Você está na página 1de 67

1

Mechanical Properties of Rubber


A. N. Gent
The University of Akron
Outline
Elasticity and Visco-Elasticity
Rubbery, Crystalline and Glassy States
Elastic and Inelastic Behavior
Effects of Rate and Temperature (WLF Principle)
Strength of Simple Rubber Compounds
Tear Strength, Tensile Strength
Visco-Elastic Contribution to Strength
Crack Growth (Mechanical Fatigue)
Strength of Adhesion

2



Outline (continued)
Friction
Rolling Friction
Sliding Friction
(a) on wet rough surfaces
(b) on dry smooth surfaces
Abrasion
Sliding Abrasion
Abrasion as Fatigue Crack Growth
Wear of Slipping Wheels
3



Rubbery solids
Properties
Soft
Highly elastic
Virtually incompressible in bulk
Molecular Structure
Long, linear, flexible molecules forming random coils
Molecular segments are mobile (Brownian motion)
Molecules are interlinked into a loose 3-D network
4



Chemical crosslinks,
usually sulfur linkages.

M
c
: Mol. wt. between
crosslinks, of order
10,000
Number of strands per unit
volume: n = A/M
c

( = density; A = Avogadros
number)
Crosslinked rubber: a network of long flexible
molecules with segments in rapid Brownian motion
5



Why are some polymers not rubbery?
Stereo-regular molecules may spontaneously
crystallize (e.g., polyethylene).

Molecules with bulky side-groups may not have
sufficient thermal energy for free rotation around
main-chain C-C bonds. They are polymeric glasses.

All polymers become glassy below a certain
temperature, denoted T
g

6



Brownian motion of molecular
segments
Rate | of segmental jumps depends strongly
on temperature
7



Elastic coefficients (moduli) for
small strains
Shear modulus G
Definition: G = t/
(Shear stress t = F/A)
Modulus K of
bulk compression
K = P/ (-AV/Vo)
8



Elastic coefficients (continued)
Tensile modulus E
E = t/c
Tensile strain c = AL/L
o

Poissons ratio v
v = (-AW/W
o
)/(AL/L
o
)
Relations between moduli

E = 9KG/(3K + G) = 2(1 + v)G = 3G when K G
v = (1/2)(3K - 2G)/(3K + G) = 1/2 when K G
9



Approximate values of elastic coefficients
for rubber
Indentation Hardness: 40 50 60 70 80
Tensile modulus E (MPa): 1.5 2.4 4 6 10
Modulus K of bulk compression
K = 2 - 2.5 GPa
Poissons ratio: v = 0.499
Linear thermal expansion coefficient:
o = 1..2 - 2 x 10
-4
/
o
C
10



Compression of a bonded rubber block
Because rubber is virtually incompressible,
it is sheared outwards by compression and
generates an internal pressure.
The force F is given by integration as:
F = E(ta
2
)[1 + (a
2
/2h
2
)]e
instead of
F = E(ta
2
)e

Thus the effective compression modulus
E
eff
is generally greater than E.
11



Degree of crosslinking from tensile
modulus E
Extension ratio
1 2 3 4 5 6 7 8 9
S
t
r
e
s
s


(

M
p
a

)
0.0
0.5
1.0
1.5
2.0
2.5
Initial slope =
modulus E

From molecular theory of
rubber elasticity:
E = 3nkT

T is absolute temperature
k is Boltzmanns constant
is Avogadros number


12



Carbon
black
filler

Crosslinkimg
(vulcanization)
Filled rubber
13



Problems with filled rubber compounds
Typical filled rubber compounds show two special features:

1. Payne Effect: A marked softening, starting at strain
amplitudes of only 0.1 %, attributed to breaking apart
aggregates of filler particles.

2. Mullins Softening: A further substantial softening at
higher strains, up to the breaking strain, attributed to
progressive detachment of rubber molecules from filler
particles.
14



Stress-softening of filled rubber at
small srains (Payne Effect)
The modulus of filled compounds
drops sharply as the amplitude
of dynamic strain increases,
typically to one-third or less of the
value at small strains.
It recovers somewhat on standing.
The effect is attributed to breaking
filler-filler agglomerates that can
slowly reform, taking weeks or
months at ambient temperature.


