Measuring Polymers using a Rotational

Rheometer in Oscillatory Mode

Steve Goodyer
Product Manager for Rheology
Anton Paar Ltd.

www.anton-paar.com
 Introduction
Viscoelastic Behavior
polymers

Polymer melts

Extrusion
(e.g. Polystyrene, PS):
extrudate swelling
and
melt fracture

Blow moulding
(e.g. Polyethylene, PE):
orange peel
or
shark skin

2
 Agenda

(A little bit of theory G and G)

Measuring Polymers with a rheometer

Amplitude sweeps lvr

Frequency Sweeps
- molecular interactions
- fingerprints
- degree of cross linking
- molecular weight from zsv
- relaxation time from x-over mmd

Temperature
-DMTA

Time Sweeps
- cure profile
- reaction kinetics
3
 Introduction
Viscoelastic Behavior
Using a simple illustrative picture:

The Rheology Road

viscous viscoelastic elastic

ideally viscous viscoelastic viscoelastic ideally elastic

liquids liquids solids (rigid) solids
like water, oils like glues, like pastes, like stone, steel
Law of Newton shampoos gels, rubbers Law of Hooke

rotational tests |
oscillatory tests
e-learning (Eiffel tower)
4
 Definitions
Shear Stress, shear deformation or shear strain

The Two-Plates Model

shear stress =
F
A
unit: 1 N / m2 = 1 Pa (Pascal)

shear deformation =
s
or shear strain h

unit: 1 m / m = 1 = 100 %

5
 Definitions
Elasticity Law

Spring Law: F/s=C

spring force F
deflection path s
spring constant C (stiffness)

Robert Hooke (1635 to 1703) G= definition of the
shear modulus

unit of the shear modulus: (1 Pa / 1 = ) 1 Pa

further units:
1 GPa = 1000 MPa = 106 kPa = 109 Pa
(Giga-pascal, Mega-pascal, kilo-pascal)
6
 Rheometry
Oscillatory Tests: Basics (1)

Two-Plates Model

Ideally elastic behavior

of a totally stiff sample
(e.g. a stone, or steel):

There is no shift between

the sine curves of
shear strain (deformation)
and shear stress : Movie
the curves of and (2-plates-model,
ideal-elastic
are in phase behavior)

7
 Rheometry
Oscillatory Tests: Basics (2)

Preset: constant frequency and constant amplitude

Result: Most samples are showing viscoelastic behavior

with the phase shift between the sine curves of the
test preset (e.g. strain) and the measuring result (then: stress),
as a retardation of the measuring response to the preset oscillation.

It counts: 0 90 Movie
(2-plates-model,
ideally elastic ideally viscous behavior visco-elastic behavior)

8
 Rheometry
Oscillatory Tests: Basics (3)

Vector Diagram
Elasticity Law of Hooke
(for oscillation): *
=
A

G
Index A for Amplitude A

G* [Pa] Complex Shear Modulus

G' [Pa] Storage Modulus, elastic portion

Physically:
G' for the stored and
G'' for the lost (dissipated)
G'' [Pa] Loss Modulus, viscous portion
of the viscoelastic behavior
deformation energy

tan [1] = G''/ G' Loss Factor or Damping Factor

as the ratio between the viscous and the elastic portion
9
 Rheometry (Oscillation)
Amplitude Sweeps, preset

Preset:
constant frequency

(e.g. the angular frequency

= 10 rad/s or s-1)

and
variable strain (deformation)

Frequency Conversion: = 2f
with angular frequency [s-1] and frequency f [Hz]
(since Hz is not an SI unit !)
Movie
(amplitude sweep)

10
 Viscoelastic Behavior
Amplitude Sweeps

Limiting value
of the LVE - range

Result:
storage modulus G' (elastic behavior),
loss modulus G'' (viscous behavior),
limiting value of the linear viscoelastic (LVE- ) range when reaching L
- at the given test conditions, i.e., at the preset (angular) frequency -

left side: G > G (gel - like structure) in the LVE - range

right side: G > G (liquid - like structure) in the LVE - range

11
 Viscoelastic Behavior
Amplitude Sweeps
polymers
105
Pa
Polymer Melt

lg G'
viscoelastic liquid,
104
lg G'' liquid-like character
since G > G

limit of the LVE range at

= 10% = 0.1
= 10 rad/s
103
T = +180C
-2 -1 0 1 2 3
10 10 10 10 10 % 10
strain lg
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 Viscoelastic Behavior
Amplitude Sweeps
polymers dispersions

