Thermal Analysis of

Rubbers and Elastomers

Mackenzie Geiger
Applications Scientist
September 6, 2017

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 Thermal Analysis

What does it measure and what is it used for?

Thermal Analysis is a series of complementary techniques to measure
various properties of materials as a function of temperature and time

▪Thermogravimetric Analysis (TGA)

 Weight loss, weight gain, compositional and thermal stability
of a material. [Sorption Analysis]
 Provides information to aid in the interpretation of DSC data.
Extremely complementary to DSC.
▪Differential Scanning Calorimetry (DSC)
 Measures Heat Flow into or out of a sample
 Modulated DSC – Separates Heat Flow into Heat Capacity,
Reversing and Non Reversing Heat Flow

▪Thermomechanical Analysis (TMA)

 Determines dimensional changes of a material, coefficient of
thermal expansion, glass transition

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 What Materials?

•Iron and Steel

•Aluminum and other metals (Mg)
•Adhesives and Sealants
•Textiles / Leather
•Rubbers and elastomers
•Thermoplastic Polymers
•Composites
•Thermosets ans Resins
•Coatings and Paints
•Fluids and Lubricants
•Glass
•Other (electronics, fuel cell, gasoline, nano-materials,
ceramics, sensors, etc.)

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Agenda

1. Thermogravimetric Analysis

Standard and Hi-Res TGATM, TGA-MS,

Decomposition and Lifetime Kinetics

2. Differential Scanning Calorimetry

Technique Overview, Conventional vs.

Modulated DSC®, Curing Kinetics

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Thermogravimetric Analysis
(TGA)

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 Thermogravimetric Analysis (TGA)

•TGA measures amount and rate of

weight change vs. temperature or
time in a controlled atmosphere

•Used to determine composition and

thermal stability up to 1000°C (Q50 &
Q500); 1200°C (Discovery TGA) &
1500°C (SDT)

•Characterizes materials that exhibit

weight loss or gain due to
decomposition, oxidation, or
dehydration

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Mechanisms of Weight Change in TGA

• Weight Loss:
▪ Decomposition: The breaking apart of chemical bonds.
▪ Evaporation: The loss of volatiles with elevated
temperature.
▪ Reduction: Interaction of sample to a reducing atmosphere
(hydrogen, ammonia, etc).
▪ Desorption.
• Weight Gain:
▪ Oxidation: Interaction of the sample with an oxidizing
atmosphere.
▪ Absorption.
All of these are kinetic processes (i.e. there is a rate at
which they occur).

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Decomposition of Elastomers in Nitrogen

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Volatilization of Plasticizers/Oils

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 Styrene-Butadiene Rubber Analysis

100
8.4% Oil

75 50.4% Polymer
Wt (%)

50 Air

36.2% Carbon Black

25 Sample weight: 30 mg
Program rate : 20°C/min
Atmosphere : N2 , Air 5% Inert Filler
0
0 200 400 600 800 1,000
Temperature (°C)
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 Sample: Cured Tire Tread Rubber Compoun
Size: 10.8690 mg
TGA of Tire Rubber File: CURED TIRE TREAD RUBBER COMPOUND.001
Run Date: 18-Nov-2005 12:06

100
12

6.122% Oil
(0.6654mg)
51.84% Polymer
(5.634mg) 10
80

Deriv. Weight (%/min)

8

60
Weight (%)

TGA Analysis
10.87 mg of Tire Rubber Compound
20°C/min to 600 °C in N2 6
20°C/min to 1000°C in air
38.96% Carbon
(4.234mg)

40
4

2
20
Residue:
3.013%
(0.3275mg)
0

0
0 200 400 600 800 1000
Temperature (°C) Universal V4.5A TA Instruments

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 TGA of Rubber in Nitrogen
Sample: Rubber 10C/min N2 - Green Colorant
Size: 10.0264 mg

120

1.202% 62.81%
(0.1205mg) (6.297mg)
100

487.73°C

Deriv. Weight (%/°C)

