closed, pressurized steam, air, hot water, or inert gas (nitrogen) is introduced
systematically (pre- programmed) into the bladder to provide internal heat and
pressure for the tire shaping and curing process. The two types of tire curing
presses which require bladders are:
1. Slideback (NRM or similar) type press which requires an AutoForm
(Bagwell) bladder.
2. Tiltback (Bag-O-Matic or similar) type press which requires a Bag-OMatic bladder.
Examples of curing bladders used by the tire industry for tire curing presses
are shown in Figure 1.
Basic Properties Required for Curing Bladder Application.
Three types of tire cure cycles can be found, a steam high pressure
hot water cure cycle, a steam inert gas cure process, and a steam steam
cure cycle. Dome temperatures can reach 190C ( mold sidewall plates at
180C) and the bladder temperatures can reach up to 220C. For a truck tire,
size 14.00R20, a simple steam hot water cure cycle time could be as
follows:
1. Steam
2. High Pressure hot water
3. Cold water flush
4. Drain
1200
3000
400
030
Total Cure Time (minutes)
4630
Given the high pressures and temperatures the bladder undergoes in

multiple cure cycles, the basic properties required for curing bladder include
the following:
1. A homogeneous, well mixed compound for ease of processing
(mixing, extruding, and mold flow).
2. Excellent heat aging resistance.
3. Resistance to degradation due to saturated steam or high pressure
hot water, or inert gas.
4. Excellent flex and hot tear resistance.
5. Low tension and compression set that maintains high elongation
properties.
6. Impermeability to air, inert gas, and water vapor.
Page 6 of 43
Attainment of these properties will enable a curing bladder to achieve an

adequate service life, i.e., number of tire cure cycles and sometimes referred
to as the pull - point. The pull - point is where the bladder is removed before
failure; thereby preventing failures during tire cure cycles which can lead to
the loss of tires during production.
Compounding of Tire Curing Bladders

Tire curing bladders must withstand continuous exposure to high
temperatures from high pressure steam, hot water, or inert gas. This is
achieved by using butyl rubber specially compounded with reactive alkyl
phenol formaldehyde resin. The selection of compounding ingredients is very
important with respect to the bladder life. The primary materials used in a
bladder compound are the polymer (butyl rubber), cure activator, carbon black,
plasticizer, zinc oxide, and curing resin.
Butyl rubber (IIR, Isobutylene isoprene copolymer) is the preferred
elastomer for tire curing bladders due to the following properties:
1.
2.
3.
4.
Excellent heat aging resistance,

Good flex and tear resistance,
Low tension and compression set, and
Impermeability to air, inert gases, and water vapor.
Butyl rubbers are typically produced via a cationic polymerization in

methyl chloride at temperatures between 90C and 100C. The unique
properties and difficult manufacturing conditions place butyl rubbers in the
special purpose elastomers category, distinct from general-purpose rubbers
such as polybutadiene (BR), natural rubber (NR), and styrene-butadiene
rubbers (SBR)1,2.
Butyl rubber is a copolymer of isobutylene and approximately 2 mol%
isoprene (Figure 2). The length of the isobutylene structural unit (0.270 nm) is
67% of that of the 1-4-isoprene structural init (0.405 nm)3. The
stereochemistry of the isobutylene unit results in close packing along the
polymer chain, low free volume fraction, and consequently low permeability.
Isoprene is incorporated in a trans-1,4 enchained head-to-tail arrangement to
produce a random, linear copolymer.
Page 7 of 43
Figure 2
Structure of Butyl Rubber2
(Structure I)
CH3
CH2
CH3
CH2
CH3
CH
CH2
.
.
(0 8 to 3 0 mole %)
Elaborating, using 1H NMR to investigate the stereochemistry of the

enchained isoprene, it was found that the majority (94%) of Structure I
isoprene units illustrated in Figure 3 are incorporated in the 1,4 configuration4,.
The term Structure I, is assigned from the description for isoprenyl units
found in chlorobutyl and bromobutyl rubbers.
Figure 3
Sterochemistry of Isoprene Incorporation4
CH3
CH3
CH2
CH
CH2
1,4 Addition
94%
Structure I
CH2
CH2
CH
C
CH
CH2
1,2 Addition
6%
CH3
CH2
3,4 Addition
0%
Structure I minor
Structure Iminor consisting of the 1,2- enchained isoprene has also been
suggested, at amounts in the order of 6%4. No 3,4-addition products have
been reported. Expanding on this work, White and coworkers further
suggested the absence of a 3,4-addition structure but also suggested that
Structure Iminor had the configuration illustrated in Figure 35. The ratio of 1,4
enchained isoprene and the minor isoprenyl derivative was dependent upon
polymerization temperature but was still present, albeit in small amounts, in
commercial grades of butyl rubber. White and coworkers have also reported
that Structure I minor is not associated with end groups, and that the R groups
arise from isobutylene and not from isoprene isoprene addition (Figure 4).
Though the authors indicated no definitive determination of the R- group but
evidence was presented showing the R- groups may be longer chains5.
Thus, though the presence of a Structure I minor is accepted, its precise
configuration remains to be further clarified, the primary difficulty being the
very low concentration of such structures.
Page 8 of 43
Figure 4
Proposed Branched Structure I minor 5
CH3
CH2
CH
CH
R'
R = Long chain branch f rom polymer

Cyclic ring due to rearrangement of chain end
Long continuing isobutylene chain
For butyl rubber curing bladders, EXXONTM Butyl 268 can be used as a
starting point in building a compound formulation. Examples of curing bladder
compound formulations can be found at www.butylrubber.com6. Table I
further illustrates a selection of the commercial grades of butyl rubber
currently available from ExxonMobil Chemical Company. The table shows the
range of polymer viscosities available, and nominal isoprene content6.
Table I
Examples of Commercial Grades of ExxonMobilTM Isobutylene
Elastomers6
Elastomer
Butyl
(low viscosity)
Butyl
(medium viscosity)
ExxonMobil Grade
Identification
065
Mooney Viscosity
(ML1+8 @ 125C)
32
Isoprene
(mol %)
1.05
068
268
51
51
1.15
1.70
Regular Butyl Grades

