Rubber Compounding For Durability

Rubber Compounding for Durability
Instructor: Christopher G. Robertson, Ph.D.
India, January 2019
© 2018 Endurica LLC cgrobertson@endurica.com

Course Agenda
1. Introduction
2. Brief overview of rubber formulations and mixing approaches
3. Testing for durability in the rubber lab
4. Framework for compounding for durability
5. Polymer selection
6. Crosslinking effects
7. Filler reinforcement
8. Stiffness and deformation control mode
9. Influence of oils, plasticizers, and resins
10. Stabilizing against aging
11. Simulation for materials selection and durability prediction
© 2018 Endurica LLC 0-2

Pre-Prototype Solutions for Elastomer Durability
Characterization Software Testing Instruments

Know Your Material Tools for Developers Our Methods, Your Lab
• Material behavior • Geometry • Intrinsic Strength Analyser

• Parameters for finite • Service History • Tear & Fatigue Analyser
• Integrates with • Instrumented Chip & Cut
element analysis Abaqus™, ANSYS™, Analyser
and MSC Marc™
Endurica LLC founded in 2008 by

Dr. William V. Mars in Findlay, Ohio
© 2018 Endurica LLC www.endurica.com 0-3

Introduction

Rubber Applications
• Vibration control
– Mounts, bushings
• Tires
• Seals
• Medical devices
• Belts
• Hoses
• Shock absorption
– Bumpers, ballistic protection

Elastomer applications are demanding

Value of manufacturing products that have
premium durability in the marketplace
• Satisfied and loyal customers

• Excellent brand image (free marketing and
advertising)
• Win competitive contracts with OEMs,
government, etc.
• Can charge a premium price
• Avoid warranty issues / recalls
• Avoid lawsuits

Product Development Costs
Team: 5 people @ $100k / year
Time: 6 months
Value at stake, PER FAILED

DESIGN ITERATION: $250k +
Materials
engineering materials + time to market
Durability 16%
Testing
34%
Product
engineering
16%
Analysis
Prototyping
8%
26%
• Understanding Compounding for Durability = Less Iterations in

Product Development

Product Liability
• Google Scholar case law search for year 2017:

✓Medical malpractice: 4180 documents
✓Tire failure: 2710 documents
• Need to develop durable products while keeping cost

of raw materials as low as possible
– Average raw materials cost for rubber compounds in tires is
$2 to $3 per kg

Elastomer Failure Words
• Cracked • Degraded
• Tore • Broke
• Blew-Out • Wore out
• Failed • No life left
• Deteriorated
− Notice the past tense!

− Durability is a catch-all term that relates to
product lifetime which can mean different things
in different applications
Rubber Failure – Human Causes
“Common Causes Of Failure In Elastomers” by Gary S. Crutchley (Smithers Rapra Technology)

http://www.iom3.org/fileproxy/461260

Rubber Failure – Service Related Causes
“Common Causes Of Failure In Elastomers” by Gary S. Crutchley (Smithers Rapra Technology)

http://www.iom3.org/fileproxy/461260

Introduction: Rubber Compounds Are Complex
Phase-Separated
Blend Morphology &
Undispersed Filler
Crosslinked Agglomerates (a) Inoue, Y., Iwasa, M., and
Polymer Chains & Filler Particle Network Yoshida, H., Netsu Sokutei 39,
41 (2012).
Polymer-Particle (b) Robertson, C. G. and
Rackaitis, M., Macromolecules
Interfaces 44, 1177 (2011).
CB (c) Sainumsai, W., Toki, S., et
aggregates BR al., Rubber Chem. Technol.
90, 728 (2017).
NR
50 nm 500 nm
5 µm
Strain-Induced
Crystallization
(c) (when stretched) (b)
(a)

Elastomer Characterization for Predicting Durability
• Material characterization is absolutely crucial to successful fatigue life
prediction, especially for rubber
• Materials such as metals possess well-defined mechanical characteristics
• In contrast, the properties of rubber depend incredibly on all sorts of details

that are in the hands of materials scientists and rubber compounders:
– Polymer type, reinforcing fillers, oils/plasticizers, crosslinking ingredients,
mixing conditions, cure conditions, etc.
– The stiffness can be tuned across more than an entire decade!
– Likewise, a wide range of strength and fatigue properties are available
• Because of this, you can almost never just use values from the literature for
rubber to make reliable predictions
• If you want to do fatigue life prediction, you will have to characterize the
material yourself

Course Objectives
• Understand how rubber fatigue and failure

characteristics are influenced by materials selection
and compound structural features
• Learn compounding strategies to improve strength
and fatigue lifetime
• Know the right testing methods to characterize
rubber durability efficiently in the lab

Brief Overview of Rubber Formulations
and Mixing Approaches

Topics
• Example rubber formulations

• Rubber processing overview
• Filler volume fraction
• Crosslink density

Example Rubber Formulations
GR Hamed, “Materials and Compounds” (Chapter 2), in Engineering with Rubber

(AN Gent, Ed.), 3rd Edition, Carl Hanser Verlag, Munich 2012





Si69 silane on
carbon black
(50 wt.% silane)
W Meon, A Blume, HD Luginsland, and S Uhrlandt, “Silica and Silanes” (Chapter 7) in Rubber
Compounding – Chemistry and Applications (B Rodgers, Ed.), Marcel Dekker, New York, 2004



Note:
Different
type of
cure system
(no sulfur)




300.5 total phr!


FKM
https://multimedia.3m.com/mws/media/1408677O/3m-dyneon-fluoroelastomers-compounding-guide.pdf

Rubber Processing
Highly
customizable
material
Typically
used as-is
from
polymer
supplier
B. P. Grady, S. L. Cooper, and C. G. Robertson, “Thermoplastic Elastomers”, Chapter 13, in The Science and Technology of Rubber, 4th Ed. (eds. J. E. Mark, B.
Erman, and C. M. Roland), Waltham, MA: Elsevier Academic Press, 2013, pp. 591-652.

Rubber Processing
• Rubber is compounded
using internal mixers, with
two main types employed:
– Tangential
– Intermeshing
Intermeshing mixers provide better filler

dispersion and temperature control
The Science and Technology of Rubber, 4th Edition (eds. J. E. Mark, B. Erman, and C. M. Roland), Waltham, MA: Elsevier Academic Press, 2013

Rubber Processing
• After rubber batches are mixed using
internal mixers, the compounds are then
processed using sheeters, two roll mills,
and/or calenders
• Some industries use two roll mills for
mixing curatives into the rubber, but it is
better to use internal mixers for dispersing
additives
– Effect of poor dispersion of curatives on
durability of rubber will be discussed in
Crosslinking Effects lecture
• Various shaping processes (extrusion,
molding, etc.) then take place followed by
curing

Filler Volume Fraction
• Filler volume fraction () is key to

 strain control higher 
application
rubber properties, especially
stiffness and related strain energy lower 
density (W)
W = area

𝑤𝑓
σ𝑓 w: weight (can use phr)
𝜌𝑓 : density
= 𝑤 Subscript f: fillers
σ𝑖 𝑖
𝜌𝑖 Subscript i: all compound ingredients including fillers

Filler Volume Fraction
Guth-Gold equation:
Guth equation:
CB Grade CB Grade
old name new name f
MT N990 2.4
FT N880 3.8
HAF N330 7.1
ISAF N220 9.3
SAF N110 11.9
PT (?) PT (?) 17.8
Fitting results for f are from Lewis Tunnicliffe
at Birla Carbon (private communication)
Y Fukahori, AA Hon, V Jha, and JJC Busfield,

Rubber Chem Technol 86, 218 (2013)
• Size and shape of filler particles are also very important to reinforcement

Crosslink Density
less crosslinking more crosslinking
Mc: average molecular weight between crosslinks

: crosslink density (number of crosslinks per volume)
Mc  1/ 
Crosslink Density
• Crosslink density is the number of crosslinks per volume
– Inversely related to molecular weight between crosslinks, Mc
• Common ways of estimating crosslink density
– Modulus
• Higher crosslink density gives higher modulus
– Swelling in a solvent
• Lower crosslink density gives more swelling
• Determining true crosslink density is challenging
– Rely upon rubber elasticity theories for both techniques
–
http://polymerdatabase.com/polymer%20
Polymer-solvent interactions affect swelling physics/RubberElasticity.html
– Trapped entanglements add stiffness and restrict swelling

– Polymer chain interactions with filler particles add stiffness and
restrict swelling

Crosslink Density
• Comparable results for Mc

from modulus and swelling
approaches in this study of
unfilled NR formulations
RUBBER CHEMISTRY AND TECHNOLOGY, Vol. 90, No. 2, pp. 347–366 (2017)

Additional Resources
• Rubber Compounding – Chemistry and Applications (B. Rodgers,

Ed.), New York: Marcel Dekker, 2004
• The Science and Technology of Rubber, 4th Edition (J. E. Mark, B.
Erman, and C. M. Roland, Eds.), Waltham, MA: Elsevier
Academic Press, 2013
• Basic Elastomer Technology (K.C. Baranwal and H.L. Stephens,
Eds.), Akron, OH: The Rubber Division American Chemical
Society, 2001

Testing for Durability in the
Rubber Lab

Testing for Durability in the Rubber Lab: Topics
• Critical tearing energy, TC
– Edge cracked planar tension geometry
Crack introduced
– Other tear testing methods (crack growth)
• Fatigue crack growth (FCG) testing
• Intrinsic strength/fatigue threshold, T0
• Cyclic fatigue to failure
– Using with FCG to determine crack
precursor size, c0 No initial crack
(crack nucleation)
• Simple tension stress-strain to break
(tensile test)
– Using with TC to estimate crack precursor
size, c0
Critical Tearing Energy / Strength
• Purpose:
– Determine critical tearing energy (tear strength), TC
– Establish upper limit for use in FCG testing
• Specimen:
– Edge cracked planar tension
• Strategy:
– Quasistatic, constant crosshead rate

Test Specimen
Front View Edge View
Pure Shear is another

name for Planar Tension
T=Wh
W: strain energy density
Virtues
h: sample height
•Energy Release Rate Independent of Crack Length
•Large width enables measurements of many different energy release rates
•Short gauge length enables high strain rate

Typical results
Engineering Stress, MPa
Material A
1
Material B
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Engineering Strain
Engineering Strain Energy Something

Stress at break, Engineering Density at break, Critical Tearing wrong with
Material MPa Strain at break mJ / mm^3 Energy, J/m2
A 2.97 0.61 0.943 9431. the data
B 5.43 0.47 5.120 5119. table

Trouser Tear
G.J. Lake, Rubber Chem Technol 68, 435 (1995)
TC = 2F/t
provided extension of the legs is negligible

What about Die B and Die C tear tests?
• Die B sample is nicked with a razor before testing

• Die C is not really a tear test (no initial crack)
Fatigue crack growth for rubber
log-log plot
dc  mm 
 
dN  cyc 
Endurance Limit
Crack growth rate

Ultimate Strength
mm
−8
10
Acknowledgement: Movie from Tenneco cyc
J 
T0 Tc T  2 
m 
Energy Release Rate

A closer look at crack growth:
Interesting fracture behavior beyond just an average dc/dN

Fully Relaxing Loading
T, J/m2
TC
Time, sec

Thomas Model
1.E-02
1.E-03 rc
Crack Growth Rate, m/cyc
1.E-04
1.E-05
F
1.E-06
1.E-07
F
dc  Tmax 
= rc   Tc
1.E-08
dN  Tc 
1.E-09
1.E+01 1.E+02 1.E+03 1.E+04 1.E+05
Peak Crack Driving Force, J/m 2

Fatigue Crack Growth
• Purpose
– Establish FCG rate law for fully relaxing conditions
• Specimen
– Edge cracked pure shear
• Strategy
– Fixed test time budget
– 2 hour test: ramp peak strain from zero to failure
strain, 1 replicate
– 20 hour test: ramp peak strain to start at smallest
observable crack growth rate and end at failure strain,
3 replicates

FCG Test Scheme
b f max
max
N test N
P t
1/ 
Courtesy Axel Products
c1
ci
N N
M

Loading vs. Unloading
 max
T = Wh WL =  d
 0
0
WU =

 d
max
0  max

Typical Results: crack tip evolution

Typical Results: c(N)
c =  (N ) 
 dc   −1
rj =   =  ( N j )
 dN  j
At least 0.5 mm of
crack growth is
required to establish
a reasonably
confident rate.