Data from C. Sun
15



Stress-softening of filled rubber
at large strains (Mullins Effect)
Filled rubber compounds
are softened more, the
greater the pre-strain.

Recovery is very slow.
16



Theory of rubber elasticity for large
strains
The deformation
is described by
stretch ratios:

1
,
2
,
3





Strain Energy W
A simple relation for the strain energy density is:
W= (E/6) (
1
2
+
2
2
+
3
2
- 3)
(This constitutive law is termed neo-Hookean)
17



Stress - strain relations
We can calculate stresses from the relation for W.
AW = f
1
d
1
. Hence: t
1
=
1
cW/c
1
+ P , etc.
where P is an
undetermined
hydrostatic
pressure
Note: we have assumed
incompressibility:

1

3
= 1
18



Example: Stress-strain relation
in tension
Simple extension
stretch ratios:


1
= ;
2
=
3
=1/
1/2

Relation between
stress and deformation
t = (E/3) (
1
2
- 1/
1
)

(Note:
1
= 1 + c)
19



Experimental relation between tensile
stress and elongation
Tensile
stress
(o = F/A
o
)
Elongation e (%)
Note: In rubber
technology, M
100

denotes force F
per unit of unstrained
cross-section, when
e = 100%
The rise at high elongations
is not predicted by
neo-Hookean kinetic theory
20



Constitutive laws for filled
rubber compounds
Because filled rubber compounds are not elastic,
i.e., they do not follow reversible stress-strain
relations, there is NO VALID CONSITUTIVE LAW.

[Even the small-strain elastic modulus E is not known
precisely, because its value depends on the previous
deformation history.]
21



Oscillatory deformation: Dynamic effects
Perfectly elastic
Slope = G (MPa)
(Shear modulus)
Visco-elastic
Slope = G (MPa)
G = Dynamic shear modulus
Area = t G
m
2
G = Dynamic shear loss modulus
Tan o = G/ G
22



Oscillations
In-phase and out-of-phase components

For an elastic solid
the strain is in phase
with the stress.

For a visco-elastic solid
the strain lags behind
the stress with a delay
of o/e (sec) where e is the frequency (rad/sec)

When o = t/2 the stress and strain are 90
o
out of phase.
Stress and strain vs time

23



Mobility of molecular segments
Rate | of segmental jumps depends
strongly on temperature
24



Dependence of segmental mobility |
on temperature
[Williams, Landel
& Ferry 1955]






Universal WLF relation:
Log (|
T
/|
Tg
) = 17.5 (T - T
g
)/ (52 + T - T
g
)
Note: Segmental jump rate at Tg
is |
Tg
= 0.1/sec
[But for butyl rubber:
Log (|
T
/|
Tg
) = 17.5 (T - T
g
)/ (100 + T - T
g
)]
25



Why is butyl rubber anomalous?
Possibly because the moving segment is unusually
long, due to steric constraints.

Other anomalous polymers are the acrylates with long
side groups which also require a relatively large amount
of free volume for molecular motion.

The anomalous WLF behavior gives butyl rubber low
resilience, low gas permeability, and good ozone
resistance at temperatures well above T
g
.
26



Use of WLF relation to predict results
at other temperatures
Frequency f at temperature T is equivalent to a
frequency f* at temperature T* , where
f*/f = |
T*
/|
T
( = a
T
)
Similarly, for strain rates de/dt, or velocities v, etc., the
results at a temperature T are the same as those at a rate
(de/dt)* at a temperature T* , where
(de/dt)* / (de/dt) = |
T*
/|
T
( = a
T
)
a
T
is termed the shift factor that corrects for the temperature
change. (Note: shift factors are not affected by adding fillers)

27



Creating a master curve of dynamic
modulus vs. log frequency at a reference
temperature T
o

Note: the horizontal shifts
agree with the WLF equation
28



Dynamic moduli G, G of natural
rubber vs log (frequency) at T
g

29



Dynamic modulus of a PU elastomer
vs. log frequency

Figure 14a. Modulus E vs log (oscillation frequency f ) for a PU elastomer
Figure 14b. Modulus E vs reduced frequency f a
T
at 42
o
C
30



Dynamic properties vs frequency
and temperature
Note: At a higher temperature,
(T
2
,) the same results appear
but at higher frequencies.

