Buiuc Alexandru

Master I.S.E.
3rd semester
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î e effects of carbon nanotubes on t e mec anical be avior of elastomeric
materials is investigated. î e large deformation uniaxial tension and uniaxial
compression stress-strain
be aviors of a representative elastomer are first presented. î is elastomer is t en
reinforced
wit multi-wall carbon nanotubes (MWNîs) and t e influence of weig t fraction of
MWNîs on t e large deformation be avior of t e resulting composite is quantified.
î e
initial stiffness and subsequent strain -induced stiffening at large strains are bot
found to
increase wit MWNî content. î e MWNîs are also found to increase bot t e tensile
strengt and t e tensile stretc at break. A systematic approac for reducing t e
experimental
data to isolate t e MWNî contribution to t e strain energy of t e composite is
presented.
A constitutive model for t e large strain deformation be avior of MWNî-elastomer
composites is t en developed. î e effects of carbon nanotubes are modeled via a
constitutive
element w ic tracks t e stretc ing and rotation of a distribution of wavy carbon
nanotubes. î e MWNî strain energy contribution is due to t e bending/unbending of
t e
initial waviness and provides t e increase in initial stiffness as well as t e retention
and
furt er en ancement of t e increase in stiffness wit large strains. î e model is
s own to
track t e stretc ing and rotation of t e CNîs wit macroscopic strain as well as
predict
t e dependence of t e macroscopic stress -strain be avior on t e MWNî content for
bot
uniaxial tension and uniaxial compression.
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Elastomeric materials ave long been reinforced by stiff fil lers suc as carbon
black

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and silica particles in order to provide increased stiffness and strengt
ysteresis
as
well as electrical conductivity (e.g.
Gut (1945)
Harwood and Payne (1966)

Dannenberg (1975)
Kilian (1994)
Bergstrom and Boyce (1999
2 000)). îypical
volume fractions lie in t e range of 0.10 to 0.40. î ese property en ancements are
invariably accompanied by a decrease in extensibility and tensile strain to failure. î e
introduction of carbon nanotubes to t e library of potential fillers offers new
possibilities to furt er tailor t e properties of elastomers via blending wit relatively
low volume fractions of fillers. Here
we explore t e influence of multi -wall carbon
nanotubes (MWNîs) on t e mec anical be avior of a representative elast omer. Over
t e past decade
t ere as been an explosion in researc investigating t e stiffness
and strengt en ancements t at carbon nanotubes potentially offer as fillers in
polymers (e.g. Baug man et al. (2002)
Coleman et al. (2006)). For example
t e
elastic modulus of single and multi-wall carbon nanotubes is approximately 1îPa
(e.g.
Wong et al. (1997)) and
ence
relatively small volume fractions could
potentially
provide tremendous increases in stiffness over t at of t e polymer matrix
(see
S affer and Windle (1999)
Qian et al. (2000)
Safadi et al. (2002)
Dalmas
et al. (2005)
). Suc improvements depend on good dispersion and alignment of
t e nanotubes as well as excellent bonding between t e nanotube and t e matrix
(e.g.
C en et al. (2000) and Cooper et al. (2002)). Alt oug t ere as been some
success in dispersing and aligning nanotubes
t ese issues ave not been
universally
resolved and bonding is still a limiting issue. î e researc as also primarily
focused on t e stiffness and strengt en ancement of t ermoplastics wit limited
attention to t e influence of carbon nanotubes on elastomeric be avior. Aspects
of alignment and bonding w ic may be beneficial to optimally en ancing
t ermoplastic
properties may actually be detrimental to en ancing elastomeric mec anical
be avior.
Elastomeric applications generally require and make use of t e large
deformation
extensibility and resilience of t e elastomer. Upon incorporation of stiff fillers into
elastomers
it is generally desired to en ance t e stiffness (i.e.
en ance t e initial
stiffness and retain t is stiffness en ancement for overall large strain deformation
be avior) w ile also retaining t e important attributes of large strain resilient be avior
and large strain-to-break. î e alignment (in terms of bot overall alignment
as well as waviness of t e nanotubes) and bonding detriments encountered w en
incorporating MWNîs into t ermoplastics may be used to advantage in t eir
incorporation
into elastomers. î e waviness t at leads to minimal stiffness en ancement
in glassy and/or semicrystalline polymers (see
for example
Brads aw et al.
(2003)) can still provide sufficient en ancement to t e stiffness and strengt of t e
comparatively very low modulus elastomer. î e property en ancement can be
ac ieved t roug t e unbending (straig tening out) of t e MWNîs wit deformation
suc t at t e extensibility of t e elastomer can be retained. Furt ermore
if
stiffness en ancement primarily results from unbending of t e waviness of CNîs
as opposed to axial straining of t e CNîs (w ic relies on good bonding and s ear
lag load transfer from t e matrix to t e CNî)
t e stiffness en ancement will not
be lost wit large strains. Experiments on elastomeric -like matrices en anced wit
CNîs ave been reported
for example
by Frogley et al. (2002)
Dufresne et al.
(2002)
Koerner et al. (2005)
and very recently C en et al. (2006).î e Frogley
study reports on silicone-based elastomers filled wit single wall CNîs (SWNîs)
and carbon nanofibers (CNFs). î e Frogley study reveals a dramatic increase in
initial stiffness wit small fractions of SWNîs
owever
t is stiffness en ancement
is lost after only 10-20 percent strain w ereupon t e tangent stiffness of t e
nanocomposites returns to t at of t e paren t elastomer due to debonding of t e
CNîs from t e matrix; t e tensile strain-to-break was found to decrease significantly
wit increase in volume fraction of eit er CNîs or CNFs. î e Dufresne
study report on a cast latex-MWNî composite and found increased stiffness wit
increasing MWNî content
retained stiffness to large strains
but reduced failure
strains wit increase in MWNî content. î e Koerner and t e C en studies report
on t ermoplastic elastomer polyuret anes (îPUs) en anced wit CNîs w ere t e
Koerner study produced t in s eets using a casting process and t e C en study
produced
extruded
melt-drawn fibers t ereby using processing to elp ac ieve axial
alignment of t e CNîs. It is important to note t at îPUs ex ibit Y
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be avior w ere
due to t eir copolymer structure
t e îPU mec anical be avior
c aracteristically ex ibits a relatively stiff small strain region followed by a rollover
at a relatively low stress level (typical of order of a few MPa to tens of MPa) to a
more compliant elastomeric-like stress-strain be avior. Bot t e Koerner study and
t e C en study report an increase in t e very initial modulus wit increasing CNî
weig t fraction
as well as an increase in t e rollover flow stress; t e post -rollover
tangent stiffness is found to parallel t at of t e neat polymer
losing t e dramatic
stiffness en ancement seen at small strains. î e Koerner study reports maintaining
t e same magnitude of tensile strain -to-break as t e parent îPU (wit a modest
decrease in strain-to-break wit increasing weig t fraction) and t e C en study
reports
modest increase in strain-to-break for t e lower weig t fraction cases and a
decrease in strain-to-break for t e ig est weig t fraction of 17.7wt percent. î ese
studies demonstrate aspects of t e en ancements t at can be ac ieved w en CNîs
are incorporated into elastomeric materials. However
t e loss in stiffness seen at
larger strains suggests t at CNî/matrix configurations w ic do not rely on straig t
well-bonded CNîS may be more beneficial for elastomeric applications t an for
t ermoplastic applications. î is is demonstrated in some of t e very recent work
of A ir and îerentjev (2005) and A ir et al. (2006) w ere MWNîs are incorporated
in a silicone-based elastomer to produce an IR -induced actuating polymer. In t e
A ir studies
t e CNîs are in a wavy configuration. W ile only limited mec anical
data is presented
t e stiffness is found to increase wit increasing volume fraction
of CNî and t is stiffness en ancement is maintained wit increasin g strain. î is
aspect of t e mec anical be avior t us contributes to t e resilient and reversible
be avior needed for actuation mec anisms. î ere is great potential for en ancing
t e mec anical performance of elastomers via incorporation of small weig t fr actions
of CNîs; t e multifunctional possibilities of furt er using suc en ancements
to produce actuators is enormous (note t e Koerner study was directed at creating
CNî-îPU actuating materials). Hence t e need for quantifying and predicting
t e large strain multiaxial stress-strain be avior of CNî-en anced elastomers wit
microstructurally-informed constitutive models will provide a tool for furt er designing
and optimizing materials for a wide range of applications (mec anical and
ot erwise).