Crack Growth Results
F
dc  Tmax 
= rc  
dN  Tc 

Crack growth rate for rubber
▪ Typical crack growth rate

behavior of rubber on a log- dc  mm 
 
log plot versus energy release dN  cyc 
rate (tearing energy) Endurance Limit
Crack growth rate

▪ The lower bound on the
fatigue crack growth rate
curve is the Fatigue
Threshold, T0 10
mm
−8
Ultimate Strength
cyc
J 
T0 Tc T  2 
m 
Energy Release Rate

Crack growth rate for rubber
log-log plot
dc  mm 
 
dN  cyc 
Endurance Limit
Crack growth rate

Ultimate Strength
mm
−8
10
Acknowledgement: Movie from Tenneco cyc
J 
T0 Tc T  2 
m 
Energy Release Rate
For crack to grow 0.5 mm at 10
Hz frequency, it takes 2 months!

Threshold fracture (intrinsic strength) of rubber
Andrews, E. H. "Rupture propagation in hysteresial
materials: stress at a notch." Journal of the Mechanics
and Physics of Solids 11, no. 4 (1963): 231-242.
T0
H1
H 2
H 3
Lake, G. J., Thomas, A. G., Proc. Royal Soc. London. Series A 300, 108 (1967). H
Bhowmick, A. K., J. Macromol. Sci., Part C: Polym. Rev. 28, 339 (1988).
T = T0 + Tz(strain, strain rate, temp., R-ratio)

Avogadro’s number
density
bond length
T0 =
molecular weight per backbone atom
bond dissociation energy
molecular weight
chain stiffness between crosslinks

Molecular view of crack growth
Dissipation in crack tip
process zone
Polymer chains breaking

Tearing, Fatigue, Intrinsic Strength / Fatigue Threshold
Strength Test T = T0 + Tz(strain, strain rate, temp., R-ratio)

mm J J
r  10 T  50 2
+ 50000 2
cyc m m
dc  mm 
 
Fatigue Test dN  cyc 
Endurance Limit
J J
Crack growth rate

mm mm
10−9
 r  10 T  50 2 + 5000 2
cyc cyc m m
Ultimate Strength
mm
10−8
Endurance Limit cyc
J J
r =0
mm T  50 2
+ 0.0005 2
cyc m m J 
T0 Tc T  2 
m 
Energy Release Rate

The role of dissipation
Lake, G. J., Thomas, A. G., 1967

Intrinsic Strength / Fatigue Threshold
• Methods:
– Lengthy cyclic crack growth testing at low energy
release rates (takes months!)
– Cutting method
– Tear testing of rubber swollen in liquids
– Tear testing of rubber at high temperatures

Cutting Method Measurement Strategy
T = T0 + Tz(strain, strain rate, temp., R-ratio)
▪ Goal
➢ Measure tearing energy under conditions that result in
vanishingly small Tz
▪ Approach
➢ Load the crack tip directly via a sharp blade
➢ Operate at slow rates of crack growth
➢ Observe under practical conditions, extrapolate to ideal
conditions
▪ Interpretation
➢ What remains is Intrinsic Strength, T0
Lake, G. J., and O. H. Yeoh. "Measurement of rubber cutting

resistance in the absence of friction." International Journal of
Fracture 14, 509 (1978)

Energy Release Rate for Cutting
Lake, G. J., and O. H. Yeoh. "Measurement of rubber

cutting resistance in the absence of friction." International
Journal of Fracture 14, 509 (1978)
U = Wht( L − c) A = ct
V = fc
d (U − V ) d Wht ( L − c) − fc 
S 0 ,c = − =−
dA d ct 
S 0 ,c = −
− Wht − f dc = Wh + f
tdc t
Sample thickness: t S 0 ,c = T + F
Sample length: L
Crack length: c

Intrinsic Strength Analyzer (ISA)
Rubber samples tested at room temperature with

an Intrinsic Strength Analyzer (ISA)
▪ Commercial instrument developed through
partnership between Coesfeld GmbH, Germany and cutting
Endurica LLC force
▪ Operated with testing methodology based on the
approach of Lake and Yeoh* stretching force
* Lake, G. J., and O. H. Yeoh. "Measurement of rubber

cutting resistance in the absence of friction." International
Journal of Fracture 14, 509-526 (1978)

Test Control
Preconditioning Step
peak strain 0.5
strain rate 60 %/min
cycles 5
 max
mm/mm
Strain,
time, min
ri
Cutting rate,
mm/min
time, min
cutting rate schedule, per opening
strain rate proposed cut distance proposed cut time
hold hold and relax 10 min
r1 10 mm/min dx1 4 mm dt1 0.4 min
r2 0.1 mm/min dx2 0.4 mm dt2 4 min
r3 0.01 mm/min dx3 0.04 mm dt3 4 min
r end -10 mm/min dx end -1 mm dt end 0.1 min

Determine S0,c from F versus T data
For small crack tip dissipation, the intrinsic cutting energy S0,c for
cutting of rubber specimen may be written as the sum of the
F
individual energy release rates for tearing (T) and cutting (F):
S 0,c = T + F
The intrinsic strength T0 (endurance limit, fatigue threshold) is

proportional to S0,c, with a proportionality constant b that is a
function of the blade tip geometry and sharpness:
T T0 = b S 0,c
The b can be evaluated by testing a calibration material for

which T0 is known.

Example Results: Raw data for SBR
Equilibration Equilibrium Stress-Strain Curve Cutting

Example Results: Cutting energy for SBR
T0 = b S 0,c
The testing of a control
Cutting Energy, J/m2
compound with known value

of T0 (direct measurement)
S0,c=916 J/m2 can be used to determine b
Ideal frictionless which depends on blade
cutting of sharpness and geometry
unstrained
material
Crack tip bond-breaking
energy under zero blade force
S 0,c = T + F
Tearing Energy, J/m2
These measurements take a few hours, in contrast to months for

traditional crack growth testing in low energy release rate regime

Relating S0,c to T0
0.12
BR
0.1
0.08
INR
Threshold, J/m2
SBR
0.06
NR/BR
0.04
NR A T0 = 0.149 Sc
0.02 NR B
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
Cutting Energy, J/m2
Lake, G. J., and O. H. Yeoh.

"Measurement of rubber
cutting resistance in the
absence of
friction." International Journal
of Fracture 14 (1978): 509-
526.

Lake-Lindley Model for FCG
1.E-02
1.E-03 rc
Crack Growth Rate, m/cyc
1.E-04 F
F
T0 dc T 
= rc  max 
1.E-05 dN  Tc 
1.E-06 dc
= A (Tmax − To )
dN
1.E-07 Tt
rc Tt F
A= F
Tc Tc (Tt − To )
1.E-08
1.E-09
1.E+01 1.E+02 1.E+03 1.E+04 1.E+05
Equivalent Crack
Peak Driving
Crack J/m2 J/m 2
Force,Force,
Driving

Simple Tension Cyclic Fatigue to Failure
(Crack Nucleation)
• Purpose
– Provide points on the strain-life
curve for establishing typical crack
precursor size and scatter
• Specimen
– Simple tension dumbbell
• Strategy
Peak Strain
– Fully relaxing cycles
– 1 Hz
– Targeting 100 < Nf < 100000
– 5 replicates x 2 strain levels
Fatigue Life, cycles

Simple Tension Cycles to Failure
A. Ramachandran, R.P. Wietharn, S.I. Mathew, W.V. Mars, M.A. Bauman “Critical
Plane Selection Under Nonrelaxing Simple Tension with Strain Crystallization”,
Paper Presented at the Fall 192nd Technical Meeting of the Rubber Division of the
American Chemical Society, Cleveland, Ohio, October 10-12, 2017
Material with crack precursors
N=0

Material with crack precursors
N=1000

Growth of Cracks
Crack 1
5 Crack 2
Crack 3
Crack 4
Crack Length, mm
4 Crack 5
Crack 6
Crack 7
3
Crack 8
Crack Initiation Model
2
0
1.E+00 1.E+01 1.E+02 1.E+03 1.E+04 1.E+05 1.E+06
Cycles

Damage Integration
cf 1
N ( ) = 
Crack Size
dc
c0 r (T ( c ))
c0
Applied Cycles

Crack Precursor Size Calibration Example
• Simple tension specimen, homogeneously

strained away from crack
• Fully relaxing cycles
• Wmax=constant
• Thomas FCG rate law
• Initial crack size c0
• Given life Nf

Calibration Example Solution
Tmax = 2Wmax c
F
T 
r = rc  max 
 Tc 

1

1 1

1
c c F dc
N=  T 
F
dc = F 
 1  c (2Wmax c )
F
dc = 0
 2Wmax 
F
rc  max  rc   0 rc  
c0
 Tc   Tc   Tc 
1 −
1
F
  
c1− F c0
F
1
− 1

c01− F − 1− F  TcF
N= = = c1− F
 2Wmax 
F
 2Wmax 
F
( F − 1) rc ( 2Wmax ) F 0
rc   rc  
 Tc   Tc 
N is finite, even though final crack length is infinity!