80
Weight (%)

424.01°C

60
141.62°C

40 Residue:
32.14%
(3.223mg)

20 -1
200 400 600 800 1000
Temperature (°C)
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 TGA Rubber in Air
Sample: Rubber 10C/min Air - Green Colorant
Size: 9.8941 mg

120 6

477.91°C

1.567% 76.50%
(0.1551mg) (7.569mg)
100
4

Deriv. Weight (%/°C)

80
Weight (%)

60

420.58°C

0
40

Residue:
21.69%
(2.146mg)

20 -2
200 400 600 800 1000
Temperature (°C)

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 TGA Rubber in Air vs Nitrogen

120 6
––––––– Rubber 10Cmin Air - Green Colorant.UA
––– ––– Rubber 10Cmin N2 - Green Colorant.UA
477.91°C
1.567%
(0.1551mg)
76.50%
100 (7.569mg)

1.202% 4
(0.1205mg) 62.81%
(6.297mg)

Deriv. Weight (%/°C)

80
Weight (%)

2
Residue:
32.14%
424.01°C 487.73°C (3.223mg)
60
420.58°C
Residue:
21.02%
(2.080mg)
0
40

20 -2
200 400 600 800 1000
Temperature (°C)
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 Hi-ResTM TGA

• In a Hi-ResTM TGA experiment the heating rate is controlled by the rate of

decomposition.

• Faster heating rates during

periods of no weight loss, and
slowing down the heating rate
during a weight loss – therefore
not sacrificing as much time

• Hi-ResTM TGA can give better

resolution or faster run times,
and sometimes both

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EPDM Rubber by TGA & Hi-Res™ TGA

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Process Oil in a Rubber Compound by Hi-Res
TGA

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 TGA-Evolve Gas Analysis (EGA)

•TGA measures weight changes (quantitative)

•Difficult to separate, identify, and quantify individual
degradation products (off-gases)
•Direct coupling to identification techniques (Mass Spec,
FTIR) reduces this problem

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TGA-MS of Styrene Butadiene Rubber (SBR)
Sample: SBR File: C:...\Bnl\Rubber\tga\SBR\Sbr1.001
Size: 1.8030 mg TGA Operator: Daniel ROEDOLF
Run Date: 31-Dec-01 16:31
Comment: Helium Instrument: AutoTGA 2950HR V5.4A

90

2mg sample
He purge,

Deriv. Weight (%/min)

40°C/min
Weight (%)

70

50

30
0 100 200 300 400 500 600 700
Temperature (°C) Universal V3.2A TA Instruments
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Fingerprint of Natural Rubber vs SBR

67
Natural
Rubber

67 91
Styrene
Butadiene
Rubber

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 Mass 45 to 170

Natural
Rubber

Styrene
Butadiene
Rubber

N
Nitrile
Rubber

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Mass 100 to 200

Natural
Rubber

Styrene
Butadiene
Rubber

Nitrile N

Rubber

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 Styrene Butadiene Rubber
500°C
64
78
48

250°C

Deriv. Weight (%/min)

400°C

Weight (%)
250°C

400°C
0 100 200 300 400 500 600 700 800

SBR Temperature (°C)

500°C

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Decomposition and Lifetime
Kinetics

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Simple Polymer Decomposition

  E 
  A exp 
 RT 
 E 
ln   A   
 RT 
where
  heating rate (C / min)
A  pre - exponential
E  Activation Energy (kJ / mol)
T  temperature (K)
R  Universal Gas Constant

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 Simple Polymer Decomposition

•Experimental
•Run TGA experiment on polymer at 4 different heating
rates. Use the same gas for each – typically nitrogen or
air.
•Obtain a temperature at an isoconversional point – for
example 2% weight loss for each heating rate
•Plot the ln of the heating rate () versus 1/T (temperature
units must be in Kelvin)
•Slope of the line is (-ΔE/R). Multiply the slope of the line by
–(8.314 x 10-3) to obtain the activation energy in kJ/mol.

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Decomposition Kinetics

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Decomposition Kinetics

1000/T (K)

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TGA Kinetics – Isoconversion Plot

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 TGA Kinetics - Estimated Lifetime

TEMPERATURE (°C)
260 280 300 320 340 360
1000000
1 century

100000 1 decade
ESTIMATED LIFE (hr.)