The curves are displaced along
the log e axis by a distance
Log a
T
that is given by the
WLF relation

31



Mechanical Properties of Rubber II

Strength of Rubber Compounds
Tear strength, Fracture energy
Tensile strength
Visco-elastic contribution to strength
Effects of rate and temperature
(WLF Principle)
Crack growth (mechanical fatigue)

32



Tear strength: Fracture energy
Tear energy G
c
(J/m
2
)

is the work of fracture
per unit area torn through





Hence: G
c
= 2P/w
When the the tear
advances by dc:
Energy supplied
= 2P.dc
Work done
= G
a
w.dc
33



Griffiths theory of tensile strength
A. A. Griffith, Phil. Trans. Roy. Soc. 221, 163 (1920)
Breaking stress o
b
is given by:
o
b
= ( EG
c
/tc)
1/2


where E = tensile modulus
G
c
= tear energy
c = depth of initial edge flaw

(We assume that all materials have flaws)
34



Evidence for natural flaws (cracks)
in rubber
Variation of tensile strength with depth of an edge cut.
(Extrapolates to a natural defect, about 50 m deep,
when NO cut is introduced.)
Fatigue life of samples with edge cuts.
(Extrapolates to a natural defect, about 50m deep,
when NO cut is introduced.)
35



Theoretical tear strength

1. For a glassy polymer:
G
c
~ 1 J/m
2
(Berry, 1960)
2. For a rubbery polymer:
G
c


~ 50 J/m
2

(Lake & Thomas, 1967)
3. Measured values:
G
c
> 500 J/m
2
(
Much higher than predicted)

Where is the extra energy expended?
36



Tear strength vs. rate of tearing and
temperature (HS-SBR vulcanizate)

G
c
varies by over 1000X
with rate of tear dc/dt
and temperature.
At low rates and high
temperatures a threshold
value G
o
is approached.
The effect resembles
visco-elastic dissipation
37



Dependence of segmental mobility |
on temperature
[Williams, Landel
& Ferry 1955]






Universal WLF relation:
Log (|
T
/|
Tg
) = 17.5 (T - T
g
)/ (52 + T - T
g
)
Note: Segmental jump rate at Tg
is |
Tg
= 0.1/sec
[But for butyl rubber:
Log (|
T
/|
Tg
) = 17.5 (T - T
g
)/ (100 + T - T
g
)]
38



Dependence of tear strength on rate of
tearing and temperature (schematic)
WLF rate-temperature
equivalence is used to
construct a Master Curve
of strength vs. (Log) rate
at a chosen temperature
39



Tear strength vs equivalent tear rate
at T
g

Resuts are shown for
three simple elastomers:
BR (T
g
= - 96
o
C)
EPR (T
g
= - 60
o
C)
HS-SBR (T
g
= - 25
o
C)
Tear strength at any rate and
temperature is determined
by two parameters only:
G
o
and T
g

40



Energy dissipation and strength
The observed strength seems to be dominated by
energy lost in internal viscous processes.

These energy losses are similar for all elastomers
at the same effective rate of tearing, or at the
same reduced temperature T T
g
.

41



Correlation between strength
and energy dissipation
For different elastomers, compounds, temperatures, crosslinking:
Breaking energy U
b
is directly correlated
with dissipated energy U
d

42



Reinforcement mechanisms
Additional energy dissipation from:
Debonding from rigid particles
Plastic yielding of inclusions
Friction at interfaces
Formation of cavities
Detachment from fibers
Sacrificial bonds
Examples:
Carbon black and silica in rubber
Sulfur crosslinks
Rubber particles in epoxy resins
Fibers in composites
43



Knotty tearing with reinforcing fillers
The tear turns sideways and
stops. Then a new tear starts,
turns sideways, and stops.
This is termed: Knotty tearing
Tear blunting is a powerful
reinforcing mechanism. It is
attributed to low strength
in the strain direction, rather than
a high resistance to tearing.

Tearing at the tip of a cut in
one edge of a tensile test-piece
44



Strain Energy Release Rate G
We have discussed the fracture energy G
c.