Calibration Example Solution
1
 N f ( F − 1) rc ( 2Wmax ) F  1− F
c0 =  F


 Tc 

Alternative Method: computed strain life
curves overlaid with nucleation test results
10 Error (E) Minimization
2
m
 acf 1 
E =   N i −  da 
a0 r (T ( ))
i =1  c 
Peak Engineering Strain
0 i
10 microns
20 microns
30 microns
0.1
100 1000 10000 100000
Life, cycles

DeMattia Flex Fatigue Test
• Mixed deformation: Bending produces tension

on outside of specimen and compression on
inside surface
• Sometimes the sample is pierced with a needle
and crack growth is followed
• Without piercing, it is a crack nucleation test
with a complex geometry
• Cannot simply relate fatigue lifetime to crack
precursor size, strain energy density, and
fundamental crack growth properties for this
heterogenous deformation

Simple Tension: Stress and Strain to Break
(Tensile Test)
• Purpose
– Characterize stress at break (tensile strength) and
strain at break (elongation at break)
– Establish upper limit for use in crack nucleation
testing
• Specimen
– Simple tension dumbbell
• Strategy
– Quasistatic strain to break, constant strain rate
– 3 replicates

Typical Results
14
12
Engineering Stress, MPa
10
8
A, Rep 1
6 A, Rep 2
A, Rep 3
4 B, Rep 1
B, Rep 2
2
B, Rep 3
0
0 1 2 3 4
Engineering Strain
Engineering Strain Energy
Stress at break, Engineering Density at break,
Material MPa Strain at break mJ / mm^3
A 11.73 3.46 32.14
B 10.87 1.82 18.66

Get estimate of c0 from tensile test and TC
2𝜋𝑊𝑐 (for simple tension)

𝑇=
1+𝜀 M. D. Ellul, “Mechanical Fatigue” (Chapter 6) in A. N. Gent
(ed.), Engineering with Rubber , 3rd Ed., Hanser 2012
Estimate W from stress at break (b) and strain at break (b) : W  ½ b b

(make sure to divide b by 100 if expressed as %)
𝑇𝐶 1 + 𝜀𝑏
𝑐0 ≈
𝜋𝜎𝑏 𝜀𝑏
Ratio of properties: [with crack introduced] / [no crack introduced]
Could be useful for monitoring mixing quality in the plant
Note: This crack precursor size is an estimate and is typically larger using this
approach compared to c0 from crack nucleation in fatigue-to-failure tests

Exercise 1: Comparing tensile strengths and
estimating c0 for two compounds
• 5 specimens each of Compound A and Compound B were tested in a
simple tension stress-strain to break test [data sheets handed out]
• Determine which compound has the best average tensile strength (b)
– Are there any outlier datapoints that confuse the comparison?
• Here are the average values of critical tearing energy for the two
materials measured in a edge cracked planar tension test:
– Compound A: TC = 18.5 kJ/m2
– Compound B: TC = 13.1 kJ/m2
• Estimate crack precursor sizes (c0)
– Compound A: _________ mm
– Compound B: _________ mm

A few words on sampling volume
(size and number of test specimens)
Typical cured rubber sheet used for lab testing (150 mm x 150 mm x 1 to 2 mm thick)
 2
1
5
4
1 2 3 4 5

Largest crack precursors shown schematically

A few words on sampling volume
(size and number of test specimens)

Tensile Strength and Crack Precursor Size Distributions:
Compound A versus Compound B
25 total tensile test specimens for each compound
(includes 5 groups of 5 specimens you separately considered in Exercise 1)
Compound A: Compound B:
b = 22.6 ± 5.6 MPa b = 22.9 ± 3.3 MPa
b = 4.41 ± 1.05 b = 4.58 ± 0.71
Measured in tear test: Measured in tear test:
TC = 18.5 kJ/m2 TC = 13.1 kJ/m2
Calculated: Calculated:
c0 = 0.161 ± 0.074 mm c0 = 0.099 ± 0.026 mm
16 10
Compound A
9
14 Compound A
8
12 Compound B Compound B
7
10 6
Count
Count
8 5
4
6
3
4 2
2 1
0
0
60 80 100 120 140 160 180 200 220 240 260 280 300 320 340
10 to 15 15 to 20 20 to 25 25 to 30 30 to 35
to to to to to to to to to to to to to to to
Tensile Strength, b (MPa) 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360
Crack Precursor Size, c 0 (m)
Tensile Strength and Crack Precursor Size Distributions:
Compound A versus Compound B
25 total tensile test specimens for each compound
(includes 5 groups of 5 specimens you separately considered in Exercise 1)
Compound A: Compound B:
b = 22.6 ± 5.6 MPa b = 22.9 ± 3.3 MPa
b = 4.41 ± 1.05 b = 4.58 ± 0.71
Measured in tear test: Measured in tear test:
TC = 18.5 kJ/m2 TC = 13.1 kJ/m2
Calculated: Calculated:
c0 = 0.161 ± 0.074 mm c0 = 0.099 ± 0.026 mm
100 100
Compound A Compound A
Cummulative Distribution (%)
Cummulative Distribution (%)

80 Compound B 80 Compound B
60 60
40 40
20 20
0 0
5 10 15 20 25 30 35 0 0.1 0.2 0.3 0.4
Tensile Strength, b (MPa) Crack Precursor Size, c 0 (mm)

Testing for Durability in the Rubber Lab
• Need to characterize both of these situations for

effective testing of durability in the rubber lab
– No initial crack (crack nucleation)
• Simple tension stress-strain to break (tensile test)
• Cyclic fatigue to failure
– A crack is intentionally introduced (crack growth)
• Fatigue crack growth testing
• Critical tearing energy, TC
• Intrinsic strength/fatigue threshold, T0

Further Reading
• W. V Mars, Fatigue life prediction for elastomer

structures, Rubber Chem. Technol. 80, 481 (2007).
• G.J. Lake, Rubber Chem. Technol. 68, 435 (1995)
• A. K. Bhowmick, J. Macromol. Sci., Part C: Polym.
Rev. 28, 339 (1988).

Framework for Compounding
for Durability

Key Components of Elastomer Fatigue and Fracture
aging affects these
crack precursors crack drivers crack growth
log [dc/dN (mm/cycle)]

Stress A
control
B

log [T (J/m2)]
c0 W T0 TC F rC
simplify
T0 TC

Crack Growth Behavior for CB-Filled NR and BR Compounds
1E-1
NR
1E-2 BR
Crack Growth Rate, dc/dn [mm/cycle]
1E-3
1E-4
1E-5
1E-6
Thomas Law Parameters
Fit Fit Measured
1E-7
Compound F rC TC
2
(mm/cycle) (kJ/m )
1E-8 Crack growth data from:
NR 1.95 0.00193 18.49 Coesfeld Tear & Fatigue Analyser
BR 5.23 0.24770 3.27
1E-9
10 100 1000 10000 100000
Tearing Energy, T [J/m2]
T0 and TC data from:

Coesfeld Intrinsic Strength Analyser

Using T0 and TC for Simplified Picture of Crack Growth Behavior
1E-1
NR
1E-2 BR 10-2
NR from To and Tc
1E-3 BR from To and Tc
1E-4 Fit Fit Measured

Compound F rC TC
2
(mm/cycle) (kJ/m )
1E-5 NR 1.95 0.00193 18.49
BR 5.23 0.24770 3.27
1E-6 Measured Measured Calculated
Compound TC T0 F
1E-7 (kJ/m2) (kJ/m2) [F = log(rC/r0)/log(TC/T0)]
NR 18.49 0.0506 2.34
BR 3.27 0.0997 3.96
1E-8 10-8
rC fixed at 10-2 mm/cycle
r0 fixed at 10-8 mm/cycle
1E-9
10 100 1000 10000 100000

1E-1
NR
1E-2 BR 10-2 Actual ultimate tearing and
NR from To and Tc intrinsic strength threshold may

occur at other crack growth rates
1E-3 BR from To and Tc
However, the crack growth rate
1E-4 assignments of 10-2 and 10-8
mm/cycle work due to curved
1E-5 transitions toward TC and T0
1E-6
1E-7
1E-8 10-8
1E-9
10 100 1000 10000 100000

𝑟
log 𝑟𝐶 6
0
𝐹≈ ≈
𝑇 𝑇
log 𝐶 log 𝐶
𝑇0 𝑇0
rC  10-2 mm/cycle (constant)

r0  10-8 mm/cycle (constant)
• The slope of the crack growth

rate curve (F) is linked to TC and T0
• This simplified approach to
representing crack growth Various rubber compounds from our database
behavior based on T0 and TC is
very useful for guiding rubber
formulation changes to improve
durability

𝑟
log 𝑟𝐶 6
0
𝐹≈ ≈ crack growth
𝑇𝐶 𝑇
log 𝑇 log 𝑇𝐶
0 0

rC  10-2 mm/cycle (constant)
r0  10-8 mm/cycle (constant)
• The slope of the crack growth rate

curve (F) is linked to TC and T0 log [T (J/m2)]
• This simplified approach to T0 TC F rC

representing crack growth behavior
simplify
based on T0 and TC is very useful for
guiding rubber formulation changes T0 TC
to improve durability

thumbnail full resolution

image image
• This simplified approach to representing crack growth behavior based on T0 and TC

is very useful for guiding rubber formulation changes to improve durability
• However, it must be remembered that this is a “thumbnail” representation, and
fatigue crack growth testing is needed for quantitative predictions of durability

Key Components of Elastomer Fatigue and Fracture
aging affects these
crack precursors crack drivers crack growth


Stress A
control
B

log [T (J/m2)]
c0 W T0 TC
How do rubber formulation ingredients impact each?

▪ Polymer selection
▪ Crosslinking effects
▪ Filler reinforcement
▪ Influence of oils, plasticizers, and resins
▪ Stabilizing against aging

Polymer Selection

Polymer Selection
• Chemical structure (microstructure)
– Thermal and oxidative stability
– Structure effects on T0
– Influence of Tg and related hysteresis on TC
– Strain-induced crystallization
• Molecular weight and branching (macrostructure)
• Contaminants
• Polymer blends

Thermal and Oxidative Stability
B. Stuck and N. Hershberger, “Effect of Different Nitrile Elastomers in Down

Hole Drilling Applications With a Review of Testing and Failure Analysis”,
Presented at the Fall 184th Technical Meeting of the Rubber Division, ACS, http://www.dupontelastomers.com/autofocus/a3/chooseRight.html
October 8, 2013

Thermal and Oxidative Stability
C=C bonds: many some some few none many none none many none none none many
* Hard domains melt/soften

in polyurethanes
• Double bonds in the chemical structure are unstable

B. Stuck and N. Hershberger, “Effect of Different Nitrile Elastomers in Down Hole Drilling Applications With a Review of Testing and Failure Analysis”,
Presented at the Fall 184th Technical Meeting of the Rubber Division, ACS, October 8, 2013

Hydrogenation of Unsaturated Elastomers to Improve Thermal Stability
NBR
HNBR
Y. Liu at al.,“Hydrogenation of acrylonitrile–butadiene copolymer latex using

water-soluble rhodium catalysts”, Catal. Sci. Technol. 3, 2689 (2013)

Threshold fracture (intrinsic strength) of rubber, T0
Lake, G. J., Thomas, A. G., Proc. Royal Soc. London. Series A 300, 108 (1967).
Avogadro’s number
density
bond length
T0 =
molecular weight

Threshold fracture (intrinsic strength) of rubber, T0
increasing M0
increasing M0
log T0
log T0
g10
T0 =
AN Gent, “The Influence of Chemical Structure on the Strength of Rubber," in Elastomers and Rubber Elasticity, ed. by J. E. Mark and J. Lal,
Plenum Press, New York, 1986, pp. 253-267."

Molecular Weight Per Backbone Bond: Some Examples
Polydimethyl
Natural Rubber (NR)
siloxane (PDMS) FKM
Synthetic Polyisoprene (IR)
(silicone rubber) M0 = 53.5 g/mol
M0 = 17 g/mol
M0 = 37 g/mol
Polybutadiene (BR) n m
M0 = 13.5 g/mol
Nitrile Rubber (NBR)
M0 depends on AN content
M0 = 18.7 g/mol, for 40 wt.% AN

Effect of Temperature on TC

Effect of Tuse– Tg on Tear Strength
AN Gent, “The Influence of Chemical Structure on the Strength of Rubber," in Elastomers and Rubber Elasticity, ed. by J. E. Mark
and J. Lal, Plenum Press, New York, 1986, pp. 253-267."