ESTIMATED LIFE
10000 1 yr.

1000 1 mo.

1 week
100
1 day
10
1.9 1.8 1.7 1.6 1.5
1000/T (K)
TA Instruments Application Note TA125
Estimation of Polymer Lifetime by TGA Decomposition Kinetics
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 Differential Scanning Calorimetry
(DSC) and Modulated DSC® (MDSC)
Overview

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Differential Scanning Calorimetry (DSC)

•Differential Scanning Calorimetry (DSC) is most popular

thermal analysis technique
•DSC measures endothermic and exothermic transitions as
a function of temperature
▪Endothermic heat flows into a sample
▪Exothermic heat flows out of the sample
•Used to characterize polymers (thermosets,
thermoplastics, elastomers)
•Also used with pharmaceuticals, foods/biologicals, organic
chemicals and inorganics
•Transitions measured include Tg, melting, crystallization,
curing and cure kinetics, onset of oxidation and heat
capacity
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What is Differential Scanning Calorimetry?

•Calorimetry is a technique for determining the quantity of heat that is

either absorbed or released by a substance undergoing a physical or
chemical change.
•A DSC measures the difference in Heat Flow Rate between a sample
and inert reference as a function of time and temperature.

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Simple Heat Flux DSC Cell Schematic

Sample

Reference Sensor Sample Sensor

An empty pan on the Heat absorbed by the

reference sensor should sample gives an
react similarly to the pan endothermic response
on the sample sensor, thus
canceling out any pan Heat released by the
contribution sample gives an
exothermic response

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DSC Heat Flow

dH dT
 Cp  f (T, t)
dt dt
Heat
Kinetic
Capacity

Crystallization
Cure reactions
Glass
Transition Volatilization
Decomposition
Denaturation

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 Endothermic Heat Flow
Heat Absorbed by Substance
Endothermic Events
•Glass transition
•Melting
•Evaporation/
volatilization
•Enthalpic recovery
Glass Transition, Tg
•Polymorphic
(Half height)
23.08 °C transitions
•Some decompositions

Exo Up

Exo Up

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 Exothermic Heat Flow
Heat Released by Substance
Exothermic Events
•Crystallization
•Cure reactions
•Polymorphic transitions
•Oxidation
•Decomposition

Exo Up

Exo Up

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 Typical DSC Transitions

Oxidation
Or
Crystallization Decomposition
Heat Flow -> exothermic

Melting
Glass
Cross-Linking
Transition
(Cure)

Composite graph

Temperature

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 Polyethylene Terephthalate (PET)
1.5

1.0

Cool

0.5
Heat Flow (W/g)

0.0 Second Heat

First Heat

-0.5

-1.0

Exo Up
-1.5
20 60 100 140 180 220 260
Temperature (°C)
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 What Does MDSC® Measure?

•MDSC separates the Total heat flow of DSC into two parts
based on the heat flow that does and does not respond to
a changing heating rate
•MDSC applies a changing heating rate on top of a linear
heating rate in order measure the heat flow that responds
to the changing heating rate
•In general, only heat capacity and melting respond to the
changing heating rate
•The Reversing and Non-reversing signals of MDSC should
never be interpreted as the measurement of reversible
and nonreversible properties

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 Reversing Heat Flow and Heat Capacity

4
2 16

Deriv. Modulated Temperature (°C/min)

0 0
Modulated Heat Flow (mW)

12
Rev Heat Flow (mW)

Rev Cp (J/(g·°C))
-2
-4
8
-2

-4
-8
-4 4

-6

-6 -12
0
-8
-50 0 50 100 150 200 250 300 350
Exo Up Temperature (°C) Universal V4.2E TA Instruments

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 MDSC Heat Flow Signals

dH dT
 Cp  f (T, t)
dt dt
Total Reversing Non-Reversing
Heat Flow Heat Flow Heat Flow
•All Transitions •Heat Capacity •Enthalpic Recovery
•Glass Transition •Evaporation
•Most Melting •Crystallization
•Thermoset Cure
•Denaturation
•Decomposition
•Some Melting