Various grades of butyl rubber can be used in curing bladder
applications depending on the final compound and bladder requirements and
tire types being produced. Some selected grades of butyl rubber can be
further described as follows:
1. EXXON Butyl 268: This is the most commonly used grade for
curing bladder compounds. It has high Mooney viscosity
(ML1+8@125C: 51 MU) and medium amount of unsaturation (1.7
mole%). Though compounds containing this grade of butyl have
good processing and mechanical properties, and good durability,
mold flow properties can be further modified by blending with lower
Mooney viscosity grades such as EXXONButyl 065.
2. EXXON Butyl 068: It has the same Mooney viscosity as
EXXON Butyl 268 but with lower unsaturation (1.15 mole%). It
can be blended with EXXON Butyl 268 to improve heat aging.
Resin level should be adjusted to obtain an optimum state of cure.
Page 9 of 43
Caution is also required as a low state of cure can result in an

increase in bladder growth.
3. EXXON Butyl 065: It has low unsaturation (1.05 mole %) and is a
low Mooney viscosity (ML1+8@125C of 32 MU) grade. It is used in
blends with EXXON Butyl 268 in large size Off The Road (OTR)
tire curing bladders for improved mold flow. OTR bladders must
sustain very long cure times at tire curing temperature.
The term mole percent unsaturation refers to the number of isoprene
molecules in 100 monomer molecules in the polymer. Thus, a one mole
percent unsaturation butyl would contain one molecule of isoprene and ninety
nine molecules of isobutylene.
Further reference, if required, should be made to the web site,
www.butylrubber.com, for additional information on these polymers6.
Activators
The crosslinking of butyl rubber is dependent on the reactivity of the
phenol-methylol groups of reactive alkyl phenol-formaldehyde resins
(octylphenol formaldehyde resin). The low levels of unsaturation of butyl
require resin cure activation by adding halogen containing materials such as
SnCl2 or halogen-containing elastomers such as polychloroprene. A more
reactive resin cure system requiring no external activator is obtained if some
of the hydroxyl groups of the methylol group are replaced by bromine. An
example of commonly used commercial resin is a brominated alkyl phenol
formaldehyde resin.
Typical grades of polychloroprene used as resin cure activators are
shown in Table II.
Carbon Black
Generally, high structure carbon black ISAF or HAF (e.g. N330) which
give a good balance of properties, are used in bladder compounds at levels
of 50 to 60 phr. Other alternative types of carbon black are the GPF grades
which show improved air aging, though ISAF grades have better steam aging
properties. Acetylene black compounds in combination with, for example,
N330 have good thermal conductivity which may reduce tire curing time.
However, acetylene black may be difficult to disperse in the butyl rubber
compound. Generally, a lower loading of carbon black (e.g. 35 phr) gives
better air aging and higher loading of carbon black (e.g. 65 phr) gives better
steam aging. In the website www.butylrubber.com, carbon black N220 (50
phr), and N660 (60 phr) are used in the model formulations6. An example of a
curing bladder compound with properties is illustrated in Table III.
Page 10 of 43
Table II
Polychloroprene Grades
Grade
Neoprene GN:
Neoprene W (1) :
Neoprene GNA :
Neoprene TW :
Neoprene TRT :
Neoprene WRT :
Properties
Shorter aging and scorch resistance.
Good processing and most commonly used.
Tends to show low scorch resistance.
Easy processing, good mechanical properties.
Crystalline resistant and good processing .
Crystalline resistant, but requires higher
organic accelerators levels.
Note: 1. Polychloroprene (W Type) is cited in the website www.butylrubber.com under

formulary section.
Plasticizers
Castor oil (5 phr) is the most commonly used plasticizer for bladder
compounds due to its low volatility at high temperature. Castor oil reduces the
tendency for a marching modulus in resin cured butyl rubber bladder
compounds. Additionally it gives lower unaged modulus and good steam
aging. If castor oil is not available, then oleic acid (5 phr) could be used.
Compounds containing either castor oil or oleic acid have better release
properties between the bladder and tire inner liner. These compounds also
show better retention in aging properties due to the high boiling point and
lower volatility of castor oil. Alternatively if castor oil is not available paraffinic
process oils (e.g. FlexonTM 876) could be used though caution is required.
Curing bladder compound properties obtained using paraffin oil in place of
castor oil have been tabulated in the model formulary on
www.butylrubber.com.
Zinc Oxide
Zinc oxide, typically at 5 phr, is added to form zinc halide that then acts
as the catalyst for the vulcanization of resin cured butyl rubber compounds.
Good dispersion of the ZnO is critical for improved tire curing bladder life.
Page 11 of 43
Table III
Model Formulary for Curing Bladder With Exxon Butyl 2686
Material
Units
Amount
PHR (1)
PHR
PHR
PHR
PHR
100.00
5.00
50.00
5.00
1.00
PHR
PHR
5.00
10.00
Units and Conditions
176.00
Typical Values
(2)
ASTM
D1646
MU@100C
MU@100C
Seconds
80.8
80.6
3.1
ASTM
D1646
MU@125C
Minutes
Minutes
62.2
7.8
26.6
180 C; Arc 0.5

dN.m
dN.m
dN.m
Minutes
Minutes
Minutes
Minutes
2.8
10.7
7.8
7.0
3.5
12.1
24.6
ASTM
D412
MPa
%
MPa
12.5
860
2.5
Hardness, Shore A
ASTM D2240
Shore A
47
Tear Strength (Die-B)
ASTM D624
KN/m
34.9
EXXON Butyl Grade 268