Tg Values for Various Elastomers
Appendix of:
A.N. Gent, “Engineering with Rubber –
How to Design Rubber Components”, 3rd
Edition, Carl Hanser Verlag, Munich 2012
Solution Styrene-Butadiene Rubber
http://www.valvemagazine.com/web-only/categories/technical-topics/7131-low-
temperature-sealing-with-elastomers-in-sour-gas.html

Effect of Tuse–Tg on Tear Strength
B. Stuck and N. Hershberger, “Effect of Different Nitrile Elastomers

in Down Hole Drilling Applications With a Review of Testing and
Failure Analysis”, Presented at the Fall 184th Technical Meeting of
the Rubber Division, ACS, October 8, 2013
http://www.ramcharan.org/pdf/NBR.pdf

Effect of Tuse–Tg on Crack Growth
Unfilled SBR
J Zhao and GN Ghebremeskel, Rubber Chem Technol 74, 409 (2001)

Effect of Temperature on Tc
For a given elastomer For a given use temp.
TC TC
Increasing Temp.

(Distance above Tg) Increase Tg

of Elastomer
T0 T0
Depends
on
Chemical
Structure
log [T (J/m2)] log [T (J/m2)]

Strain-Induced Crystallization
M. Tosaka, S. Kohjiya, S. Murakami, S. Poompradub, Y. Ikeda, S. Toki, I. Sics, and

B. S. Hsiao, RUBBER CHEM.
TECHNOL. 77, 711 (2004).

increasing
crosslink
density
W. Sainumsai, S. Toki et al. Rubber Chem

Technol 90, 728 (2017)

Crystallization Under Dynamic Load
NR with 40 phr N234 CB
Edge crack region of planar tension sample
70% strain shown in image below (cyclic deformation)
Strain-induced crystallization in crack tip region

Red: WAXD pattern from crystallinity
Black: Purely amorphous region
Reproduced with
permission of K. Bruning
Brüning, Karsten, Konrad Schneider, Stephan V. Roth, and Gert Heinrich. "Kinetics of
strain-induced crystallization in natural rubber studied by WAXD: dynamic and impact
tensile experiments." Macromolecules 45, no. 19 (2012): 7914-7919.
▪ The movie shows an edge crack
region in NR reinforced with 40 phr of
N234 carbon black that is
experiencing cyclic deformation from
0% to 70% planar tension at a
frequency of 1 Hz.
Reproduced with
permission of K. Bruning
▪ Each pixel at each time in the video
represents a wide-angle X-ray
diffraction pattern collected in real
time while stretching in a synchrotron
X-ray beam, with red color used to
indicate crystallinity and black for
purely amorphous regions.
▪ You can see the crystals form during
stretching which self-reinforces the
K. Brüning, K. Schneider, S. V. Roth, and G. Heinrich, “Strain-induced rubber at the crack tip region to resist
crystallization around a crack tip in natural rubber under dynamic load”,
Polymer 54, 6200 (2013) further growth of the crack.

AN Gent, “The Influence of Chemical Structure on the Strength of Rubber," in

Elastomers and Rubber Elasticity, ed. by J. E. Mark and J. Lal,
Plenum Press, New York, 1986, pp. 253-267."

How can crystallization occur at temperatures above the normal melting
temperature (Tm  30 °C for NR)?
G = H - TS 𝐻𝑙−𝑐
𝑇𝑚 =
For phase change: G  0 𝑆𝑙−𝑐
Sliquid - Scrystal
Without deformation, many ways of

arranging the chain coil between the two
ends (high entropy)
When stretched, there are fewer ways of

arranging the chain between the two ends;
only one conformation is possible in the
limit of full orientation (low entropy)
Stretching (orienting) polymers increases the melting temperature!

P. J. Flory, “Thermodynamics of crystallization in high polymers. I. Crystallization induced by stretching”,
Journal of Chemical Physics 15, 397 (1947).

http://endurica.com/strain-induced-crystallization-in-high-cis-butadiene-rubber-fact-or-fiction/



Strain-Induced Crystallization (SIC)
TC
log [dc/dN (mm/cycle)] increase
extent of SIC
T0
log [T (J/m2)]

Molecular Weight
12 chains with molecular weight M 3 chains with molecular weight 4M
(24 chain ends) (6 chain ends)
Same
crosslink
density
Ineffective
network
chain segments
at ends
(act as “diluents”
which reduce
stiffness)

Molecular Weight
J Zhao and GN Ghebremeskel, “A Review of Some

of the Factors Affecting Fracture and Fatigue in
SBR and BR Vulcanizates”, Rubber Chem.
Technol. 74, 409 (2001)
Mode of Control Effect

Modulus
same amount
of curatives
Molecular Weight

Molecular Weight
SBR compounds SBR gum polymers
Tensile Strength

Contaminants as Crack Precursors
GRADES OF TECHNICALLY SPECIFIED RUBBER (TSR)
The TSR grades most widely used by the tire and rubber industry are the TSR-20 and TSR-10 grades. TSR-20
products from Indonesia, Thailand and Malaysia are known as SIR20, STR20 and SMR20, respectively.
http://www.natural-rubber.com/tsr.php
ISO 249:2016
Rubber, raw natural -- Determination of dirt content
Sieve, of nominal size of openings 44 - 45 µm (325 mesh) of corrosion-resistant wire
gauze, preferably stainless steel, complying with ISO 565
Size of dirt in natural rubber: > 45 m (0.045 mm)

Exercise 2: Contaminants as Crack Precursors
• For a TSR 10 grade of natural rubber with maximum allowable
level of dirt (0.08 wt.%), how many dirt particles would be inside
a standard tensile sheet used for testing in the rubber lab?
– Assume NR is the only ingredient in the formulation such that the sheet is
all NR
– Density of NR: 0.93 g/cm3
– Tensile sheet has dimensions: 15 cm x 15 cm x 0.15 cm
– Assume spherical dirt particles with density of 2.65 g/cm3 (e.g. sand
particle (quartz))
– Perform the calculations for two different values of dirt particle diameter:
• 50 m (0.05 mm) Number of dirt particles per sheet: _________
• 500 m (0.5 mm) Number of dirt particles per sheet: _________

Polymer Blends
Phase-Separated
Blend Morphology
• Miscible blends of polymers
are rare due to mixing
entropy limitations for long BR
chains (Flory Huggins theory NR
of polymer blend
thermodynamics)
• Most elastomer blends have
5 µm
phase-separated domains of
the separate polymers and
exhibit two glass transition
temperatures
(a) Inoue, Y., Iwasa, M., and Yoshida, H.,
Netsu Sokutei 39, 41 (2012).

Polymer Blends
D Klat, A Kępas-Suwara, J Lacayo-Pineda, and S Cook, MORPHOLOGY AND NANOMECHANICAL CHARACTERISTICS OF

NR/SBR BLENDS. Rubber Chem Technol 91, 151 (2018).

Polymer Blends
S. Datta, “Elastomer Blends” (Chapter 12) in Science and Technology of Rubber
• IIR and CIIR are nearly identical in structure (chlorination only 1 to 2 % in CIIR), so they
are miscible
• The only other miscible combination is BR and SBR (and that only occurs for high cis
BR and SBR with low to medium styrene contents)
• Mixing less polar (less oil resistant) elastomer with more polar (more oil resistant)
elastomer results in larger phase separated domain sizes that can be crack precursors

Polymer Blends
S. Datta, “Elastomer Blends” (Chapter 12) in

Science and Technology of Rubber
NR/SBR blends NR/NBR blends

Polymer Blends
1E-1
NR
1E-2 BR
1E-3
1E-4
1E-5
1E-6
1E-7
50 phr N339 CB
1E-8 50 phr N330 CB
1E-9
10 100 1000 10000 100000
Tearing Energy, T[J/m2]
Matthias Wunde and Manfred Klüppel (2016) INFLUENCE OF
CG Robertson, JD Suter, MA Bauman, R Stoček, and WV Mars,
PHASE MORPHOLOGY AND FILLER DISTRIBUTION IN
“Finite Element Modeling and Critical Plane Analysis of a Cut NR/BR AND NR/SBR BLENDS ON FRACTURE
and Chip Experiment for Rubber”, Presented at the Spring 193rd MECHANICAL PROPERTIES. Rubber Chemistry and
Technical Meeting of the Rubber Division, ACS, May 8-10, 2018 Technology: December 2016, Vol. 89, No. 4, pp. 588-607.

Polymer Blends
unfilled
50 phr N339 CB
50 phr N339 CB
Matthias Wunde and Manfred Klüppel (2016) INFLUENCE OF PHASE MORPHOLOGY AND FILLER DISTRIBUTION IN NR/BR AND NR/SBR BLENDS
ON FRACTURE MECHANICAL PROPERTIES. Rubber Chemistry and Technology: December 2016, Vol. 89, No. 4, pp. 588-607.
• Filler distribution among the phase-separated elastomer domains is also important

Summary
• Double bonds in the chemical structure are not good for thermal and
oxidative stability (aging)
– Hydrogenation converts double bonds to fully saturated bonds to yield elastomer
grades with improved stability, but then other crosslinking methods are needed
• Selecting a strain-crystallizing elastomer is one of the best ways to
improve resistance to fatigue and fracture of rubber compounds, but
there are only a few choices available: NR > IR, CR > BR (high cis)
• An elastomer with a higher glass transition temperature is preferred
when possible due to greater hysteresis which improves TC
TC TC

increase
Increase Tg
extent
Of Elastomer
of SIC
T0
T0
Depends
on
Chemical
Structure
log [T (J/m2)]
log [T (J/m2)]
Summary (continued)
• Intrinsic strength is affected by molecular characteristics of the
polymer repeat unit, especially molecular weight per backbone
bond (M0), with lower M0 giving higher T0
• For best durability, the highest possible polymer molecular
weights should be used that do not cause processing issues
• Contaminants in elastomers – such as dirt content in NR – can be
crack precursors
• Most elastomer blends are immiscible systems, so attention
must be paid to reduce characteristic sizes of phase-separated
domains which can be crack precursors
– Do not combine widely dissimilar polymers (i.e. non-polar
with polar)
– Use more intensive mixing processes

Crosslinking Effects

Crosslinking Effects
• Influence of crosslink density on intrinsic
strength / fatigue threshold (T0)
• Influence of crosslink density on critical
tearing energy (TC)
• Crosslink type effects
• Effect on strain-induced crystallization
• Dispersion of curatives and effect on c0
• Unconventional rubber networks
– Bimodal networks
– Double networks

Threshold fracture (intrinsic strength) of rubber
bond length
T0 =
molecular weight of repeat unit
molecular weight
chain stiffness
between crosslinks

Influence of Crosslink Density on T0
T0 = KM 1/ 2
c
Remember:
Crosslink density
inversely related to Mc
1/2
Anil K. Bhowmick (1988): Threshold Fracture of

Elastomers, Journal of Macromolecular Science,
Part C: Polymer Reviews, 28:3-4, 339-370

Influence of Crosslink Density on T0
Be careful: This is a crosslink

density effect, not a
universal modulus effect!
The opposite is seen when

-1/2 filler particle loading is used
to increase modulus (to be
discussed later in Filler
Reinforcement lecture)

Part C: Polymer Reviews, 28:3-4, 339-370

Effects of Crosslink Density on Properties
The Science and Technology of Rubber; Mark, J.E., Erman, B., Eirich F.R., Ed.; Elsevier: New York, 2005