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Calculated MDSC Heat Flow Signals

Quenched PET – 8.99mg

.424/40@4

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 PET/ABS Blend - Conventional DSC

-0.2 120.92°C
67.38°C first heat on molded part
70.262°C (H)
235.36°C
-0.3 22.63J/g
Heat Flow (W/g)

-0.4
111.82°C
-0.5 9.016J/g

249.75°C
-0.6
second heat after 10°C/min cooling
(Curve shifted on Y axis to avoid overlap)
-0.7
9.22 mg sample, nitrogen purge
10°C/minute heating rate
-0.8
50 100 150 200 250
Temperature (°C)

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 PET/ABS Blend - MDSC

-0.10 first heat on molded part -0.04

-0.02

-0.11 -0.05

) Nonrev. Heat Flow (W/g)

-0.03

) Rev. Heat Flow (W/g)

Heat Flow (mW)

-0.12 -0.04 -0.06

67.00°C
-0.13 +72.89°C (H)
-0.05 -0.07
PET Tg
104.45°C
107.25°C (H)
-0.14 -0.06 -0.08
8.46mg sample ABS Tg
nitrogen purge

(
2°C/minute heating rate, ±1°C amplitude, 60 second period

(
-0.15 -0.09
20 40 60 80 100 120 140 160 180 200
Temperature (°C)
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Elastomer Tg by DSC
0.0

-0.5

Elastomer - 10.18mg
-1.0 DSC - 10°C/min
Heat Flow (mW)

-1.5 -62.63°C(H)

-2.0

-2.5

-3.0
-80 -60 -40 -20 0 20
Exo Up Temperature (°C) Universal V4.3A TA Instruments

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Elastomer Tg by DSC & MDSC
0.0 0.2

Elastomer - 10.46mg
-0.2
-64.57°C(H) MDSC - 0.48/60@3°C/min 0.0

Rev Heat Flow (mW)

Heat Flow (mW)

-61.08°C(H)

-0.4 -0.2

-0.6 -0.4
-80 -60 -40 -20 0 20
Exo Up Temperature (°C) Universal V4.3A TA Instruments

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Curing Kinetics

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 Typical properties of crosslinking reactions

• Crosslinking reactions are generally • Crosslinking reactions are generally

exothermic. As the chemical reaction accompanied by a sharp change in the
takes place, it is almost always material’s mechanical properties.
accompanied by a release of heat.
• Increase in modulus that may be
accompanied by shrinkage.
• The reactions can be easily monitored
using a DSC.
• The reactions can thus be monitored
▪Heat of reaction using a Thermo-mechanical Analyzer
▪Residual cure (TMA)/Dynamic Mechanical Analyzer
▪Glass transition (DMA)/Rheometer.
▪Heat capacity ▪Viscosity
▪Modulus
▪Glass transition
▪Dimension change (shrinkage)

These techniques give useful information about the impact of the polymerization
conditions on the end product’s thermo-mechanical properties.

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 Curing reactions are kinetic in nature
6
172.86°C 1°C/min
5.792W/g 2°C/min
5°C/min
10°C/min
20°C/min
160.93°C
4 3.431W/g
Heat Flow T4 (W/g)

149.93°C
1.972W/g
2
137.04°C
0.9506W/g
128.29°C
0.5594W/g

0
122.26°C 141.85°C 162.53°C
323.9J/g 315.1J/g 320.5J/g
130.12°C 151.92°C
315.5J/g 320.0J/g

-2
100 120 140 160 180 200 220 240
Temperature (°C)
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Use of Kinetic Modeling for Characterization of Curing
Reactions

•Predict how long a reaction takes to go to completion

•Optimize polymerization, curing

•Quantify parameters that characterize time-temperature-

dependent process behavior under conditions that may not
always be experimentally feasible.