Polychloroprene (W Type)
Carbon Black, N220
Castor Oil
Stearic Acid
Zinc Oxide
Heat Reactive Octylphenyl Formaldehyde Resin
Total PHR
Properties
Mooney Viscosity ML1+4
Mooney Viscosity ML1+8
MRI
Mooney Scorch
Minimum Viscosity
Time to 1 pt rise
Time to 5 pt rise
MDR Rheometer
ML (Minimum torque)
MH (Maximum torque)
MH-ML ( T)
Tc2 (time to 2 torque unit increase)
Tc10 (time to 10% torque increase)
Tensile Strength
Elongation
300 % Modulus
Test Method
Based on
ASTM
D5289
Note:
1. PHR: Parts per Hundred Rubber.
2. Values given are typical and should not be interpreted as a specification.
Page 12 of 43
Antioxidant
Generally, antioxidants are not effective in improving heat resistance of
resin cured butyl compounds. Some of the antioxidants (e.g. amines) could
significantly retard the cure rate of regular butyl rubber compounds, sulfur
based vulcanization systems, and resin curing system.
Process Aids
Depending on the equipment, resin cure bladder compounds may be
difficult to mix and process. To facilitate good dispersion and flow properties,
it may be necessary to use process aids such as organosilicone compounds.
There are several commercially available process aids such as
organosilicones and calcium fatty acid soaps suitable for curing bladder
compounds7.
Reactive Phenol Formaldehyde Resin as Curing Agent
Resin cured butyl rubber compounds may display better resistance to
detrimental effects of exposure to high temperatures when compared with
sulfur cured butyl rubber vulcanizates, which tend to soften during prolonged
exposure at elevated temperatures (e.g., 1500C to 2000C).
The resin cure mechanism in butyl rubber is based on the reaction of
the methylol groups in the phenol-formaldehyde resin with allylic hydrogen in
butyl, usually with a Lewis acid catalyst, to yield carbon-carbon crosslinks that
are thermally stable2. Tire curing bladders are cured by alkylphenol
formaldehyde derivatives containing methylol groups. Examples of tire curing
bladder compounds, using heat reactive octylphenol formaldehyde curing
resins, are given in the website www.butylrubber.com6 under Formulary
section and in Table III. Commercially, there are several suppliers
manufacturing reactive phenol formaldehyde resins (octylphenol
formaldehyde resin).
Reactive bromomethylated alkylphenol formaldehyde resins are also
used. While using brominated reactive resin, the bladder compound does not
require an external source of halogen such as polychloroprene. However
when using such resins, compound tack can increase resulting in the need to
conduct additional factory compound process development.
The simplified chemical structure of vulcanizing resin is given in Figure
5 and its possible cross-linking structures are given in Figure 6 (Van der
Meer) and Figure 7 (Greth) 8,9.
The vulcanizing resin is a chain of phenolic rings connected by
methylene groups as illustrated in Figure 5. The terminal methylol groups (CH2OH) are the points at which the resin molecule crosslinks with the butyl
polymer molecule. Van der Meer has postulated that the -OH from the
methylol group combines with hydrogen on the carbon atom to double bond,
establishing a carbon-carbon linking between the resin and butyl molecules at
that point as shown in Figure 6. A vulcanizate crosslink is formed when this
takes place at both ends of the resin molecule.
Page 13 of 43
Figure 5
Simplified Structure of a Vulcanization Resin
OH
H2 COH
OH
OH
CH 2
CH 2
CH2 OH
Figure 6
Crosslinking through - hydrogen8
OH
OH
HC
H 3C
H 2C
OH
CH 2
CH 2
CH2
CH
C
CH 2
CH 3
CH
CH
CH2
CH 2
It has also been suggested that the cure mechanism involves both the
phenolic and methylol hydroxyls in a substitution reaction across the double
bond, resulting in a chroman structure as shown in Figure 7.
Figure 7
Crosslinking Through Chroman Structure Formation8,9
CH2
H 2C
CH 2
OH
CH3
CH2
CH 3
CH 2
CH 2
In summary, at this point the accepted mechanism for the resin

crosslinking mechanism is illustrated in Figure 8. Following the elimination of
water in the reaction sequence, the exomethylene group and carbonyl oxygen
react with an isoprenyl unit in butyl rubber to form a chroman ring.
Chromonone ring structures are very stable and are frequently found in
natural product biosynthesis.
Page 14 of 43
Figure 8
Resin Curing of Butyl Rubber10
OH
OH
HO CH2
OH
R'
CH2
OH
HO CH2
R'
CH2
heat
- H2O
R
CH2
Formation of a
Chroman ring
H
OH
CH2
OH
HOCH2
CH3
C
HO CH2
R'
CH2
R
CH2
O
CH
CH3
C
CH
CH2
R'
CH3
C
CH
CH2 CH3
C
CH
O
CH2
CH3
CH
CH2
R'
CH C
CH2
Crosslinked Butyl Network Evolution

R
Model Formulary for Tire Curing Bladders

Reference should be made to the web site, www.butylrubber.com for
model compounds which provide starting points for additional development
work. A simplified summary of a model compound is shown in Table III. This
includes processing properties and physical properties.
Processing of Curing Bladder Compounds
The service condition of the tire curing bladder is unique in that it is
subjected to severe conditions of heat, pressure and flexing. Therefore, good
dispersion of the ingredients especially carbon black, zinc oxide,
polychloroprene and curing resin is very important to achieve an adequate
service life. Good dispersion of the compound ingredients enhances physical
properties and allows better retention of physical properties.
Page 15 of 43
Processing of Tire Curing Bladder Compounds

The service conditions of the tire curing bladder are unique. It is
subjected to severe conditions of heat, pressure and flexing. Therefore, good
dispersion of the ingredients, especially carbon black, zinc oxide,
polychloroprene and curing resin, is very important to achieve adequate
service life. A good dispersion of the compounding ingredients can improve
physical properties and also retention of physical properties.
The manufacturing process flowchart for a tire curing bladder is
illustrated in Figure 9. Briefly, the major processing steps are:
1.
2.
3.
4.
5.
6.
7.
8.
9.
Masterbatch mixing,
Straining,
Final batch mixing,
Extrusion of slugs/blanks,
Cutting of slugs/blanks,
Blank splicing,
Vulcanization (compression molding or injection molding),
Post-cure or conditioning, and,
Storage of bladders.
Figure 9
A Flow Chart for Curing Bladder Production
Not every step in this comprehensive schematic of curing bladder production

may be necessary. For example, use of high quality butyl rubber and
compounding materials may eliminate the need for straining. Modern cold
feed extruders can eliminate the need for warm-up mills. However, strainers
on the extruder die can represent good practice and may help in obtaining a
more uniform extrudate.
Page 16 of 43
Guidelines for Mixing

Butyl rubber is primarily a saturated polyisobutylene copolymer with
1.05 to 2.30 mol% of isoprene. It is important to avoid contamination of
unsaturated elastomers such as natural rubber, SBR and polybutadiene
rubber with butyl rubber. Due to the difference in the state of cure between
butyl and other unsaturated elastomers, contamination could lead to loss in
compound physical properties. Bale cutters, internal mixers, two roll open
mills, strainers and extruders which are used to process butyl rubber and
other unsaturated rubbers should be cleaned thoroughly with a clean-out
compound.
Depending on specific factory processes, it is sometimes suggested
that butyl rubber ibe pre-masticate for 45 seconds in an internal mixer or
open roll mill. Alternatively preheating for 24 hours at 50C will help. An
internal bale temperature of 45C to 50C, or pre-mastication of butyl rubber,
facilitates the easy incorporation of compounding ingredients. Butyl rubber
compound mixing is done in two stages in the internal mixer (Banbury mixer);
the first stage, non-productive, or masterbatch contains all the ingredients
except the curatives.
It is also sometimes suggested to separately pre-masticate polychloroprene
rubber to improve homogeneity of bladder mix compound. The 2nd stage is
the final or productive step where the vulcanization system is added.
Masterbatch Mixing
Masterbatch mixing of tire curing bladder compounds may be carried
out in an internal mixer. In order to improve dispersion and to prevent trapped
air, it is suggested that the masterbatch weight be increased by 10% to 20%
compared to natural rubber or emulsion SBR compounds at an equivalent
specific gravity.
There are varieties of loading sequence practiced in the industry as
shown in Table IV and Table V. It is suggested that the starting temperature
of an internal mixer for masterbatch mixing be set at 75C to 80C.
Straining & Cooling
Upon discharge from the internal mixer it is suggested that the
masterbatch or first stage mixed compound be immediately passed through a
strainer pack of 20 to 30 mesh or 30 to 40 mesh. This will eliminate the need
for re-warming the stock for straining. The strained stock then can be stored
on a tray, which has been lightly dusted with talc.
Page 17 of 43
Table IV
Mixing Procedure for a Model Curing Bladder Compound
First Stage Masterbatch Mixing in an Internal Mixer
Time / Dump Temperature
Operation Sequence
0 Minute
Add butyl rubber and polychloroprene
(if included in the formulation)
3/4 Minute
Add carbon black, oil, other