Crosslink Density and Ineffective Network Chains
less crosslinking more crosslinking
ineffective network
chains (dangling ends)
Mc: average molecular weight between crosslinks

: crosslink density (number of crosslinks per volume)
Mc  1/ 
The role of dissipation
Adding more
crosslinks reduces
the mobility and
related hysteresis of
the polymer chains
Lake, G. J., Thomas, A. G., 1967

Connectivity / Integrity
Effect of Crosslink Density on TC
Energy Dissipation
Tear Strength
Network
Crosslink Crosslink Crosslink

Density Density Density

Influence of crosslink density on TC
Peroxide cured
SBR (unfilled)
Tear Strength
Crosslink
Density

Effect of Crosslink Density on Tensile Strength
25
20
Stress (MPa)
15
10
1.4 phr sulfur
1.6 phr sulfur
5 1.8 phr sulfur
N.P. Warasitthinon and C.G. Robertson,
2.2 phr sulfur
0 Rubber Chem. Technol., Online First (2018),
doi:10.5254/rct.18.82608
0 100 200 300 400 500 600
Strain (%)

Common Types of Crosslinking in Rubber
• Sulfur Vulcanization
• Peroxide Curing
• Phenolic Resin Curing
• Metal Oxide Curing

Sulfur Vulcanization
Accelerated sulfur vulcanization is suitable for unsaturated rubbers with available
C=C double bonds:
Polybutadiene (BR)
Natural Rubber (NR) m

n
Synthetic Polyisoprene (IR) Nitrile Rubber (NBR) statistical copolymer
CH2 CH CH CH2 CH CH2

n 0.3n
n 0.02 n Styrene Butadiene Rubber (SBR)

Butyl Rubber (IIR) [statistical copolymer]
CH3
CH2 CH2 CH CH2 CH CH

x y z
Ethylene Propylene Diene

Rubber (EPDM) H
C
© 2018 Endurica LLC CH3 6-13

Sulfur Crosslink Types
and Chain Modification
High sulfur to
accelerator ratio
Low sulfur to
accelerator ratio
The Science and Technology of Rubber; Mark, J.E., Erman, B., Eirich F.R., Ed.; Elsevier: New York, 2005

Types of Sulfur Crosslinking Systems in NR
Conventional Semi-efficient Efficient
Vulcanization Vulcanization Vulcanization
Ingredients
Sulfur, phr 2.5 1.2 0.33
CBS accelerator, phr 0.5 1.8 3.00
TMTD accelerator, phr 0.0 0.06 2.00
Accelerator to sulfur ratio: low medium high

Crosslink type(s): polysulfidic mixture monosulfidic
Properties
Mooney scorch time
t₅ at 120˚C, min 18.5 16 8
Fatigue life, KC 162 120 50
Compression set, % 31 18 15
John G. Sommer, “Engineered Rubber Products”, Hanser, 2009

Effect of Accelerator to Sulfur Ratio in NR
% Monosulfidic Cross-links
The Science and Technology of Rubber; Mark, J.E., Erman, B., Eirich
F.R., Ed.; Elsevier: New York, 2005

Effect of Cure Temperature on Sulfur Rank

Selected Accelerated Sulfur System Recipes
for Unsaturated Elastomers
The Science and Technology of Rubber; Mark, J.E., Erman, B., Eirich F.R., Ed.; Elsevier: New York, 2005.

Peroxide Curing
• Peroxide curing is popular with saturated elastomers
such as:
• Silicone rubber
• Hydrogenated nitrile rubber
• Ethylene propylene rubber
• Peroxide curing creates a C – C bond
• Phenolic resins also create a C – C bond

Metal Oxide Curing
Commonly used on rubber containing:
Active chlorine species as in halobutyl rubber and
neoprene rubber (polychloroprene, CR)
Cl Cl
CH2 C CH CH2 CH2 C

m 0.015m
CH
Neoprene rubber CH2

Metal Oxide Curing
Details:
1. Allylic chlorine moiety is quite active to react with metal oxide,
like ZnO.
However, ZnO is quite scorchy because the generated zinc

chloride (ZnCI₂) is a very strong catalyst.
2. To moderate the cure, magnesium oxide (MgO) is added. MgO

reacts with the generating zinc chloride.
ZnCI₂ + MgO ZnO + MgCI₂

Metal Oxide Curing
Cl
ZnO
CH2 C CH2 C
CH CH
CH2
CH2
OZnCl
Results in C-0-C Crosslink

CH2 C
CH
CH2
ZnCl2 + O
CH2
ZnCl2 + MgO ZnO + MgCl2
CH
The Science and Technology of Rubber; Mark, J.E., Erman,
B., Eirich F.R., Ed.; Elsevier: New York, 2005 CH2 C
Bond Strengths for Different Crosslink Types
• The stability of the crosslink depends on the bond dissociation
energy (kJ/mol) which is required to break the covalent bond.
Type of
Dissociation
Bond Crosslinking
energy (kJ/mol)
System
peroxide;
–C–C 335
phenolic resin
–C–O–C 358 metal oxide
–C–S–C 310
–C–S–S–C 226 sulfur
– C – S – Sn – S – C 142

Labile Crosslinks

Types of Sulfur Crosslinking Systems in NR
Conventional Semi-efficient Efficient
Vulcanization Vulcanization Vulcanization
Ingredients
Sulfur, phr 2.5 1.2 0.33
CBS accelerator, phr 0.5 1.8 3.00
TMTD accelerator, phr 0.0 0.06 2.00
Accelerator to sulfur ratio: low medium high

Crosslink type(s): polysulfidic mixture monosulfidic
Properties
Mooney scorch time
t₅ at 120˚C, min 18.5 16 8
Fatigue life, KC 162 120 50
Compression set, % 31 18 15
John G. Sommer, “Engineered Rubber Products”, Hanser, 2009

Role of Zinc Oxide in Vulcanization
Zinc oxide + stearic acid zinc stearate + water
ZnO + CH₃ – (CH₂)₁₆ – COOH (CH₃ –(CH₂)₁₆ – COO)₂Zn + H₂O
ZnO is insoluble
Zn++ salt becomes soluble in the rubber and available for

reaction (activator for sulfur vulcanization)
Only a fraction of the ZnO added to the rubber reacts with

stearic acid (big ZnO particles; do not soften/melt; etc.)

Crack Precursor Origins
zinc
oxide
zinc oxide
Influence of the formulation on the fatigue properties

of industrial elastomers, I. Masquelier, Ph.D. thesis,
University of West Bretagne , France, 3 Dec 2014
B. Huneau, I. Masquelier et al. Rubber

Chemistry and Technology: March 2016,
Vol. 89, No. 1, pp. 126-141

Zinc Oxide as Crack Precursors
• Zinc oxide particles are quite large compared to the reinforcing
fillers used (CB, silica, etc.)
– Major source of crack precursors in rubber
• Finer grades are available (“nano” zinc oxide), but are more
expensive
• The end goal is to generate zinc stearate for use as cure activator
– To reduce number and size of crack precursors, why not add
zinc stearate instead of zinc oxide + stearic acid?
– The in-situ reaction of large zinc particles (low surface area)
with excess stearic acid during rubber compounding is very
inefficient, so do not add too much direct zinc stearate if you
try this idea to improve rubber fatigue properties

Effect on Strain-Induced Crystallization
• Onset strain for SIC not significantly

affected by crosslink density or sulfur
rank in this study for unfilled NR
W. Sainumsai, S. Toki et al.

Effect on Strain-Induced Crystallization
• An increase in
crosslink density
reduces total %
crystallinity and
reduces size of
crystallites
increasing
crosslink
density
B. Huneau, Rubber Chem. Technol. 84, 425 (2011).

S. Trabelsi, P. A. Albouy, and J. Rault, Macromolecules 36, 7624 (2003).

Dispersion of curatives and effect on c0
• Accelerator particles that do
not melt during mixing
become crack precursors
that reduce tensile strength
and fatigue lifetime
• For the final (productive)
mixing batch, maximum
temperatures are 100°C to
110°C in most compounding
processes, but temperatures
(size of particles added to mixer) can be even lower for mill
mixing of curatives into
rubber
Oil extended E-SBR filled with 40 phr N330 CB
Range of particle sizes achieved from sieving of unmilled accelerators
F. Ignatz-Hoover and B.H. To, “Effective Curative Dispersion for Uniform Mechanical
Properties”, Paper Presented at the Fall 178th Technical Meeting of the Rubber Division
of the American Chemical Society, Milwaukee, WI, October 12-14, 2010

Bimodal Networks
S. J. Garcia, European Polymer Journal 53, 118 (2014)

Bimodal Networks

Double Networks

Double Networks
Benefit is lower for rubber which
cannot strain crystallize
Rubber Chem Technol 76 892 2003

Exercise 3: Double Networks
• Think about your rubber
application in terms of double
networks
– Are there opportunities to
introduce double networks for
enhanced durability?
– Given the processing steps in
making your product, is it possible
that double networks are being
created unintentionally?
• Please keep these thoughts to
explore later within your
company.

Summary of Crosslinking Effects
• Adding crosslinks reduces T0
TC
• TC goes through a maximum with crosslink

density
– Competing effects of lower number of
ineffective network chains and reduced T0
viscoelastic energy losses at crack tip zone as
more crosslinks are added increase crosslinking
• Poorly dispersed curatives can become crack log [T (J/m2)]
precursors
– Keep in mind melting points of accelerators
– Beware of zinc oxide which is a significant
source of crack precursors, and consider using
zinc stearate or finer ZnO grades
• Labile crosslinks that can break and reform (like
polysulfidic linkages) are preferred for durability
• Unconventional elastomer networks – such as
double networks – provide opportunity for
innovative product development

Filler Reinforcement

Filler Reinforcement Topics
• Stiffness and crack driving force (W)
• Effect on strain-induced crystallization
• Intrinsic strength, T0
• Influence on energy dissipation (hysteresis)
and related critical tearing energy, TC
• Crack blunting
• Undispersed filler agglomerates as crack
precursors

Typical particles used in the rubber industry
d = primary particle diameter
D = aggregate diameter
S = surface area
C. G. Robertson, “Dynamic Mechanical Properties”, Section 3: Rubbers and Elastomers, in Encyclopedia of Polymeric
Nanomaterials (eds. S. Kobayashi and K. Müllen), Berlin: Springer-Verlag Berlin Heidelberg, 2015.
• The typical carbon black and silica particles that are used industrially to reinforce rubber
are nanometer sized
• The particles are agglomerated within the filler granules/beads/powders used in rubber
compounding, and effective mixing must break-up agglomerates and disperse the filler to
get the full reinforcing potential
• The typical filler volume fractions used in the rubber industry lead to filler networks
(jammed / percolated structures)
Effect of Particle Size and Volume Fraction on Stiffness and W
Guth equation:
10
8
6
G/G0
SAF
4
Guth fit
2
0
0 0.1 0.2 0.3 0.4 CB Grade CB Grade
Strain
old name new name f
MT N990 2.4
FT N880 3.8
HAF N330 7.1
10
8 ISAF N220 9.3
FT
6 SAF N110 11.9
G/G0
Guth fit
4
2
PT (?) PT (?) 17.8
0 Fitting results for f are from Lewis Tunnicliffe
0 0.1 0.2 0.3 0.4 at Birla Carbon (private communication)
Strain
Y Fukahori, AA Hon, V Jha, and JJC Busfield, Rubber Chem Technol 86, 218 (2013)
• Adding reinforcing filler particles increases stiffness and crack driving force (W)
– Is increased stiffness better or worse for durability? This depends on the
mode of control in the application which will be discussed in a later lecture

Effect of Filler on Strain-Induced Crystallization
• Adding reinforcing filler particles increases the local strain within

the elastomer, and this can be expressed using the strain
amplification factor, X
𝑃𝑜𝑙𝑦𝑚𝑒𝑟 𝑆𝑡𝑟𝑎𝑖𝑛 𝑖𝑛 𝐹𝑖𝑙𝑙𝑒𝑑
=𝑋=
𝑃𝑜𝑙𝑦𝑚𝑒𝑟 𝑆𝑡𝑟𝑎𝑖𝑛 𝑖𝑛 𝑈𝑛𝑓𝑖𝑙𝑙𝑒𝑑
• The higher local strain promotes more strain-induced

crystallization which improves durability
𝐻𝑙−𝑐 Stretching (orienting) the polymer chains

𝑇𝑚 = increases the melting temperature
𝑆𝑙−𝑐
Sliquid - Scrystal

Effect of Filler Loading on
Crystallization at Crack Tip
D. J. Lee and J. A. Donovan (1987) Microstructural Changes in the Crack Tip Region of Carbon-Black-Filled
Natural Rubber. Rubber Chemistry and Technology: November 1987, Vol. 60, No. 5, pp. 910-923.

