Applications Elastomers

VKRT Bijeenkomst 8 Februari 2007. Hay Berden

Author: J. Schawe Date: June 06 Vers.1 Approved: Ni Jing

Agenda

1. Do you need to know the influence the glass transition temperature has on your product? 2. Is your product used in an area that requires it to be thermal stable? 3. You are interested in measuring the product formulation in % or phr? 4. Does part of your process optimization involve vulcanization development? 5. Do you need to understand the influence different fillers have on your material?

Internal usage only

Agenda

6. Would you like to know whether your materials swell in contact with solvents or moisture? 7. Are you interested in process simulations to improve product output? 8. Is the cross-linking density of your product important for the final application? 9. Do you need to understand the effect of high and low frequency vibrations on your product?

Internal usage only

Introduction
Typical questions regarding elastomers

Internal usage only

1 Glass transition
Do you need to know the influence the glass transition temperature has on your product?

The glass transition - determines the working range of a material - determines the mechanical behavior - allows analysis of the decomposition

TA Handbook, Collected Applications: Elastomers Chapter 4.1.2, 4.5.3, 4.5.5, 3.4.3

4
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1 Glass transition
Rubbers show different glass transition temperatures
^exo Glass Trans ition of Different Rubbers 07.07.2002 13:03:33

Polymer
E-SBR NBR L-SBR

Tg In C 123 62 53 37 50 32 20

cp In J/gK 0.32 0.46 0.43 0.33 0.54 0.50 0.45

0.2 Wg^-1

Silicone rubber NR

CR

EPDM CR E-SBR

NR silicone rubber

EPDM

-120
Schawe: JSchawe

-100

-80

-60

-40

-20

0 C

METTLER TOLEDO STAR e System

NBR L-SBR

Internal usage only

1 Glass transition
Analysis of polymer blends by DSC
^exo

NBR/CR NR/SBR

DSC of Incom patibl e Polym er Bl ends 07.07.2002 15:43:53 Glass Transition Midpoint ASTM,IEC -49.68 C Delta cp ASTM,IEC 0.105 Jg^-1K^-1

NBR/CR blend: 24.4% NBR 24.4% CR 33.7% Fillers NR/SBR blend:

Glass Transition Midpoint ASTM,IEC Delta cp ASTM,IEC

-13.60 C 0.110 Jg^-1K^-1

0.1 Wg^-1
Glass Transition Midpoint ASTM,IEC Delta cp ASTM,IEC

-58.85 C 0.155 Jg^-1K^-1 -44.10 C 38.906e-03 Jg^-1K^-1

25.5% NR 7.2% SBR 53.3% Fillers

Glass Transition Midpoint ASTM,IEC Delta cp ASTM,IEC

-120
Schawe: JSchawe

-100

-80

-60

-40

-20

0 C

METTLER TOLEDO STAR e System

Glass transition temperature identification Glass transition intensity content determination

6
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1 Glass transition
Glass transition measurement by DMA
Temperature Scan of Unvulcanized SBR 08.07.2002 10:01:55

Pa 10^8 10^7 10^6 10^5

G' 1 Hz10 Hz
100 Hz 1000 Hz

G"

-40 2 1 0 -40
Lab: JSchawe

-20

20

40

60

80 C

1 Hz 10 Hz 100 Hz 1000 Hz

tan

-20

20

40

60
e

80 C

METTLER TOLEDO STAR SW 7.00 B10+

DMA characterizes the glass transition and mechanical properties

7
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1 Glass transition
Glass transition measurement of blends by DMA
Shear Modul us of an SBR/NR Bl end 15.07.2002 11:29:54

Pa 10^9

G'
1 Hz 10 Hz 100 Hz

40% NR 60% L-SBR

10^8 G"

10^7

10^6

10^5

10^4 -80
Lab: JSchawe

-60

-40

-20

20

40

60

80 C

METTLER TOLEDO STARe SW 7.00 B10+

Internal usage only

2 Thermal stability
Is your product used in an area that requires it to be thermal stable?

TGA shows differences in thermal stability

TA Handbook, Collected Applications: Elastomers Chapter 4.1.1,

9
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2 Thermal stability
Comparison of different SBR materials
TGA of SBR 07.07.2002 12:40:55

% TGA

3 VSL5025-0 2 Krylene 1500

50
4

0 100 200 300 400 500 600 700 C

Emulsion polymerized SBR contains more volatile components than SBR polymerized in solution.

50 %min^-1

DTG

100
Schawe: JSchawe

200

300

400

500

600

700
e

METTLER TOLEDO STAR System

TGA delivers information of thermal stability

10
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3 Compositional analysis
You are interested in measuring the product formulation in % or phr?