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Fundamental equation for kinetics

d
 f (T ) • f ( ) Where:
dt
 fraction reacted
=
or converted
d = reaction rate
dt
f(T) = a function of Temp.
f() = a function of 

d d d f(T)*f()
dt f(T) dt f() dt

T
Our Goal: Use DSC to solve for these functions
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Fundamental equation for kinetics: the
temperature factor
•Fundamental equation for kinetics
d
 f (T ) • f ( )
dt

•Arrhenius temperature dependence

Where Ea is activation energy
f (T )  Ze  Ea / RT Z is the “frequency factor”
R is the gas constant
•Derived from dilute gas T in kelvin
or solution, refined for solids
•Physical significance: Molecules
colliding with sufficient kinetic energy to E Ea
overcome Ea cause a reaction
•Pre-exponential factor, Z, “frequency factor”
accounts for steric effects

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 Selection of appropriate model – the “” factor

•Fundamental equation
d
 f (T ) • f ( )
dt

•Many models, three simple ones

▪nth order reaction: f ( )  (1   ) n n is reaction order
▪Modelling technique:
1
 n = 1: ASTM E698 /Ozawa, Wall and Flynn method
2

 n ≠ 1: ASTM E2041 /Borchardt and Daniels method

3 4

▪Autocatalyzed reaction: f ( )   (1   ) n and m are reaction orders

m n

▪Modeling technique:
5
 ASTM E2070 /Sestak and Berggren method (Isothermal

kinetics)6
1ASTM E698, ASTM Annual Book of Standards 2005 volume 14.02 5ASTM E2070, ASTM Annual Book of Standards 2005 volume 14.02
2Ozawa, T.J. J. Thermal Analysis, 1970, v2, p301 6Sestak, J., and Berggren, G., Thermochim. Acta, 1971, vol 3, pg 1
3ASTM E2041, ASTM Annual Book of Standards 2005 volume 14.02
4Borchardt, H.J., and Daniels, F.J., Am. Chem. Soc. 1956, v79, pg 41
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Obtaining kinetics information from a DSC
experiment

DSC gives us  and d/dt

vs time and temperature

Sample: Thermoset File: C:\TA\Data\DSC\DSC-CURE.001

Size: 5.5360 mg DSC Operator: C. Jay Lundgren
Method: RT to 250°C at 10°C/min
Comment: He Purge = 25ml/min
2.0

1.8
90

1.6
70

Area percent (%)

Heat Flow (W/g)
1.4

50

1.2

Running integral option 1.0

30

provides  as a direct function 0.8

10

of time/temperature
0.6
40 60 80 100 120 140 160 180 200
Exo Up Temperature (°C) Universal V4.5A TA Instruments

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 Kinetic analyses can provide valuable
information
Half-life of the reaction: Use as litmus test
for validity of kinetic model

Predict the cure temperature for one hour half

life and carry out the iso cure in the DSC. Cool
the sample after 1 hour and rerun. Was the
residual reaction ½ the total heat of reaction?

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Case Study: DSC of Green Colorant Rubber

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Case Study: Isothermal DSC Curing

Method:
1. Equilibrate to 150 °C (160, 170, or 180 °C)
2. Mark end of cycle
3. Isothermal for 30 minutes
4. Mark end of cycle
5. Equilibrate to -100°C
6. Ramp 10°C/min to 300°C

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Case Study: DSC Isothermal at 150 °C

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Case Study: Green Colorant Rubber Sample
Ramp After Iso Hold at 150C

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Case Study: DSC Isothermal Treatments

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 Case Study: Summary

• Differential scanning calorimetry can be used to simulate

plant processing of thermosetting materials with limitations
•Common limitations are:
▪ Too high a curing temperature to get good DSC data
▪ Too low small or no curing exotherm
 Examples: low level peroxide crosslinkers, vulcanization,
highly cured specimens

• DSC can be used both to thermally condition the

thermoset and then determine the extent of cure
• DSC kinetic model can be highly predictive
• Ongoing cutting edge academic studies

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 Section Summary

•Thermal analysis – both TGA and DSC – are widely used

in the rubber industry
▪ Material characterization (QC, R&D, etc.)
▪ Process optimization through cure kinetics
▪ Stability (thermal, oxidative)

•TA Instruments is a premier supplies of thermal analytical,

rheological, thermal physical and other instrumentation to
all technology based industries

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Any questions?

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