compounding additives.
170C to 180C
Dump.
Final Productive Batch or Second Stage Mixing

Finalization can be carried out in the internal mixer or two roll open mill. For
final or productive batch mixing in internal mixer, it is suggested that the
batch weight starting point setting be 80% of the mixer volume, and then
optimized for the specific equipment.
Table V
Second Stage or Productive Mixing in an Internal Mixer
Time & Dump Temperature
Operation Sequence
0 Minute
Add half masterbatch, zinc oxide and
powered curing resin, then remaining
half of masterbatch
100C to 110C
Dump
Three Stage Mixing (Masterbatch and Final Batch)

Three stage mix cycles are suggested if a lower Mooney viscosity compound
is required. This may be needed to improve mold flow properties such as
when injection molding bladders (Table VI).
Suggested Precautions when Mixing
Suggestions include the following:
1. The mixing equipment is cleaned before and after mixing butyl rubber to
avoid contamination.
2. Carbon black should be added to the mixer before the oil.
3. If carbon black blends are used, it is suggested that the high structure
carbon black be added first .
4. If zinc oxide dispersion is a concern, then the addition of polychloroprene
and zinc oxide could be reversed.
5. If brominated alkyl phenol formaldehyde resin is used, it is suggested that
zinc oxide be added with the carbon black in the masterbatch.
Page 18 of 43
6. It is suggested that the curing resin be added with the last 1/3 of the
masterbatch and folded into the compound stock on the conveyor belt of
internal mixer feed hopper.
7. After dumping it is suggested that the batch be cooled immediately.
Table VI
Time & Dump Temperature
1st Stage / Masterbatch
Three Stage Mixing

Operation Sequence
0 Minute
1 Minute
130C
160C to 170C
2nd Stage
Add butyl rubber, polychloroprene

Add black, oil, stearic acid
Cleaning
Dump
0 Minute
130C
3rd Stage / Final Batch
Master batch, zinc oxide

Dump
0 Minute
100C
2nd stage batch and powdered resin

Dump
Guidelines for Mill Feeding for Hot Extrusion

Some guidelines and suggestions include:
1. Auto feeding (no manual feeding) is suggested.
2. It is suggested batches be blended at the mill before feeding to the
extruder.
3. Avoid addition of reworked compound.
4. Control the mill nip setting, especially the feed mill (for large size slugs,
feed width has to be adjusted)
5. Maintain a consistent rolling pencil bank on the feed mill and maintain
constant feed strip dimensions (thickness and width) for the particular size
of slug.
6. Strip feeding temperature should be kept at 85C to 95C.
Guidelines for Extrusion of Blank Slugs by Hot Feed Extrusion
Both hot feed and cold feed extrusion are used for blank extrusion.
However special care should be taken to minimize trapped air in the extruded
blank especially for hot feed extrusion processes. Some additional
suggestions and points are listed as follows:
1. Two warm-up mills are suggested to ensure optimum rolling blank to
minimize porosity.
2. Force fed extruders fitted with powered feed rolls are suggested so as
to minimize trapped air.
Page 19 of 43
3. Maintain a full extruder barrel and maximum back-pressure to help

prevent porosity.
4. Generally, die head temperature can be set at around 110C to 130C.
Compound temperature will also depend on compound Mooney
viscosity and the extruder head pressure.
5. While extruding, good water circulation in the screw (typical
temperature of the barrel and screw can be in the order of 55C to
65C) should be maintained, with the screw cooler than the barrel.
6. It is suggested that the extruded stock temperature is maintained at
less than 120C and internal slug temperature is between 95C to
120C.
7. The speed of feed conveyor, extruder rpm, take-off conveyor and
cooling line speed should be synchronized to prevent pulling and drawdown of slugs dimensions.
8. Cool down the extruded blank with a chilled water bath or chilled water
spray.
The extruded dried blanks should be stored on clean trays and away
from airborne dust and foreign materials.
Guidelines for Cold Feed Extrusion
Some suggestions include:
1. Use a force feed roller for extruder feeding. Do not fold feed strips
2. Keep the extruder barrel filled with the compound to avoid porosity.
3. Vented cold feed extruders may reduce the chance of porosity.
4. Vacuum type cold feed extruders with degassing capability can reduce
porosity significantly.
5. Optimize extruder screw speeds (rpm) for a particular slug size.
6. Suggested extruder temperatures for barrel and screw are 55C and
45C respectively, and for the die head it is between 110C to 120C.
7. Like hot feed extrusion, it is suggested that the speed of the feed
conveyor, extruder rpm, take-off conveyor, and cooling line speed
should be synchronized to prevent pulling of slugs and draw-down of
slug dimensions.
8. Cool down the extruded blank with a chilled water bath or chilled water
spray .
The Advantages of Cold Feed Over Hot Feed Extruder
These include:
1. Two roll mills are not required, resulting in floor space savings and
lower capital cost.
2. Less staff.
3. Longer length (L) of screw over smaller screw diameter (D), L/D ratio of
the cold feed extruder can result in a more uniform viscosity of the
compound.
4. Capability of handling high and low Mooney viscosity compounds.
5. In cold feed extrusion, it may be easier to control stock temperature
and slug dimensions.
Page 20 of 43
Secondary Processing Suggested Improvement Guidelines