Compositional analysis, to determine the different components and the related content of a formulation: - Competition analysis - Quality control

TA Handbook, Collected Applications: Elastomers Chapter 3.2.1, 4.5.1, 4.5.4

11
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3 Compositional analysis
Different standards: ASTM E 1131, ASTM D 6370, ISO 9924, NFT 46-047, UNI 8698, VDA 675135, etc. Example 1: ASTM E 1131
(50 ml/min nitrogen) (50 ml/min oxygen)

1. RT to 600 C at 10 K/min 2. 600 C to 750 C at 10 K/min

Example 2:
1. 2. 3. 4. 5.

ASTM D 6370
(75 ml/min nitrogen) (75 ml/min nitrogen) (75 ml/min nitrogen) (75 ml/min nitrogen) (75 ml/min oxygen)

50C for 2 min 50C to 560 C at 10 K/min 560 C to 300 C at -30 K/min 300C for 2 min 300C to 800 C at 10 K/min

12

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3 Compositional analysis
Simple compositional analysis
TGA Analysis of El as tomers 06.07.2002 19:12:16

1st step
Step -3.0646 % -0.4047 mg

2nd step

3rd step DTG

Analysis results:
volatiles: polymer: carbon black: ash: 3.06% 62.89% 31.52% 2.29%

Step -62.8888 % -8.3045 mg

50 %

Step -31.5186 % -4.1620 mg Residue 2.2912 % 0.3025 mg

0.5 %C^-1 TGA

volatiles: 4.8 phr polymer: 100.0 phr carbon black: 50.1 phr ash: 3.6 phr

200
Schawe: JSchawe

400

600

METTLER TOLEDO STAR e System

phr (part per hundred rubber) Example: CB in phr = 31.52*100/62.89

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3 Compositional analysis
If carbon black a pyrolysis product:
TGA of CR with Different Methods 07.07.2002 14:55:55

% 100 80 60 40 20 0 200
Schawe: JSchawe

10 K/min

30 K/min

Analysis results:
The carbon black content is 43%. 10% is pyrolysis product.

DTG TGA 1 %C^-1

Step -10.4131 % -1.4571 mg Step -42.9756 % -6.0136 mg Step -52.5130 % -9.8099 mg

400

600

800

METTLER TOLEDO S TAR e System

14

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3 Compositional analysis
Polymers with different decomposition temperature
TGA of NR Blends 07.07.2002 15:26:25

Analysis results:
Two peaks in the decomposition step

100 % TGA 1 DTG

2 3 E 4

D C B A

10 %min^-1

D C A B

200
Schawe: JSchawe

400

600

800

METTLER TOLEDO STAR e System

15

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3 Compositional analysis
Polymers with similar decomposition temperatures (12.6%SBR/25.5% EPDM)
TGA of an EPDM/SBR Bl end 13.07.2002 13:40:04

^exo

%
Step -14.1539 % -1.5020 mg

DTG

5 mW
0.5 %C^-1
EPDM
Glass Transition Midpoint ASTM,IEC Delta cp ASTM,IEC

DSC of a EPDM/SBR Blend 13.07.2002 13:42:51 Glass transition of EPDM Overlap of the glass transition of SBR and the EPDM melting process

80 TGA
2 K/min

60

Polymer Step -39.0583 % -4.1448 mg

-57.14 C 0.135 Jg^-1K^-1

Integral -48.75 mJ normalized -1.72 Jg^-1 Baseline Type tang. right

SBR
Glass Transition Midpoint ASTM,IEC Delta cp ASTM,IEC -40.41 C 57.898e-03 Jg^-1K^-1

-120 -100 -80

100
Schawe: JSchawe

-60

-40

-20

20

200

300

400

C
Glass Transition Schawe: JSchawe Integral TOLEDO STAR e System -48.75 mJ METTLER

METTLER TOLEDO STAR e System

EPDM =

p c p ,EPDM
c p ,EPDM + c p ,SBR

This calculation gives a value of 27.3% for EPDM, and consequently 11.7% for SBR.

TGA delivers the polymer content; DSC separates the polymer components
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4 Vulcanization kinetics
Does part of your process optimization involve vulcanization development?

Most technical reason for elastomer failure is insufficient vulcanization. Vulcanization is energy and time consuming.

TA Handbook, Collected Applications: Elastomers Chapter 3.1.3

17
Internal usage only

4 Vulcanization kinetics
Vulcanization of different elastomers
Enthapy of reaction
^exo Vulcanization Reaction 19.06.2002 16:04:15

depends on filler crosslinker etc.