Effect of Filler on Intrinsic Strength of Rubber, T0
What happens when

filler particles are
introduced?
Avogadro’s number
density
bond length
T0 =
molecular weight

T0 =
Possible Scenarios
• Extra force needed to • Polymer chains • Crack blunting by filler
slide and desorb covalently attached – Crack has a more
polymer chains away to filler surfaces (e.g. tortuous path
from surfaces (e.g. chain rubber-silane-silica which effectively
segments adsorbed onto system) increases the
carbon black) – Bonds act to apparent T0
– Adding filler reduce MC which
increases T0 reduces T0

Possible Scenarios
• Extra force needed to slide • Polymer chains covalently • Crack blunting by filler
and desorb polymer chains attached to filler surfaces – Crack has a more
away from surface (e.g. (e.g. rubber-silane-silica tortuous path which
chain segments adsorbed system) effectively increases
onto carbon black) – Bonds act to reduce the apparent T0
– Adding filler increases MC which reduces T0
T0
Bhowmick, A. K., J. Macromol. Sci., Part C: Polym. Rev. 28, 339 (1988). T0 increased by CB
Unfilled Rubber

Endurica unpublished results from Intrinsic Strength Analyser

Possible Scenarios
• Extra force needed to slide • Polymer chains covalently • Crack blunting by filler
and desorb polymer chains attached to filler surfaces – Crack has a more
away from surfaces (e.g. (e.g. rubber-silane-silica tortuous path which
chain segments adsorbed system) effectively increases
onto carbon black) – Bonds act to reduce the apparent T0
– Adding filler increases MC which reduces T0
T0
T0 decreased by Silica-Silane?
M. Kluppel, Macromol. Mater.

Eng. 294, 130 (2009)

Effect of Filler Loading on Hysteresis
Increasing :
• Increases stiffness
• Gives bigger area
N550 filled NBR between increasing and
stress-strain decreasing stress-strain
loops in
compression loops
– This is from increased
filler-related viscoelastic
hysteresis
– Improves tear strength, TC
W E Mahmoud et al. “The mechanical behaviour of NBR/FEF under
compressive cyclic stress–strain” J. Phys. D: Appl. Phys. 39, 2427 (2006)

Effect of Filler Loading on Hysteresis
• Increasing  gives higher
tan due to more extensive
filler networking
• Similar effect noted when
reducing particle size (e.g.
N550 to N330 to N110 CB)
at constant filler volume
fraction
 = 0.268
0.216 Filler Particle Network
0.186
0.155
CB
aggregates
N.P. Warasitthinon and C.G. Robertson, Rubber Chem. Technol., Online First (2018),
doi:10.5254/rct.18.82608

Effect of Carbon Black on Crack Growth Curve for Various Rubbers
Gum
Filled with 50 phr N330
carbon black (fine)
N
da/d
+ Filled with 50 phr N990
carbon black (coarse)
TC
add filler
T0
log [T (J/m2)]
Lake & Lindley, Rubber J., 146 (10), 24 (1964)

Effect of Filler on Crack Growth Curve for SBR
TC M. Kluppel, Macromol. Mater. Eng. 294, 130 (2009)
Add CB
T0
log [T (J/m2)]
TC
Add Silica-Silane
Si69 silane
T0
?
log [T (J/m2)]

Crack Blunting
• Small amount of nanodispersed
clay improved fatigue life of CB-
filled SBR due to proposed crack
blunting mechanism
Y.-P. Wu, W. Zhao, L.-Q. Zhang, Macromol. Mater. Eng. 291,
944 (2006)
Also possibly crack blunting:

• Silica (often without silane!) is commonly added in small
amounts – in addition to main CB filler – in tread compounds
for off-the-road (mining / agricultural) tires to improve tear
resistance and cut & chip resistance
Effect of Filler Loading on Tensile Strength
(Filler Agglomerates as Crack Precursors)
0.216
 = 0.268 0.186
0.155
• The decrease in tensile strength at the highest loading is commonly observed

and attributed to undispersed filler agglomerates
– Dispergrader (and other microscopy techniques) will typically not inform about this
until extreme dispersion issues. Need to determine c0 from crack nucleation and
growth tests.
N.P. Warasitthinon and C.G. Robertson, Rubber Chem. Technol., Online First (2018),
doi:10.5254/rct.18.82608

Undispersed Filler Agglomerates as Crack Precursors
B. Huneau, I. Masquelier et al. Rubber Chemistry and

Technology: March 2016, Vol. 89, No. 1, pp. 126-141

Unpublished study (Endurica; PRL – Zlín)




Exercise 4: CB Dispersion, Crack Precursor Size, and
Fatigue Lifetime
• Determine the crack precursor sizes for the “poor” CB dispersion and
“good” CB dispersion SBR compounds
• If the “good” dispersion SBR compound could be improved further by
reducing the crack precursor size to 0.010 mm (10 m), what would be
the fatigue lifetime?
Recall from Chapter 3 for Thomas Law crack growth behavior:

1
 N f ( F − 1) rc ( 2Wmax ) F  1− F
c0 =  F


 T c 
T = 2 W c
• Remember: larger crack gives a larger tearing energy which gives a

faster crack growth
• Initial crack size (crack precursor size) is very important!


Filler Effects vs. Crosslinking Effects on Durability
TC TC
Add CB

T0 T0
increase crosslinking
log [T (J/m2)]
log [T (J/m2)]
• Based on relative effects of carbon black and crosslink density,

one strategy for improving durability is to reduce curative
levels and increase filler loading to maintain stiffness

Summary: Filler Effects on Durability
Adding filler:
• Increases stiffness which influences
crack driving force
TC
• Increases energy dissipation
increase 
(hysteresis) and related critical tearing

energy, TC
• Increases intrinsic strength, T0 (with T0
possible exception of silica-silane filler
system)
• Causes strain amplification which log [T (J/m2)]
promotes strain induced crystallization
• Crack blunting effects noted
• Undispersed filler agglomerates are
crack precursors

Stiffness and
Deformation Control Mode
© 2015 Endurica LLC W. V. Mars 8-1

Dealing with Stiffness Variations
• We just discussed the two main techniques for
influencing the modulus/stiffness/hardness in rubber
compounds
– Type and loading of fillers
– Extent of crosslinking
• How can fatigue performance differences between
rubber compounds be interpreted when there are also
differences in stiffness and mode of control in the final
application?
• What if your lab test runs in one mode (e.g. strain
control) but your application is governed by another
mode (e.g. load control or energy control)?

Outline
• Purpose
– How can fatigue performance differences
between rubber compounds be interpreted
when there are also differences in stiffness and
mode of control?
• Agenda
– Balancing properties in compound development
– Quantifying mode of control
– Example
Role of Stiffness in Balancing Properties in
Compound Development for Durability
• Large available stiffness range

• Unintended stiffness changes may accompany
changes made to other properties
(viscoelasticity, fatigue, friction, etc.).
– Achieved through recipe, processing, cure…
• Without proper accounting, these changes can
obscure the relation between lab specimen test
results and product test results, adding risk
when inferring product performance from lab
measurements.

Two Compounds, 3 Modes of Control
Stress control Energy control Strain control
  1
 = C 
2
  
The ranking of the compounds depends not only on their
fatigue properties, but also on stiffness properties and mode of
control.

Partitioning the Linear Elastic Law
1− X 1+ X
−
p =E 2
=E 2
n=2 n =1 n=0
X = −1 X =0 X =1
p = =E =E 1 0 p =  =  E 0 =  E −1
p = 2w =  E1/ 2 =  E −1/ 2
p = that which is held constant X = the specifier for the partition type

Implications…
X −1 If we know the deformation
  E 2 index, the reference and new
=  stiffnesses, and the reference
 0  E0  strain, energy or stress, then we
know the new strain, energy and
X stress !
W  E 
= 
W0  E0  We can also derive Futamura’s
relation for hysteresis…
X +1
  E  2
n = 1− X
= 
 0  E0  n
Q E E  " *
= "  0
*
Q0 E0  E 
Application
Typical strain-life fatigue relationship

Application
FB for typical rubbers is in

the range -4 < FB < -8

Example: ranking compounds
Modulus Fatigue Lab testing

Fatigue life
Life 100% strain
Compound MPa Cycles (strain = 1)
A 1.00 1000
B 0.75 1300
C 1.33 800
D 0.75 2500
E 1.33 400

Relative Operating Strain
1.40
1.20
1.00
Strain / StrainA
0.80
A
0.60
B, D
0.40
C, E
0.20
0.00
-1 -0.5 0 0.5 1
Mode of Control X

Relative Operating Stress
1.40
1.20
1.00
Stress / StressA
0.80
A
0.60
B, D
0.40
C, E
0.20
0.00
-1 -0.5 0 0.5 1
Mode of Control X

Fatigue Life
Using F = -4
10000
A
B
C
D
E
Fatigue Life
1000
100
-1 -0.5 0 0.5 1
Mode of Control X

Example: estimating X
Given: Two finite element analyses were run, with care

taken to establish realistic boundary conditions, differing
only in the stiffness of the rubber, and showing that:
Modulus SED
FEA 1 2.5 MPa 0.764
FEA 2 2.0 MPa 0.905
Find: What is the deformation index? Which

compound, of the 5 shown in prior example, will give
longest fatigue life?

Solving for X
X
W  E 
= 
W0  E0 
logW − logW0
X=
log E − log E0
log 0.905 − log 0.764

X= = −0.759
log 2.0 − log 2.5

Fatigue Life
10000
A
Compound C will endure the B
longest in this application C
D
E
Fatigue Life
1000
100
-0.759
-1 -0.5 0 0.5 1
Mode of Control X

Key Points
• Fatigue ranking depends strongly on mode
of control and stiffness
• Know the mode of control for the lab test
and for the service application
• If the lab test differs in mode of control
from the service condition, then use theory
to estimate how mode of control will affect
compound performance and ranking

Further Reading
• W. V. Mars, ANALYSIS OF STIFFNESS VARIATIONS
IN CONTEXT OF STRAIN-, STRESS-, AND ENERGY-
CONTROLLED PROCESSES, Rubber Chem. Technol.
84, 178 (2011); doi:10.5254/1.3570530
• Futamura, Shingo, and Art Goldstein. "A simple method
of handling thermomechanical coupling for temperature
computation in a rolling tire." Tire Science and
Technology 32, no. 2 (2004): 56-68.