Mold flow, scorch resistance, and heat degradation are three major process
and product concerns encountered with tire curing bladders.
1. Guidelines on Flow Improvement: Good compound flow and knitting
properties are important criteria to ensure improved properties during the
molding process and to improve bladder life. These properties are
particularly important for larger bladders and for injection molding of
bladders. Typical approaches in tuning compounds can include:
i.
Increase plasticizer (process oil).
ii.
Blending with low Mooney viscosity butyl rubber such as
EXXONTM Butyl 065 (75phr) with EXXONTM Butyl 268 (25 phr).
iii.
Use about 2phr of process aids such as calcium acid soap or
organosilicone compound.
2. Guidelines on Scorch Retarder: For tire curing bladder compounds based
on EXXONTM Butyl 268 and W type polychloroprene, scorch time can be
adjusted by:
i.
Addition of magnesium stearate (0.25 to 0.5 phr).
ii.
Reduction of the level of reactive alkyl phenol formaldehyde
resin (curing resin).
iii.
Use a curing resin with a lower methylol content.
3. Improvements in Heat Resistance: Resin cured butyl rubber compounds
posses good heat resistance as illustrated in the model compound
Formulary on the website, www.butylrubber.com. By blending low
unsaturation, low Mooney viscosity polymer and eliminating process oil,
heat resistance can be enhanced.
4. Polymer Blends: When low unsaturation polymers are used in large
proportions, then caution has to be taken for possible bladder growth
during service. Examples of blends which can be used include:
i.
Blend EXXONTM Butyl 268 and EXXONTM Butyl 068 with
process oil.
ii.
Blend EXXONTM Butyl 268 (25 phr) and EXXONTM Butyl 065 or
EXXONTM Butyl 165 (75 phr) without process oil.
Guidelines for Slug Handling
Some suggestions include:
Keep the slugs on clean trays.
Do not use lubricant when cutting the slugs.
Slugs should be rectangular in cross section for easier molding.
Keep the slug weight more than the final trimmed weight of bladder by
10% to 15%.
Guidelines for Slug Splicing
Slugs should be skived cut and ends pressed together as a scarf joint,
ensuring that there is no air entrapment.
Page 21 of 43
Spliced slug must fit the mold ledge with no overlap or extra pieces.
Slug ends should not to be heated before splicing.
If slugs have to be preheated before curing, then it is suggested that a
circulating air oven (not electrical lamps) is used for uniform heating.
Generally, slugs can be heated 1 to 4 hours at 80C
After splicing, wrap the spliced area with polyethylene film to avoid
contamination by air borne dust.
Guidelines for Bladder Vulcanizing (Compression Molding)

Some suggestions and guidelines include:
Keep molds clean, free from flash, and free from plugged vents.
Mold release agent should be used as little as possible. It is preferred to
avoid mold release agents if possible.
Badder curing temperature should always be set higher than the
temperature the bladder is expected to encounter during tire curing
service life.
Cure temperatures for a bladder should be in the range of 190C to 210C.
Higher temperature curing can allow more stable cross links and state of
cure.
Cure time and temperature should be set to obtain optimum tension set
and compression set properties.
Close the press as rapidly as possible and reach pre-programmed
hydraulic pressure within 30 seconds.
Keep the core straight and tight.
Mold halves should be aligned properly.
Adequate rib venting and patio venting should be provided while
designing the mold to allow venting trapped air during the molding
process.
Guidelines for Post Curing of Bladders
Post curing suggestions include:
Generally, post curing of bladders helps to get better stabilization of
crosslinking and state of cure that eventually offers improved bladder life
(higher number of heats). Post curing can be done in an autoclave for 2 to
4 hours at 140C to 160C.
If post curing is not done, then it is suggested to over cure the bladder for
better crosslinking stability.
Guidelines for Storage of Bladders
Bladders should be stored in the warehouse (open and free from ozone
and ultra violet lights) for about 2 weeks after curing. This storage period
helps to stabilize crosslinks and relaxes stress. Generally bladders, after
storage, exhibit better life (more number of heats) than those bladders used
immediately after curing.
Page 22 of 43
Types of Tire Curing Presses and

Operation Sequence of Tire Curing Bladders
An example of a typical operation sequence for an AutoForm tire curing
bladder is shown in Figures 10 and 11. An illustration of a typical operation
sequences for a Bag-O- Matic tire curing bladder is shown in Figures 12 and
13.
Figure 10
Structure of a Bladder Press
Page 23 of 43
Figure 11
Sequence of Operation for Curing MPT and AFV Bladders
4
3
2
Page 24 of 43
Figure 12
Operation of a Bladder Press
Page 25 of 43
Figure 13
Sequence for Operation of BOM Bladder press
Page 26 of 43
Curing Bladder Design

Since the bladder is mechanically stretched and folded at temperatures
up to 200C with each cure cycle, avoidance of stress concentrations is
important. The most effective approach from the design perspective is to
reduce the gauge of the bladder wall. In injection molding processes, the
bladder wall thicknesses can be reduced to 4.0 to 5.0 mm for passenger tire
applications.
Bladder Sidewall Thickness
The primary purpose of the bladder is to prevent steam from leaking
into the innerliner or tire casing. Since heat is transferred through the bladder,
there is a requirement to make the bladder wall as thin as possible, while
maintaining necessary mechanical properties. If the bladder is too thin it will
rupture during service. If it is too thick it will reduce heat transfer and the
clamp area could be damaged.
Surface Design on the Bladder
The bladder surface design will be a function of several factors:
1. A manufacturer may use the design as trade mark or as a unique
company characteristic.
2. The design may be chosen to permit ease of venting trapped air
between the green tire and the bladder as the mold closes.
3. Improve the uniformity of the tire innerliner surface appearance.
Frequently the chosen bladder design will meet these parameters. Some
venting is necessary and typically runs from the crown area to the bead region.
Venting channels, if required, should be molded into the bladder surface and it
is important to ensure that vent markings are clean, have no flash, and are
such that no foreign material can get trapped on the bladder surface. This
would cause a weak spot and upon subsequent flexing the bladder could fail,
particularly if the mold flash or other material is covered, over-cured, or
covered with a layer of mold release. Bladder vent marks can affect innertube
durability so for tube type tires vent markings it is suggested that the curing
bladder be designed taking this into consideration. For tubeless tire - bladder
combinations, good venting is more important.
Bladder Venting and Etching
The design of etching is chosen in order to give venting of air
entrapped between the "green" unvulcanized tire and the bladder during the
press / mold closing operation (Figure 14). Generally venting runs from the
crown area of the bladder to the bead area. Venting channels are preferably
molded into the bladder surface. In addition, irregularities such as stamping
information on the bladder wall can create flaws in the tire innerliner which
can then be a site for crack initiation. Any markings or emblems should
therefore designed to prevent any later product performance concerns.
Page 27 of 43
Figure 14
Types of Venting
Examples of Slideback and Tiltback presses are shown in Figures 15

and 16. Figure 17 shows a cured tire being removed from the curing press.
The tire curing bladder collapses so as to pull the wall away from the tire.
Then the tire is raised over the retracted bladder, dropped onto a cooling rail
for several minutes before being transferred to final inspection.
Page 28 of 43
Figure 15
Slide-back AutoForm Style Curing Press
Figure 16
Tilt-Back Bag-O-Matic Style Curing Press
Page 29 of 43
Figure 17
Tire Removal from the Curing Press Showing the
Collapsed Tire Curing Bladder
Guidelines on Bladder Maintenance