Integral 528.54 mJ normalized 11.29 Jg^-1 Peak 179.74 C

Silicone elastomer 0.2 Wg^-1 Integral 126.00 mJ normalized 4.59 Jg^-1 Peak 153.64 C

NBR

-50
Schawe: JSchawe

50

100

150

200

250

METTLER TOLEDO STAR e System

18

Internal usage only

4 Vulcanization kinetics
Kinetic evaluation of vulcanization reaction (DSC measurements)
^exo Vulcanization Reaction of NBR 06.07.2002 18:47:46

20 K/min

0.1 Wg^-1

15 K/min 10 K/min 5 K/min 2 K/min 1 K/min

100
Schawe: JSchawe

150

200

METTLER TOLEDO STAR e Sys tem

19

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4 Vulcanization kinetics
Kinetic evaluation of vulcanization reaction (MFK evaluation)
^exo Model Free Ki netics of Vul canization 06.08.2002 10:32:34

% 1 K/min 80

2 K/min 5 K/min

Activation energy kJmol^-1 140 120 100 50 % 80 60 140 130 120 110 % C C C C

60

40

20

40 20

100 C

0 100
Schawe: JSchawe

0 150 C 0 20 40 min
METTLER TOLEDO STAR e Sys tem

MFK evaluation helps for process optimization.

20
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5 Filler influence
Do you need to understand the influence different fillers have on your material?

The interaction between filler and polymer matrix improves the mechanical behavior of elastomers. TGA for identification TMA and DMA for determination of mechanical properties

TA Handbook, Collected Applications: Elastomers Chapter 4.3.3, 4.3.4, 4.3.5, 4.5.5

21
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5 Filler influence
Determination of the filler content:
TGA of EPDM wi th Carbon Black 07.07.2002 14:42:47

% Volatiles 100 Polymer

Analysis results:
carbon black u combustion step
W305

Carbon black

50

W309 W313

inorganic filler u residue

100 10

200 20

300 30

400 40

500 50

600 60

700 C min

Schawe: JSchawe

METTLER TOLEDO STAR e System

22

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5 Filler influence
Comparison between different carbon blacks:
TGA of EPDM wi thMidpoint Di fferent Carbon Blacks 13.07.2002 12:52:45 563.77 C

%
W312 Step -43.9601 % Midpoint 554.42 C w314 Step -44.5310 % Midpoint 563.77 C w313 Step -44.1928 % Midpoint 577.78 C w311 Step -44.3938 % Midpoint 602.18 C

Analysis results:
higher reactivity u lower midpoint temperature of the combustion step

80 60 40 20 0

100
Schawe: JSchawe

200

300

400

500

600

700

METTLER TOLEDO STAR e Sys tem

23

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5 Filler influence
Young modulus in the rubbery plateau by TMA: s Isotherm 26 kracht tussen 0.05 en 1 N variabel. C.
DLTMA of EPDM with Different Fil lers 13.07.2002 12:54:56

Analysis result:
Filler type N990 N550

Force : 50 mN / 1 N

21.0% N550 34.7% N550 44.3% N550

25

99

Young's modulus in MPa

2.2 2.4 2.6 2.8 3.0 3.2 3.4
e

20

15

98

10

97

96 2.0

min
0 20 25 30 35 40 45

Schawe: JSchawe

METTLER TOLEDO STAR System

Carbon black content in %

The filler influence of the modulus in the rubbery plateau can be measured be DLTMA
24
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6 Expansion coefficient
Is your product affected by expansion or contraction when the temperature changes?

Measurement of the Thermal expansion coefficient by TMA

TA Handbook, Collected Applications: Elastomers Chapter 3.3.1

25
Internal usage only

6 Expansion coefficient
The thermal expansion by TMA:
Expansi on Coeffi cient 19.06.2002 16:58:23

Expansion Coefficient C ppmC^-1 50.00 208.42 100.00 202.19 150.00 203.67 200.00 203.96 250.00 201.02 300.00 176.57

% 106 104

Sample B

silicone elastomer with

Sample A

61.6% inorganic filler (sample A) 56.0% inorganic filler (sample B)

102 100

ppmC^-1
Expansion Coefficient C ppmC^-1 50.00 257.73 100.00 247.70 150.00 258.77 200.00 253.45 250.00 251.06 300.00 238.01

100

200

Load 0.02 N.
200

5mm thick
150 100 200 C

Schawe: JSchawe

METTLER TOLEDO STAR e System

The expansion coefficient depends on polymer and filler

26
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7 Swelling in solvent
Would you like to know whether your materials swell in contact with solvents or moisture?

Swelling is important for application in - automotive industry - petrochemical industry - medicine technology - sealing techniques - recycling etc.