If the applied force is too small to cause fracture,
then the AVAILABLE energy is termed the
Strain Energy Release Rate, denoted G (J/m
2
).
In Linear Elastic Fracture Mechanics, the corresponding
quantity is the Stress Intensity Factor K
(critical value K
c
)
K = (EG)
1/2

45



Tearing under repeated stressing
(Fatigue crack growth)
When energy G (< G
c
) is made
available for fracture, a crack
grows by a small distance dc
each time the stress is applied.
dc depends strongly upon G.
The Parris empirical relation is:
dc/dN = BG
o

where B and a are crack growth
constants.

But the actual behavior is more complex.
N is the number of stress
applications
46



Crack growth rates for various rubber
compounds
Note: Lower slopes
for NR (H) and
cis-polyisoprene (F)
47



Fatigue crack growth parameters
Crack growth constants
1: Index o is greater for low-loss materials
NR compounds: o = 2 (!)
SBR compounds, o = 3 - 4
BR compounds, o = 4 6
2. Crack growth constant B is related to Go
B = B/ G
o
o


Thus, dc/dN = B (G/G
o
)
o

where B is about 1 .

48



Strain-induced crystallization at a
crack tip
Even at quite small applied strains,
some stereo-regular elastomers
(NR, Butyl, Neoprene) show
strain-induced crystallization
at crack tips, where the local strains
are high.
As a result, tearing does not continue under a steady load
and fatigue crack growth rates are much lower.
49



Effect of non-relaxing strains on
fatigue life of NR
Fatigue life N for cylinders of NR cycled between a minimum
strain c
min
and a maximum strain c
min
+ Ac
Note that the fatigue life is
increased in both tension
and compression when c
min

is greater than zero.
There is no comparable effect
in non-crystallizing elastomers
e.g., SBR
50



Friction and Abrasion
Friction
Rolling friction
Sliding friction
(a) on wet rough surfaces
(b) on dry smooth surfaces

Abrasion
Abrasion mechanisms
Abrasion compared with crack growth
Wear of Slipping Wheels


51



Coefficient of friction
The coefficient of friction is defined as :
= F/N
when the block is sliding (F = F
max
)
But, for soft rubber sliding on a
smooth surface, the frictional
force F is more or less
constant, independent of the
load N, or pressure P.
Thus, the coefficient of friction
decreases continuously as the
pressure increases.
52



Imperfect contact on rough surfaces
However, there is a coefficient of friction, independent
of pressure, for harder rubber compounds, sliding against
a rough surface.
Apparently, in this case, contact is incomplete.
An increase in pressure creates a larger true area of contact,
and hence a larger frictional force.
53



Rolling friction
Elastic wheel
Reaction force acts
through the wheel center
M = 0
Visco-elastic wheel
Reaction force moves
towards loading side
because stresses are
lower in unloading:
M = Nz = FR
Torque M = FR,
where F is the
frictional force
54



Rolling friction and tan o
[ J. A. Greenwood, H. Minshall and D. Tabor, Proc. Roy. Soc. A259, 480 (1961) ]
Displacement z of the center of pressure,
and hence , depend on speed and temperature
in the same way as the loss factor tan o.

= 0.33 (N/GR
2
)
1/3
tan o
Note: has the same temperature dependence as tan o
at the effective frequency of rolling (about 10 Hz at 30 mph)
Conclusion: Rolling friction is mainly due to energy dissipated
as rubber is compressed and released in the contact patch.
55



Sliding friction on a lubricated rough surface
[K. A. Grosch, Proc. Roy. Soc. Lond. A274, 21 (1963)]
Grosch noted that the curve for vs. sliding speed v resembles the curve for
tan o vs. frequency f. [And they both obey WLF temperature shifts.]
The characteristic length d (d = v
m
/f
m
) was about 1 mm, equal to the
spacing of asperities.
Conclusion: Friction is due to energy dissipated as rubber is
compressed and released by asperities.
56



Schaperys analysis of lubricated sliding
[R. A. Schapery, Tire Sci. Technol. 6, 3 and 98 (1978)]
When a simple viscoelastic solid slides over a rigid
sinusoidal surface, the maximum energy dissipation
(when contact is complete) corresponds to = 0.25
In practice,
max
= 1 to 2
How is the extra energy expended?
57