During service, bladders are exposed to severe conditions such as
high heat (steam or hot water), gas pressure, and excessive flexing under
pressure. Bladder service life is a function of a variety of factors and the root
causes of potential failures requires detailed statistical analysis.
Bladder Life During Service
Bladder life can be improved by taking proper care during service. For
example:
1. After curing, bladders should be stored in appropriate conditions as
discussed earlier.
2. Bladders should be protected from ozone and UV light if stored for
extended periods.
3. The clamping rings should to be tightened to 10 to 15% compression
and the compression should be uniform around the bladder.
4. It is suggested that the internal curing media (steam, inert gas) contain
less than 150 pphm oxygen and be free from metallic compounds,
especially copper.
5. Control of bladder stretching to within 65% circumferentially and 20%
laterally is suggested.
6. The correct size of bladder and tire fitment are important to maximize
bladder life.
Page 30 of 43
7. If the correct bladder size is not available, a smaller size bladder is

preferred. Selection of larger size bladders should be avoided to
prevent any buckles as the bladder inflates inside the green tire.
8. Periodic surface lubricant coating of the bladder or use of a green tire
lubricant is beneficial to extend bladder life.
Statistical Quality Assessment for Bladder Life
Bladder life can be analyzed statistically by recording the following variables:
1. Type of curing medium.
2. Type of bladder (Bag-O-Matic, Autoform, Toroidal).
3. Bladder size.
4. Tire size.
5. Press / machine number.
6. Number of heats (bladder life).
7. Failure type and possible causes of failure.
8. Examine the defects and determine corrective actions.
9. Implement corrective actions.
Typical Examples of Bladder Failure Modes
A number of failure modes can be found for tire curing bladders. For
illustrative purposes, some examples would include:
1. Delamination (rough surface or smooth surface).
2. Surface hardening.
3. Broken at bead clamping (upper or lower).
4. Blistering / Porosity (localized area or evenly).
5. Inside softening (localized area or evenly).
6. Bladder surface cracks (evenly or at corners of vent grooves).
7. Tearing of bladder.
8. Splice opening.
9. Bladder growth.
10. Small hard lumps in bladder.
Details on some examples of bladder failures with possible reasons and
corrective guidelines are presented in Appendix 1 and 2.
Pre-Pull Policy of Tire Curing Bladder to Save Tire Scrap
Based on the statistical failure data analysis, tire producers can set the
time limit of pre-pull policy (example, after 500 heats or cure cycles). This
reduces the possibility of tire casing losses due to bladder failure. This is also
economical for the tire producer as it prevents an unscheduled stoppage of
tire production and saves scrapping of tires due to a failed tire cure press
bladder.
Page 31 of 43
Special Tests for Curing Bladder Compounds

Since curing bladder service is under high heat and high pressure
conditions, several laboratory tests have been designed for curing bladders.
These are laboratory hot milling, hot elongation, hot tear, and hot tension set.
Hot Elongation (190C)
Physical testing at room temperature can give some useful information,
but in many cases the properties of a compound can change when measured
at the temperature used in service. This test uses a normal stress-strain
tensile tester with an electrically heated oven. The sample is subjected to a
temperature of 190C in the oven for 5 minutes and then mounted in the jaws
of the tensile tester. After mounting of the sample in the oven chamber, the
temperature of the oven is allowed to stabilize at 190C before carrying out
the test. It is only necessary to measure the hot elongation at 190C, as this
simulates the condition of inflation and deflation of the bladder in service .It is
suggested that hot elongation at break is in the range of 400% to 800%.
Hot Tear
This is an important parameter to predict the durability of the bladder.
Measurement at 190C temperature is suggested.
Hot Tension Set
Hot tension set is another important parameter to assess compound
quality. Test samples are elongated 300% for one hour at 100C and then
relaxed for 24 hours. Tension set property is then measured. The tension set
should be less than 10%.
Other Testing Guidelines
In addition to the specific tests highlighted above, the tire curing bladder
compounder will want to study other material properties such as tensile
strength, tear strength, and hardness. The Formulary on the web site,
www.butylrubber.com6, provides a set of typical properties that can provide as
guideline for the compounder. Compound aged property retention is
important for the bladder to achieve an adequate service life.
Page 32 of 43
New Technology and Tire

Curing Bladder Market Trend
All tire manufacturers want longer bladder service lives. In addition,
service conditions are becoming more severe. For example, some trends
include:
Tire curing temperatures are increasing and in some instances internal
temperatures may exceed 200C.
Tire cure cycles under 10 minutes can be found for passenger tires.
Expected service life may be significantly over 500 cure cycles or heats for
passenger tire curing bladders.
Use of steam and inert gas (nitrogen) as cure heating media are the preferred
means of tire curing. These curing media may enable an increase in bladder life
and allow some further reduction of cycle times.
These ongoing demands for greater productivity also influence how curing bladders
are produced.
New Technology Trends
With regard to new technology trends in curing bladders, curing bladder
production using injection molding methods is becoming more popular because of
precision of gauge control. Figure 18 provides an illustration of both horizontal and
vertically configured injection molding machines.
Figure 18
Bladder Injection Molding Machines
Bladder Injection Molding

Machine
Vertical Bladder Injection

Molding Machine
Page 33 of 43
The bladder design is changing, providing less gauge in the center, which
gives more flexibility and also allows rapid and more uniform heat transfer. Such a
design helps to cure the tire tread region faster (which can be the thickest part of the
tire), but it also shortens the cure cycle, thus saving energy.
When injection molding curing bladders, the screw, barrel, and extruder
head dwell times should be as short as possible. It is suggested that filling of
the injection screw should not to be longer than 15 seconds prior to injection
operation. Key requirements for injection of butyl rubber compounds are:
Compounds should have good flow properties, which can be achieved by

blending low Mooney viscosity butyl rubber with high Mooney viscosity
butyl rubber (e.g. EXXONTM Butyl 065 with EXXONTM Butyl 268).
Scorch times at injection molding temperatures such as 180C to 200C
must be adequate since the compound travel distance and transferring of
the compound flowing to the mold takes longer time than the other
applications.
The compound from the check valve, injection cylinder, and nozzle should
have no porosity and should have a provision for evacuation of air from the
closed mold.
As in any other extrusion operation, the extruder on the injection molding

machine should be maintained and inspected for items such as screw
tolerances and barrel condition to ensure no dead zones in the barrel and no
air is being trapped in the compound . Examples of molds are illustrated in
Figure 19.
Figure 19
Injection Bladder Mold
Page 34 of 43
Advantages of Injection Molding over Compression Molding

Injection molding can provide:
Reduced compound waste.