TA Handbook, Collected Applications: Elastomers Chapter 4.8.1

27
Internal usage only

7 Swelling in solvent
isothermal 25 Force 0.1N C
Swel li ng Measurements by TMA 07.07.2002 16:54:56

%
MQ

MQ: methyl-silicone rubber EPDM: ethylenepropylene-diene terpolymer NBR: acrylonitrilebutadiene rubber FPM: fluororubber

130
EPDM NBR

120

110

FPM

100 0
Schawe: JSchawe

10

20

30

min

METTLER TOLEDO STAR e System

Swelling of different elastomers in toluene

28
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8 Improve product output

Are you interested in process simulations to improve product output? The product output is mainly determined by:

- degree of vulcanization - vulcanization temperature and time - the used filler and filler content
For simulation physical properties also important:

- heat capacity, glass transition temperature - thermal expansion coefficient - mechanical modules - cross-linking density - reaction kinetics
These topics are described in point 1, 4, 5, 6, 7, 9, 10
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9 Cross-linking density
Is the cross-linking density of your product important for the final application?

The cross-linking density Influences the mechanical behavior: - modulus - hardness - flow behavior - mechanical long term stability - swelling behavior - damping behavior
TA Handbook, Collected Applications: Elastomers Chapter 4.8.1, 4.2.2
30
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9 Cross-linking density
Creep measurement of o-rings by TMA:
Creep Measurements with TMA 07.07.2002 16:51:17

0.01 N

1 N

0.01 N

Increasing crosslinking density decreases viscous flow and increases the modulus. Increasing filler content increases the modulus but has only a small influence on the flow behavior.

5 %

FPM EPDM

0
Schawe: JSchawe

20

40

60

80

min

METTLER TOLEDO STAR e System

The creep recovery behavior depends on the cross-linking density

31
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9 Cross-linking density
Influence of the degree of cross-linking on the mechanical behavior
SBR wi th Differ ent Network Densities 15.07.2002 11:19:11

Pa

G'
SBR1 SBR2 SBR3 SBR4

10^8

Influence of vulcanization on the mechanical properties

SBR1: 0.5 phr sulfur SBR2: 2 phr sulfur SBR3: 4 phr sulfur SBR4: 8 phr sulfur Cross-linking density, , can be estimated from the plateau modulus G:
80 C

10^7 G'' 10^6

10^5

10^4 -40
Lab: JSchawe

G 2 RT

-20

20

40

60

METTLER TOLEDO STAR e SW 7.00 B10+

DMA determines the mechanical properties at different degree of vulcanization

32
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10 Vibration damping
Do you need to understand the effect of high and low frequency vibrations on your product?

The knowledge of the vibration behavior is important for the vibration and sound damping.

TA Handbook, Collected Applications: Elastomers Chapter 4.5.5

33
Internal usage only

10 Vibration damping
Temperature scan at different frequencies:
Temperature Scan of an NBR/CR Elastom er 15.07.2002 11:42:15

MPa 10^2 10^1 10^0

G'

Analysis result: NBR 24.4%

CR 24.4% 33.7% Filler

G"

-80 tan 0.4 0.2 0.0 -80

Lab: JSchawe

-60
1 10 100 1000

-40
Hz Hz Hz Hz

-20

20

40

-60

-40

-20

20

40

METTLER TOLEDO STAR e SW 7.00 B10+

This material shows a large loss factor around room temperature

34
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10 Vibration damping
Expansion of the frequency range by master curve:
Mastercurve
MPa

07.06.2006 17:59:25

Analysis result:

G'
10^3

reference temperature: 30.5 C

10^2

G''
10^1

10^0

10^-1

10^-5 10^-4 10^-3 10^-2 10^-1 10^0 10^1 10^2 10^3 10^4 10^ 5 10^ 6 10^7 10^8 10^9 10^10 10^11 10^12 10^1310^14 10^15

Hz

Lab: METTLER

STARe SW 9.01

Master curves allows the determination of the mechanical behavior in a very wide frequency range
35
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Conclusion
DSC Glass transition Composition Thermal stability/ decomposition Oxidative stability Viscoelastic behavior Elasticity modulus Damping behavior Filler content/ carbon black content Filler activity Carbon black activity Evaporation/ desorption/ vaporization Softening temperature Expansion, contraction Swelling in solvent Vulcanization Vulcanization system Melting and crystallization Reaction enthalpy Characterization of additives
36

TGA M M !

TMA !

M ! ! M

DMA M !

! ! ! M

M M M M

! M M M M

M !

M ! M M M !

! ! !

!
Internal usage only