1000
kPa
Sealant

100

paste-like, viscoelastic
lg G' gel-like character
10 in the LVE range
lg G'' since G > G

1 Limit of the LVE-range at

= 0.026% = 2.6 10-4
(with 10% tolerance deviation)
= 10 rad/s
T = +25C
0.1
0.001 0.01 0.1 1 10 % 100
strain lg

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 Frequency Sweeps

Measure time dependency

of viscoelastic properties.

Frequency of applied strain
with constant amplitude is
logarithmically varied.

Results typically plotted as
G, G vs frequency, f (or
f).
= 2

Generally speaking the
shorter the timescale the
more elastic a material
behaves.

Consider as viscoelastic
spectrum.

Results relate to molecular
t=0 t= 5 min structure of the sample.
14
Frequency Sweep
Visco-elastic liquid (no gel, unlinked, no filler)

Long term: newtonian behaviour

Short term: viscoelastic behaviour

Complex viscosity
No network

structure

No links between
macro-molecules
G G
1
2
1
1
Angular frequency

15
 Viscoelastic Behavior
Frequency Sweeps
polymers
Typical behavior of an unlinked polymer

0 = 35 kPas PDMS
5 (poly - di - methyl
10
- siloxane)
Pa
4 4
10 10
lg G' Pas
3
lg G'' 10
lg |*|
2 3
10 10

1
10
> G crossover G > G
G = 10 %
T = +23C
-3 -2 -1 0 1 2 3
10 10 10 10 10 10 10
rad/s
angular frequency lg
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Frequency Sweep
Visco-elastic, partially linked

No long term relaxation

Gel stability due to 3D-network structure

G
Slope:
G
Strength of
structure at rest

Absolute value:

Stiffness of gel

Complex viscosity Damping G/G

Damping
behaviour

Angular frequency

17
 lg G'
Frequency Sweep
4 the Regions
G1

2 1

lg

1 Unlinked polymer with narrow MWD

2 Unlinked polymer with broad MWD
3 Lowly cross-linked polymer, soft gel or dispersion with weak structure
4 Highly cross-linked polymer. stiff gel or dispersion with strong structure

18
Frequency Sweep
Example for Polymersolutions & Melts
The most important parameter

Zero Shear Viscosity 0 (n 1)

(Direct Relation MW) (

= (0 ) 1 + ( x )
a
) a +

0 = kMw
4 3, 4 7
10 10

Pas Pa
3
10 5
10 Polystyrol 200C]
4 |*| Complex Viskosity
10
2 G'
|*| 10 3
G' Storage Modulus
10 G''
G'' Loss Modulus
2
1 10
10
Cross Over Point 1
10
0 0
10 10
-1 0 1 2 3 4 5 6
10 10 10 10 10 10 10 1/s 10
Angular Frequency
Physica Messtechnik GmbH

19
Frequency Sweep
Molar Mass MW & Distribution MMD

higher average > narrow <

molar mass (>MW ) MMD G'

G''

longer / branched GX, X

molecules
lower average
molar mass (<MW )

shorter / less
branched molecules

< wide MMD >

Angular Frequency

20
Frequency Sweep Master Curve
Horizontal shift towards the reference temperature T0

TTS example: shift of storage modulus G

The range abover the transition region is called glassy region

21
Frequency Sweep Master Curve
Horizontal shift towards the reference temperature T0

TTS example: horizontal shift of storage modulus G

Storage modulus G

160C
180C

200C

230C
260C

Angular frequency
22
 From Frequency Sweep to Master Curve (I)
7
10
142 C
Pa

5
10
G'
4
10 Shift Factor aT

G'' 3
10

2
10
170 C
1
10
-2 -1 0 1 2 3
10 10 10 10 10 1/s 10
Angular Frequency

23
 From Frequency Sweep to Master Curve (II)
7
10
142 C shifted
142 C
Pa
RESULT
5
10 Enlarged
G' frequency range
4 at
10 Shift Factor aT 170C