Good bladder gauge uniformity.
Reduced cure times in bladder production.
Improved bladder service life.
Absence of splice related defects in injection molded bladders.
Bladders with no flash.
Page 35 of 43
Appendix 1
Typical Bladder Failures and Corrective Guidelines
Bladder failure can occur at any time during its service and in many
instances it can be difficult to assess the true cause. Failure of a curing
bladder in service often results from many different factors. A useful guide to
bladder life is the average number of cures before failure and the type of the
failure'. It is also beneficial to record any statistical data such as failure modes
for each supplier or manufacturer of bladders. This guideline describes types
of bladder failures and possible methods to be considered in correct them.
1. Curing Bladder Compound Mixing
Page 36 of 43
2. Blank Preparation and Molding
Page 37 of 43
2. Blank Preparation and Molding.cont.
Page 38 of 43
3. Curing Bladders in Service
Page 39 of 43
3. Curing Bladders in Service.cont.
Page 40 of 43
Appendix 2
Check List of Failures, Possible Reasons, and Comments
(The common failures that occur during operation)
Failure
Delamination
(rough surface)
Delamination
(smooth surface)
Possible reason
GPR contamination
Scorching
Lubricant / solvent
contamination
Surface
Hardening
Vent cracking
Curative migration from tire
Bladder too small

Poor ageing properties
Bladder growth
Tension set too high
Softening inside
Bladder
Oxidation
Metal contamination (Cu, Ni,
Mn, Co)
Porosity
Small hard lumps in

bladder
Tearing
Check mixer/mill operating

conditions
Straining /Extrusion temps
too high
Cured chloroprene
Hard lumps in carbon black
Low hot elongation
Splice opening
Poor consolidation
Lubricant contamination
Solvent contamination
Dirty mold
Bladder too big
Poor surface on new

bladder
Surface folds
Comment
Ensure mixers / extrudes are free from GPR
Reduce polymer unsaturation.
Reduce resin level
Reduce methylol content of resin
Improve black dispersion to reduce straining
temps
Do not use solvent cements in the process
Use surface coating for bladder
Consider use of brominated resin
Improve hot elongation
Reduce resin level
Reduce polymer unsaturation
Increase crosslink density
Increase cure time or cure temperature
Increase resin level
Install contact heater
Oxygen in steam or water (max 150 pphm)
Check for presence of brass ferrules in the
bladder which is used for bladder raising /
lowering mechanism.
Porosity caused by high extrusion temp.
often causes scorching
First stage masterbatch should be strained
Improve hot elongation

Reduce resin level
Reduce polymer unsaturation
Do not use solvents or lubricants when
splicing the blank
Clean mold regularly

Unplug vents
Check if the bladder is too big; caused by
growth during service or wrong selection of
bladder or wrong selection of the size.
Page 41 of 43
References
1. RM Thomas and WJ Sparks. Butyl Rubber. In Synthetic Rubber. Ed GS
Whitby. John Wiley and Sons, Inc., New York. 1954.
2. WH Waddell, AH Tsou. Butyl Rubber. In Rubber Compounding, Chemistry and
Applications. Ed MB Rodgers. Marcel Dekker, Inc. New York. 2004.
3. MF Tse, KO McElrath, HC Wang. Relating De Mattia Cut Growth to Network

Structure of Crosslinked Elastomers. Polymer Eng & Science. Vol 42 (6), P 12101219, 2002.
4. DM Cheng, IJ Gardner, HC Wang, CB Frederick, AH Dekmezian.

Spectroscopic Studies of the Structure of Butyl and Bromobutyl Rubbers.
Rubber Chemistry and Technology. Vol 63 (2). P265 275. 1990.
5. JL White, TD Shaffer, CJ Ruff, JP Cross. Incorporation of Isoprene in
Isobutylene / Isoprene Copolymers: NMR Identification of Branching in
Butyl Rubber. Macromolecules. Vol 28. P 3290-3300. 1995
6. www.butylrubber.com.
7. Technical Bulletin. Rubber Processing Additives. Struktol Corporation. 2006
8. WC Smith. The Vulcanization of Butyl, Chlorobutyl rubber, and Bromobutyl
rubber. In Vulcanization of Elastomers. Ed G Alliger & IJ Sjothun.
Reinhold Publishing Corp, NY. 1964.
9. Butyl and Halobutyl Rubbers by J.V. Fusco and P. Hous, Exxon
Chemical Company- Published in The Vanderbilt Rubber
Handbook, Thirteenth Edition, 1990.
10. S Solis, MB Rodgers, N Tambe, BB Sharma, WH Waddell. A Review of
the Vulcanization of Isobutylene-Based Elastomers. Presented at a
meeting of the American Chemical Society Rubber Division, San Antonio
TX. 2005
2014 Exxon Mobil Corporation. While the information is accurate to the best of our knowledge and belief
as of the date compiled, it is limited to the information as specified. No representation or warranty,
expressed or implied, is made regarding the information, or its completeness, merchantability, or fitness for a
particular use. The user is solely responsible for all determinations regarding use and we disclaim liability
for any loss or damage that may occur from the use of this information To the extent the user is entitled to
disclose and distribute this document, the user may forward, distribute, and/or photocopy this copyrighted
document only if unaltered and complete, including all of its headers, footers, disclaimers, and other
information. You may not copy this document to a Web site. ExxonMobil does not guarantee the typical (or
other) values. Analysis may be performed on representative samples and not the actual product shipped.
The information in this document relates only to the named products or materials when not in combination
with any other product or materials. We do not represent, warrant, or otherwise guarantee, expressly or
impliedly, the merchantability, fitness for a particular purpose, suitability, accuracy, reliability, or
completeness of this information or the products, materials, or processes described. The user is solely
responsible for all determinations regarding any use of material or product and any process in its territories
of interest. ExxonMobil makes no representations or warranties against patent infringement or noninfringement of the intellectual property rights of any third party. Likewise ExxonMobil does not grant any
license, express or implied, under any patents or patent applications owned by ExxonMobil to make, use,
sell, offer for sale or import any product based upon this formulation. We expressly disclaim liability for any
loss, damage, or injury directly or indirectly suffered or incurred as a result of or related to anyone using or
relying on any of the information in this document. There is no endorsement of any product or process, and
we expressly disclaim any contrary implication. The terms we, our, ExxonMobil Chemical, or
ExxonMobil are used for convenience, and may include any one or more of ExxonMobil Chemical
Company, Exxon Mobil Corporation, or any affiliates they directly or indirectly steward. ExxonMobil, the
ExxonMobil Logo, the Interlocking X Device and all other product names used herein are trademarks of
ExxonMobil unless indicated otherwise.
Page 42 of 43
2006 Expansion of halobutyl capacity by 17,000 tons per year at