Influence of Oils, Plasticizers & Resins

Topics
• Oil versus plasticizer

• Effect of oil on T0
• Effect of oil on TC
• Use of resins

Oil versus Plasticizer
• One definition of plasticizer is that it is a liquid that dilutes the polymer and softens the
rubbery modulus
– Affected by miscibility of the liquid with the elastomer
• Another definition of plasticizer is that it is a liquid that reduces the glass transition of
the polymer
– Affected by miscibility of the liquid with the elastomer
– IMPORTANT: This will depend on relative Tg values for elastomer and liquid
1000 1000 1000
Modulus (MPa)
Modulus (MPa)
Modulus (MPa)
100 100 100
10 10 10
no oil no oil no oil
with oil with oil with oil

1 1 1
e.g. SBR + TDAE oil e.g. NR + TDAE oil e.g. BR + TDAE oil
Temperature Temperature Temperature

Glass Transition Temperatures of Various Elastomers
Appendix of:
A.N. Gent, “Engineering with Rubber –
How to Design Rubber Components”, 3rd
Edition, Carl Hanser Verlag, Munich 2012
Solution Styrene-Butadiene Rubber
http://www.valvemagazine.com/web-only/categories/technical-topics/7131-low-
temperature-sealing-with-elastomers-in-sour-gas.html

Glass Transition Temperatures of Various Oils

Relating Swollen T0 to Unswollen
Polymer chain crossing the plane
 =1
𝑇0,𝑢𝑛𝑠𝑤𝑜𝑙𝑙𝑒𝑛
𝑇0,𝑠𝑤𝑜𝑙𝑙𝑒𝑛 =
2𝑠

Part C: Polymer Reviews, 28:3-4, 339-370 s

Effect of Oil on T0 (Chain Dilution)
𝑇0,𝑢𝑛𝑠𝑤𝑜𝑙𝑙𝑒𝑛
𝑇0,𝑠𝑤𝑜𝑙𝑙𝑒𝑛 =
2𝑠
Adding oil expands the volume.
The expansion ratio for one dimension of the expanded cube of material is given by:
1
𝑤𝑝 𝑤𝑜 3 w: weight (can use phr)
𝜌𝑝 + 𝜌𝑜 : density
𝑠 = 𝑤𝑝 Subscript p: polymer
𝜌𝑝 Subscript o: oil
1
Example: 100 𝑔 37.5 𝑔 3
+
100 phr dry polymer (dry; not oil extended) 0.92 𝑔/𝑐𝑐 0.96 𝑔/𝑐𝑐
𝑠 = = 1.11
37.5 phr oil 100 𝑔
0.92 𝑔/𝑐𝑐
o = 0.96 g/cc
p = 0.92 g/cc 𝑇0,𝑢𝑛𝑠𝑤𝑜𝑙𝑙𝑒𝑛
𝑇0,𝑠𝑤𝑜𝑙𝑙𝑒𝑛 = = 0.81 𝑇0,𝑢𝑛𝑠𝑤𝑜𝑙𝑙𝑒𝑛
2𝑠
37.5 phr oil reduces T0 by 19%
Want to increase fatigue threshold, T0?
Remove oil and other diluents from the formulation
Effect of Oil on Hysteresis and TC
• Diluting the polymer chains with a liquid pushes the polymer chains apart from each
which reduces hysteresis and decreases TC
– Swelling in a liquid produces similar effect to adding oil in the rubber formulation
– If the liquid also decreases the Tg of the elastomer, then hysteresis and TC will be reduced even
further due to the Tuse – Tg effect discussed in the Polymer Selection lecture
• Adding oil to the system is like increasing temperature
Slope shows rate dependence

(reflecting energy dissipation at crack tip)

Effect of Oil on Hysteresis
Palm biodiesel (B100)

Effect of Swelling on Crack Growth

TC
hysteresis effect +
chain dilution effect
TC
hysteresis effect

swollen
swollen
T0 dry T0 dry
chain dilution effect

log [T (J/m2)]
(not adjusted) log [T (J/m2)]
(adjusted)
TC
hysteresis effect
swollen

dry
T0
log [T (J/m2)]
(adjusted)

Effect of Plasticizer Loading on TC for Bromobutyl Rubber
A significant part of the softening

and lower hysteresis is coming from
a reduction in filler volume fraction
as more plasticizer is added

Effect of Plasticizer Loading on TC for Bromobutyl Rubber
A significant part of the TC decline is coming

from a reduction in filler volume fraction as
more plasticizer is added

Effect of Diluents
• Adding oil in the formulation (everything else
constant)
– Reduces filler volume fraction which reduces
stiffness and hysteresis
𝑤𝑓
σ𝑓
𝜌𝑓
= 𝑤
σ𝑖 𝑖
𝜌𝑖
w: weight (can use phr)

: density
Subscript f: all fillers
Subscript i: all compound ingredients including fillers

Effect of Swelling on Fatigue Life
Stress controlled test (pressure-driven bubble inflation)
Hydraulic fluid IRM903
Swelling or adding oil to a rubber formulation

increases crack growth by reducing both T0 and TC,
but modulus is also reduced which affects W
(see next slide)

Effect of Oil Content (or Swelling) on W
Stress control Strain control

 low oil  low oil
high oil high oil
 
The ranking of the compounds depends not only on their fatigue
properties, but also on stiffness properties and mode of control.

Resins
J. E. Duddey “Resins” (Chapter 9), in Rubber Compounding: Chemistry and Applications, 2nd Edition (ed. B.
Rodgers), Boca Raton, FL: CRC Press, 2016.

Viscoelastic Effects of Oil vs. Resin
C. G. Robertson, “Glass Transitions in Elastomer-Particle Systems”, The University of Akron College of

Polymer Science and Polymer Engineering Alumni Day and Elastomer Symposium, October 16, 2015

Tg Effects of Oil vs. Resin
Fox Equation
Tg : glass transition of blend (in K)

Tg,i : glass transition of component i
wi : weight fraction of component i
1 𝑤1 𝑤2
= +
𝑇𝑔 𝑇𝑔,1 𝑇𝑔,2
Tg = Tg,Fox – Tg,Blend
Smaller Tg indicates

better compatibility
C. G. Robertson, “Glass Transitions in Elastomer-Particle Systems”, The University of Akron College of
Polymer Science and Polymer Engineering Alumni Day and Elastomer Symposium, October 16, 2015
• It is expected that TC and crack growth resistance can be increased by using miscible
hydrocarbon resins due to increased glass transition temperature (see Tuse – Tg discussion in
Polymer Selection lecture)

Reinforcing Resin Networks in Tire Applications
▪ Stiff reinforcing resin

network is co-continuous
with crosslinked elastomer
network
▪ Network forms during tire
curing which provides
significant reinforcement
without rubber
processability penalty
▪ However, network can be
permanently broken by
strain, so typically only used
in low-strain regions of tire
such as bead filler
compound (fragile www.akrochem.com/pdf/technical_papers/reinforcing_phenolic_resins01.pdf
structure) https://www.tireworks.net/understanding.htm
21

Summary
• Adding oil to the formulation (or TC
swelling the rubber) decreases hysteresis effect +
both TC and T0 to give faster chain dilution effect
crack growth

• Need to keep in mind that oil extended
adding oil to the formulation or swollen
without making other compound
adjustments will reduce filler T0
volume fraction, such that filler dry
reinforcement – and influence on
durability – will also be affected
• Adding a miscible resin to the
compound may improve TC and chain dilution effect
crack growth resistance due to log [T (J/m2)]
effect of increasing glass
transition temperature of the
elastomer

Stabilizing Against Aging

Topics
• Some history
• Stabilizing against ozone attack
• Oxidative degradation and antioxidants
• Lab testing for aging effects on durability

Some History
Received 1956 Goodyear Medal from ACS Rubber Division
https://en.wikipedia.org/wiki/Sidney_M._Cadwell

Some History
Received 2011 Goodyear Medal from ACS Rubber Division
https://en.wikipedia.org/wiki/Joseph_Kuczkowski

Ozone Cracking
A. Y. Coran, “Chemistry of the Vulcanization and Protection of Elastomers: A

Review of the Achievements”, J. Appl. Polym. Sci. 87, 24 (2003)
• Double bonds are attacked
• Anti-ozonants react with
O3 before it can react with
polymer
Many C=C Bonds
Many C=C Bonds • Stretching makes polymer
chains more susceptible to
ozone cracking
Handbook of Polymer Science and Technology, Vol
2 (N.P. Cheremisinoff, ed.) CRC Press, 1989

Effect of Ozone Concentration
NR
rz
Butadiene-
Styrene co-
polymer
M. Braden and A. N. Gent (1960) Rubber Chemistry and Technology: Vol. 33, pp. 1142-1155.

Effect of Ozone on Crack Growth
T0 • Due to the stress concentration, elastomer
network chains at a crack tip are energetically
favorable for reaction with ozone
• Ozone reacts with carbon-carbon double bonds
in the main polymer chain, causing scission of
the chain.
• Crack growth due to ozone attack occurs
whenever the instantaneous energy release rate
exceeds a small threshold, GZ, which is typically
much smaller than the mechanical fatigue
threshold T0.
• For unprotected rubber, GZ ≈ 0.1 J/m2. The
presence of antiozonants can increase GZ by a
factor of 10 or more.
WV Mars and A Fatemi, Rubber Chem Technol
77, 391 (2004)

Mechanical Requirement – Single Crack
rz
unprotected
protected
For unprotected rubber, Tz ≈ 0.1 J/m2. The presence of

antiozonants can increase Tz by a factor of 10 or more.
G. J. Lake (1970) Rubber Chemistry and Technology: Vol. 43, pp. 1230-1254

Protection Against Ozone Attack
▪ Para-phenylenediamines (PPDs) are
effective in reducing ozone cracking
in diene rubbers and there is good
evidence that they react directly with
ozone, competing with the ozone-
rubber reaction
▪ However, there are no additives that
enable unsaturated elastomers to
resist ozone as well as saturated ones
▪ Combinations of microcrystalline wax
(protective physical barrier) with
PPDs (chemical protection) provide
good stabilization results
Handbook of Polymer Science and Technology, Vol

GR Hamed, “Materials and Compounds” (Chapter 2), in Engineering with Rubber 2 (N.P. Cheremisinoff, ed.) CRC Press, 1989

Ozone-Critical Stress, Strain
Tz
Wz = k 3
2ka
Tz 1  z2 1 2
Wz = = = E z
2ka 2 E 2
Tz E Tz
z = z =
ka Eka
(crack size, a, sometimes given symbol c)

Strain Dependence and Crack Density
7.5% 15% 30%
Doreen M. Smith and V. E. Gough (1954) Ozone Cracking a Cinematographic Study.