G'' 3
10

2
10
170 C
1
10
-2 -1 0 1 2 3
10 10 10 10 10 1/s 10
Angular Frequency

24
 From Frequency Sweep to Master Curve (III)
7
10

Pa

5
10
G' 4
10
G'' 3
10
Long term behavior short term behavior
2
10 LONG SHORT Interactions
MOLECULES MOLECULES between
dominant dominant MOLECULES
1
10
-2 -1 0 1 2 3 4 5
10 10 10 10 10 10 10 1/s 10
Angular Frequency

25
 Frequency Sweep Molar Mass MW, MMD
MMD in just 2 analysis steps
4 6
10 10

Frequency Sweep [1/s] Pas

Pa
4

1
10

or
3
3 10 G'
|*| 10 2
10
G''

Master Curve
1
10
0
10
2 -1
10 10
0,001 0,01 0,1 1 10 100 1/s 1.000
Kreisfrequenz
Relaxtation Time Spectrum

5
10
1.000

2 Relaxation Time
Pa
10
3

1
Pas

600

Spectrum [s] )
H( 10

-1
400
)
H(

10 200
-3
10 0
-4 -3 -2 -1 0 1 2 3
10 10 10 10 10 10 10 s 10
Relaxationszeit
Additional parameter
from literature! 0,5
0,45
0,4
0,35
0,3
0,25
wi
0,2

MMD: 0,15

3 MMD Bimodal or MMD Kernels (for the experts)

0,1
0,05
0
10.000 100.000 1.000.000 g/mol 10.000.000

26
[g/mol] Molmasse M i
 Frequency Sweep The Regions

Glassy State
Tg Region
5 7
10 Terminal Flow 10
Pas
Rubbery Plateau Pa
4 Slope in the region
10 of 0 5
10
3 4 G'
*| 10
| 1:1
10
3 G''
2
10
10 2:1 2
10
measured
1 1
10 10
-2 -1 0 1 2 3 4 5
10 10 10 10 10 10 10 1/s 10
Angular Frequency

27
 Viscoelastic Behavior
Temperature - dependent Behavior

amorphous partially crystalline cross-linked

Tg...glass transition temperature Tm...melting temperature

28
 Partially Crystalline Polymer - DMTA

29
 Rheometry
Fixtures for Solids

Torsion Bar
Fixture

typical
bar dimensions:

50 x 10 x 1
(in mm)

30
 Viscoelastic Behavior of Solids
Dynamic Mechanical Thermo-Analysis (DMTA)
Temperature - dependent Behavior
polymers

10

GPa reinforced Laminate

1

unmodified Laminate
lg G'
0.1
lg G''

softening
0.01 = 10 rad/s
= 0.01 %
Summary: shift of Tg from +132 to +152C dimensions
of the solid bar :
50x10x1 (in mm)
+20 50 100 150 C 180
temperature T
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 Viscoelastic Behavior
Time - dependent Curing
coatings polymers
106 melting curing 200
Comparison
180
Pa C of two
160 Powder
105 Coatings
140

PC 1
lg G'
104 PC 2
lg G'' T

= 0.1 %
103
Analysis: = 10 rad/s
1) Minimum of G' or G'' preset: T = T(t)
2) crossover G' = G''
3) end of curing disposable
measuring
102 0 200 400 600 800 1000 plates
s
time t
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 Reaction Kinetics for Thermosetting
Polymer

33
EC-TwistTM
Modular Dynamic Mechanical Analyzer

Material
Melts characterization DMTA

Sealants,
Adhesives
Mechanical
properties

Elastomers Time, temperature, frequency Curing

34 http://www.anton-paar.com/DE/de/Web/Document/download/11158?clng=en
 Learn More about Rheology ?

Rheology Workshop
University of Nottingham
2 day course at 399
Contact steve.goodyer@anton-paar.com

Free Sample Work / Rheology Audit

Rheology Handbook, Thomas Mezger

British Society of Rheology

http://www.bsr.org.uk/

35