Kashima (Japan) plant
2008 Expansion of halobutyl capacity by 60 percent at Baytown (USA)
plant
First application of Exxcore DVA resin based tire innerliners,
setting the stage for lighter and more durable tires that hold air
longer and help reduce fuel consumption and CO2 emissions
Saudi Basic Industries Corporation (SABIC) and affiliates of
ExxonMobil Chemical sign a Heads of Agreement (HOA) to
progress detailed studies for a new elastomers project at their
petrochemical joint ventures at Kemya and Yanpet (Saudi Arabia).
The project would establish a domestic supply of over 400 KTA of
carbon black, rubber and thermoplastic specialty polymers
including butyl rubber, EPDM, TPO and SBR/PBR to supply local
and international markets.
2009 Successful pilot-plant demonstration of next generation of butyl
rubber, benefiting from nanocomposite technology, with the goal
of doubling the number of tire innerliner applications that can be
served from existing halobutyl capacity to meet growing demand.
At the forefront of technology
and innovation
ExxonMobil Chemical has been at the
forefront of technology and innovation in
the rubber industry since inventing and
patenting butyl rubber in 1937. Today
we market high-quality synthetic rubber
worldwide and are a global leader in
butyl technology, services and products.
2010 Increase in butyl rubber production capacity by 18,000 tons

per year at the Japan Butyl Co. Ltd. (Kawasaki) Plant. This
expansion will increase plant capacity by 23% to 98,000 tons
per year utilizing new ExxonMobil proprietary process technology.
2013 ExxonMobil Chemical will build facilities to manufacture premium
halobutyl rubber and Escorez hydrogenated hydrocarbon resin
in Singapore, completion anticipated in 2017. This expansion
project will add production capacity of halobutyl rubber to 140,000
tons per year and hydrogenated hydrocarbon resin production
capacity to 90,000 tons per year.
Let our technology-driven focus and

commitment to improve processes and
products help your business meet its
supply requirements and grow profitably.
Benefit from access to our global marketing
and product expertise, as well as our
state-of-the-art technology centers.
Learn more at:
B1011-598E98
butylrubber.com

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ExxonTM butyl rubber curing bladder technology

ExxonTM butyl rubber curing bladder technology manual Ref. B1011-598E98

ExxonTM butyl rubber curing bladder technology manual Ref. B1011-598E98

Curing Bladder Performance Requirements....

Compounding of Tire Curing Bladders...

Processing of Tire Curing Bladder Compounds....

Types of Tire Curing Presses and Operation Sequence of Tire

Curing Bladder Design ..

Guidelines for Bladder Maintenance..

Special Test for Curing Bladder Compounds. .

New Technology and Curing Bladder Market Trends

ExxonTM butyl rubber curing bladder technology manual Ref. B1011-598E98

ExxonTM butyl rubber curing bladder technology manual Ref. B1011-598E98

ExxonTM butyl rubber curing bladder technology manual Ref. B1011-598E98

Curing Bladder Performance Requirements

Total Cure Time (minutes)

Given the high pressures and temperatures the bladder undergoes in

ExxonTM butyl rubber curing bladder technology manual Ref. B1011-598E98

Attainment of these properties will enable a curing bladder to achieve an

Compounding of Tire Curing Bladders

Excellent heat aging resistance,

Butyl rubbers are typically produced via a cationic polymerization in

ExxonTM butyl rubber curing bladder technology manual Ref. B1011-598E98

Elaborating, using 1H NMR to investigate the stereochemistry of the

ExxonTM butyl rubber curing bladder technology manual Ref. B1011-598E98

R = Long chain branch f rom polymer

Regular Butyl Grades

ExxonTM butyl rubber curing bladder technology manual Ref. B1011-598E98

Caution is also required as a low state of cure can result in an

ExxonTM butyl rubber curing bladder technology manual Ref. B1011-598E98

Note: 1. Polychloroprene (W Type) is cited in the website www.butylrubber.com under

ExxonTM butyl rubber curing bladder technology manual Ref. B1011-598E98

Units and Conditions

180 C; Arc 0.5

Tear Strength (Die-B)

EXXON Butyl Grade 268

ExxonTM butyl rubber curing bladder technology manual Ref. B1011-598E98

ExxonTM butyl rubber curing bladder technology manual Ref. B1011-598E98

In summary, at this point the accepted mechanism for the resin

ExxonTM butyl rubber curing bladder technology manual Ref. B1011-598E98

Crosslinked Butyl Network Evolution

Model Formulary for Tire Curing Bladders

ExxonTM butyl rubber curing bladder technology manual Ref. B1011-598E98

Processing of Tire Curing Bladder Compounds

Not every step in this comprehensive schematic of curing bladder production

ExxonTM butyl rubber curing bladder technology manual Ref. B1011-598E98

Guidelines for Mixing

ExxonTM butyl rubber curing bladder technology manual Ref. B1011-598E98

Add carbon black, oil, other

Final Productive Batch or Second Stage Mixing

Three Stage Mixing (Masterbatch and Final Batch)

ExxonTM butyl rubber curing bladder technology manual Ref. B1011-598E98

Three Stage Mixing

Add butyl rubber, polychloroprene

Master batch, zinc oxide

2nd stage batch and powdered resin

Guidelines for Mill Feeding for Hot Extrusion

3. Maintain a full extruder barrel and maximum back-pressure to help

ExxonTM butyl rubber curing bladder technology manual Ref. B1011-598E98

Secondary Processing Suggested Improvement Guidelines

Guidelines for Bladder Vulcanizing (Compression Molding)

ExxonTM butyl rubber curing bladder technology manual Ref. B1011-598E98

Types of Tire Curing Presses and

ExxonTM butyl rubber curing bladder technology manual Ref. B1011-598E98