Dry sliding on a smooth surface
Again, the curve for vs. sliding speed v resembles the curve for tan o
vs. frequency f. But it is displaced to much lower speeds than before.
Thus, the characteristic length d (= v
m
/f
m
) is now only about 5 nm,
a molecular distance.
Conclusion: Friction in dry sliding on a smooth surface is due
to energy dissipated as rubber sticks and slips on a molecular scale.
58



Sliding on a rough dry surface
Dry sliding on a rough track
In this case, two dissipative
processes appear at different
speeds, corresponding to
different length scales:
asperities and molecules.
Conclusion: Several contributions to can arise
at the same sliding speed
from stick-slip processes occurring at different length scales.
59



Measurement of abrasion
Schallamachs empirical relation
(1958) for rate of abrasion:
Volume abraded away frictional work*
o = AF
where A is termed Abradability (m
3
/J).
Typical values of A = 0.1 - 0.5 mm
3
/J
and for different compounds:
A ~10
-3
/U
b
where U
b
= tensile breaking energy
*We now know that a better relation is
o = AF
o

where the exponent o is 2 - 3 ( not 1).
60



Abradability A under frictional force F
vs. sliding velocity v
aT

Schallamachs results for
A show a marked dependence
on speed and temperature,
and obey the WLF relation.
Minimum abrasion occurs at
high speeds, near the glass
transition, when the tear strength
is a maximum.
61



Abrasion by a scraper:
Schallamach Abrasion Pattern
Schallamach saw that lines are formed perpendicular to the scraping direction..
They are ridges of a characteristic pattern , with the crests leaning towards the
scraper. The spacing is 0.5 to 5 mm apart, smaller for harder compounds.
Abrasion occurs at the base of the ridges, which bend over and protect the
lee slopes.
Abrasion particles are bimodal: small (~ 5m) from direct abrasion and
large (up to several mm) when the undermined ridge crests fall off.
62



Abrasion as a fatigue cracking process
Thomas and Southern noted
that the Schallamach abrasion
process resembles tearing:
G = F/w
where F is the frictional force.
They suggested that abrasion is a fatigue process, like crack
growth. The pseudo-cracks grow at the base of ridges,
at a shallow angle u.
63



Crack growth vs fracture energy and
Abrasion rate vs frictional energy
Thomas and Southern
compared rates of abrasion
(points) with rates of crack
growth (lines) in the
lower diagram and found
good agreement in two
cases: SBR and an
isomerized NR
(non-crystallizing).

But NR (triangles), which
has excellent fatigue
resistance but poor abrasion
resistance, is anomalous.
64



Tire distortion and side-slip in cornering
The diagram shows sidewards
deflection in the contact patch.
It increases towards the rear,
where the tread slides back
in the slip zone.

Abrasion occurs in the slip zone.
It will be lower for tires and treads
that have:
(i) Higher lateral stiffness
(less deflection)
(ii) Lower resilience
(less energy returned).
65



Factors affecting tread wear
1. Rate of wear Work of sliding x Abradability A of tread
[A = abrasion loss per J of frictional work]
2. Work of sliding = Work input x Resilience (R)
3. Work input F
2
/K
L
, where F = applied side force (Mv
2
/R)
and K
L
= Lateral stiffness of tread and carcass together
4. Thus, rate of tire wear in cornering ARF
2
/K
L
and depends on three properties of the tread compound:
Abradability, Resilience, and Elastic Modulus (through K
L
)
66




Bibliography

Engineering with Rubber, 2nd. Ed., ed. by A. N.
Gent, Hanser Publications, 2001.

Science and Technology of Rubber, 3rd. Ed., ed. by J. E. Mark, B.
Erman and F. R. Eirich, Elsevier (Academic Press), New York,
2005.

The Pneumatic Tire, ed. by A. N. Gent and J. D. Walter, US
National Highway Traffic Safety Administration, Washington
D.C., 2005. [Available from Univ. of Akron Res. Foundation
(TEL: 1-330-972-8054; FAX: 1-330-972-2368 as a CD at $10.]

67



Thank you for your attention.
I applaud your continued interest in learning.
Alan Gent (gent@uakron.edu)