Rubber Chemistry and Technology: March 1954, Vol. 27, No. 1, pp. 175-191

Crack Density
Crack density as a
function of stress or
strain maps directly
to crack size
distribution!
 z (a) a
= 0
 z (a0 ) a
M. Braden and A. N. Gent (1960) The Attack of Ozone on Stretched Rubber

Vulcanizates. II. Conditions for Cut Growth. Rubber Chemistry and
Technology: September 1960, Vol. 33, No. 4, pp. 1156-1165.

Critical Strain for Ozone Attack
Z. W. Wilchinsky and E. N. Kresge (1974) A Quantitative Test for Ozone Andrews, E. H. (1967). Resistance to ozone
Resistance of Rubber Vulcanizates. Rubber Chemistry and Technology: cracking in elastomer blends. Rubber
September 1974, Vol. 47, No. 4, pp. 895-905. Chemistry and Technology, 40(2), 635-649.

Exercise 5: Critical Strain for Ozone Attack
• Given
– Tz = 5 J m-2
– a0 = 0.100 mm (crack precursor size)
– E=1 MPa
• What is the critical strain for ozone attack?
• If T0 = 50 J m-2, what is the threshold strain for
fatigue?

Oxidative Degradation and Antioxidants

▪ Amine antioxidants inhibit the

free radical oxidation process
A. Y. Coran, “Chemistry of the Vulcanization and Protection of

Elastomers: A Review of the Achievements”, J. Appl. Polym. Sci.
87, 24 (2003)

Greater Oxidation Effects at Rubber Surfaces
L. G. Pierre-Yves “Predictive ageing of elastomers: Oxidation driven modulus changes for

polychloroprene”, Polymer Degradation and Stability 130, 348 (2016)

Oxidative Aging: Crosslinking vs. Scission
http://polymerdatabase.com/polymer%20chemistry/Thermal%20Degradation%20Elastomers.html

Oxidative Aging: Crosslinking vs. Scission
http://polymerdatabase.com/polymer%20chemistry/Thermal%20Degradation%20Elastomers.html

Effect of Oxidative Aging on Properties:
Relative Crosslinking and Scission Effects


Effect of Oxidative Aging on Crack Growth
Filled NR
P Soma, N Tada, M Uchida, K Nakahara, Y Taga, J Solid Mech and Mat Eng, 4, 727, 2010.

Effect of Antioxidants on Crack Growth
Air, Gum NR, No AO

Vaccum, Gum NR, No AO
Air, Gum NR, +AO
Lake & Lindley, Rubber J., 146 (10), 24 (1964)

Oxidative Degradation is a Significant Contributor
to Rubber Abrasion (Wear)
Air
A. Schallamach (1968) Recent Advances in
Knowledge of Rubber Friction and Tire Wear.
Rubber Chemistry and Technology: March
1968, Vol. 41, No. 1, pp. 209-244.
▪ Abrasion of rubber involves both mechanical fracture and thermal-oxidative

effects (aging/degradation)
− A. N. Gent and C. T. R. Pulford, “Mechanisms of Rubber Abrasion”, J. Appl. Polym. Sci.
28, 943 (1983).
▪ Want to improve wear resistance of applications like tire treads?
− Try adding more (x2) antioxidant to the formulation!

Lab Testing for Aging Effects on Durability
log[E (MPa)]
23 C
50 C
75 C
100 C
log[T0 (J/m2)]
log[TC (kJ/m2)]

Arrhenius Law
Activation
Energy
Ea
−
k = Ae RT
Absolute
Reaction Temperature
rate prefactor Gas
Constant
-Ea/R

Aging Master Curves
k ( )
E (t ,  ) = f ( t ref )
k ( ref )
Ea  1 1
k ( )


k ( ) − −
R    ref 
T0 (t ,  ) = g ( t ref )
=e 
k ( ref )
k ( ref )
k ( )
Tc (t ,  ) = h( t ref )
k ( ref )
Error minimization
 ( Ea ) =  wi (T0,i − T0 ( Ea ,  , t ))2 +  wi (Tc ,i − Tc ( Ea ,  , t ))2 +  wi ( Ei − E ( Ea ,  , t ))2

 ,t  ,t  ,t

Aging Master Curve at Reference Temperature
log[E (MPa)]
23 C
50 C
75 C
100 C
log[T0 (J/m2)]
log[TC (kJ/m2)]

Extrapolated Master Curves
log[E (MPa)]
log[T0 (J/m2)]
log[TC (kJ/m2)]

Summary
• C=C double bonds (unsaturation) in the structure of many
elastomers makes them vulnerable to oxidative degradation and
ozone attack
• Combination of microcrystalline wax (physical protection) and
PPDs (chemical protection) is widely used for stabilizing rubber
against ozone cracking
• Various amine antioxidants are available for slowing oxidative
degradation
• Changes in rubber properties reflect crosslinking at lower aging
temperatures and scission at higher aging temperatures
• Measuring modulus, T0, and TC as functions of aging time and
temperature – and applying Arrhenius law master curve
methodology – is an efficient approach for determining aging
effects on durability in the lab

Further Reading
• A. Y. Coran, “Chemistry of the Vulcanization and Protection of

Elastomers: A Review of the Achievements”, J. Appl. Polym.
Sci. 87, 24 (2003)
• John M. Baldwin and David R. Bauer (2008) Rubber Oxidation
and Tire Aging - A Review. Rubber Chemistry and Technology:
May 2008, Vol. 81, No. 2, pp. 338-358.
• GR Hamed, “Materials and Compounds” (Chapter 2), in
Engineering with Rubber (AN Gent, Ed.), 3rd Edition, Carl
Hanser Verlag, Munich 2012

Simulation for Materials Selection
and Durability Prediction

Solution Approach
11
12
Given the material properties

and strain history of a rubber  22
component, compute the
 33 = 0
number of cycle repeats that
Material Properties
will be endured before the
Strain History
fatigue process produces
cracks of a given size.
Nominal Strain
Crack growth rate
11
22
12
Time
Crack Driving Force

Fatigue Life Prediction
(Jaguar exhaust hanger mount)
crack precursor size

Critical Plane Analysis in Endurica CL Durability Solver for FEA
▪ Predicts location and

orientation of cracks
▪ Conservative approach to
lifetime prediction
▪ Continuum / nucleation
viewpoint
▪ Accounts for finite
straining
▪ Crack closure in
compression
▪ Failure plane
identification
▪ Crack precursor loading
experience

Fatigue Analysis Software for Finite Element Analysis

Fatigue Analysis Software for Finite Element Analysis
Inputs
• Fatigue parameters for your materials
– Crack precursor size, crack growth rate law, etc.
• Finite element analysis (FEA) of your product
design in complex, multi-axial loading
– Integrates with Abaqus™, ANSYS™, and MSC Marc™
Outputs
• Fatigue lifetime for every element of the model
which is mapped back onto the FEA mesh
• Crack orientations from critical plane analysis
Benefits
• Adjust design and/or material properties to
resolve short lifetime areas before building and
testing prototypes
– Reduce number of iterations in product
development cycle
• Virtual testing for materials development
– Sensitivity analysis of crack precursor size with
relevance to filler dispersion and mixing quality
– Change elastomer type through material inputs
including strain crystallization parameters
– Many other possibilities
Road Loads Validation
4000
2000
Fx, N
0
-2000
0 200 400 600 800 1000 1200 1400
500
Fy, N 0
-500
0 200 400 600 800 1000 1200 1400
5000
Fz, N 0
-5000
0 200 400 600 800 1000 1200 1400
Barbash, Kevin P., and William V. Mars. Critical Plane

Analysis of Rubber Bushing Durability under Road Loads.
No. 2016-01-0393. SAE Technical Paper, 2016.

Multi-Axis FLCA Bushing Validation
Test Inputs Radial Axial Torsional Radial & Torsional

Test Conditions +/- 7,000N +/- 2,000N +/- 43° +/- 4,500N & +/- 30°
Termination Conditions +/- 9.5 mm +/-22 mm 80,000 Cycles +/-7.75 mm Radial Travel
fe-safe/Rubber Cycles (1 mm Tear) 17,257 65,912 37,668 12,162
Cycle of Initial Rate Change 24,132 77,275 50,000 13,362
Part Rate Life vs Prediction 140% 117% 133% 110%
Bench Durability Cycles 28,142 83,685 79,195 21,374
Tear Length End of Test 14.32 mm 17.55 mm 23.57 mm 19.57 mm
Goossens, Joshua R., William Mars, Guy Smith, Paul Heil, Scott
Braddock, and Jeanette Pilarski. Durability Analysis of 3-Axis Input to
Elastomeric Front Lower Control Arm Vertical Ride Bushing. No. 2017-01-
1857. SAE Technical Paper, 2017.

Critical Plane Validation for Non-Relaxing Fatigue of
Strain-Crystallizing Rubber
With strain crystallization parameters, Endurica CL critical plane analysis predicted

the angles of cracks in non-relaxing fatigue testing of natural rubber compounds
A. Ramachandran, R. P. Wietharn, S.I. Mathew, W. V. Mars, and M. A. Bauman, “Critical Plane
Selection Under Nonrelaxing Simple Tension with Strain Crystallization”, Presented at the Fall 192nd
Technical Meeting of the Rubber Division, ACS, Cleveland, Ohio, October 10-12, 2017 (Paper #E15).

M1 Abrams Tank Track Backerpad
Thermal Analysis Fatigue Analysis Failure Mode
Mars, William V., Matthew Castanier, David

Ostberg, and William Bradford. "DIGITAL TWIN
FOR TANK TRACK ELASTOMERS: PREDICTING
SELF-HEATING AND DURABILITY.“, GVSETS, 2017.

Forward Paths…
Learn More about Characterize Analyze Durability of your

Principles and Practices Your Material Finite Element Model
Training Opportunities
• Experiments
• Analysis
• Compounding
Test My
Material!
For more information, contact:

Chris Robertson
www.endurica.com cgrobertson@endurica.com

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Instructor: Christopher G. Robertson, Ph.D.

India, January 2019

© 2018 Endurica LLC cgrobertson@endurica.com

© 2018 Endurica LLC 0-2

Characterization Software Testing Instruments

• Material behavior • Geometry • Intrinsic Strength Analyser

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Value at stake, PER FAILED

• Understanding Compounding for Durability = Less Iterations in

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− Notice the past tense!

“Common Causes Of Failure In Elastomers” by Gary S. Crutchley (Smithers Rapra Technology)

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“Common Causes Of Failure In Elastomers” by Gary S. Crutchley (Smithers Rapra Technology)

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• Materials such as metals possess well-defined mechanical characteristics

• In contrast, the properties of rubber depend incredibly on all sorts of details

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• Understand how rubber fatigue and failure

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• Example rubber formulations

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GR Hamed, “Materials and Compounds” (Chapter 2), in Engineering with Rubber

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GR Hamed, “Materials and Compounds” (Chapter 2), in Engineering with Rubber

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GR Hamed, “Materials and Compounds” (Chapter 2), in Engineering with Rubber

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GR Hamed, “Materials and Compounds” (Chapter 2), in Engineering with Rubber

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GR Hamed, “Materials and Compounds” (Chapter 2), in Engineering with Rubber

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GR Hamed, “Materials and Compounds” (Chapter 2), in Engineering with Rubber

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300.5 total phr!

GR Hamed, “Materials and Compounds” (Chapter 2), in Engineering with Rubber

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Intermeshing mixers provide better filler

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• Filler volume fraction () is key to

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Y Fukahori, AA Hon, V Jha, and JJC Busfield,