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 In t is paper
we study t e mec anics of MWNî -elastomer composites. A
series of
material compositions wit a range in weig t fraction of MWNîs are produced and
evaluated in large deformation uniaxial tension and compression testing. î e
contribution
of t e MWNîs to t e deformation is t en evaluated in a systematic reduction
of t e strain energy contributions of t e elastomer matrix and t e MWNîs to
t e overall composite strain energy. A t ree -dimensional constitutive model is t en
developed and s own to capture t e d ependence of t e large deformation stress
-strain be avior of t e elastomer nanocomposites subjected to different types of
deformation (uniaxial tension and uniaxial compression).
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î e elastomer is a brominated polymer derived from a copolymer of
isobutylene
and paramet ylstyrene (PMS) wit a trademark name of EXXPRO (or BIMSM in
accordance to ASîM) (Powers et al. (1992)). Specifically
EXXPRO 3745 from
ExxonMobil C emical Company wit 1.2 mole % bromine was t e BIMSM elasto mer
used. î is BIMSM elastomer as a specific density of 0.92 and is known
to possess a good combination of properties including temperature resistance
eat
stability
low permeability
ig damping and ozone/weat ering resistance (Kresge
andWang (1993))
Multi-wall carbon nanotubes (MWNîs) of type PR19 -PS MWNî
were obtained from Applied Science. î e MWNîs ad a diameter range of
approximately
70nm to 150nm as estimated from SEM and îEM micrograp s.
Blends of BIMSM and MWNîs were prepared using a Banbury i nternal mixer
directly operating at 100 RPM under 60psi RAM pressure. î e polymer was added
first w ereas MWNîs were added 30s later. All mixes were removed from t e
internal mixer at a dump temperature of 145°C or lower wit a total mix time of
3 to 5 minutes. Curatives of 1 p r (parts per undred of polymer) zinc oxide and
1.5 p r stearic acid were subsequently added using a roller mill operating at 90°C to
100°C. î ese blends were t en compression molded and cured to form 2
t ick plaques in a curing p ress. î e cure temperature was set at 160°C and cure
time applied was t90 + 5 (5 minutes plus t e time required to reac 90 % cure as
measured by an oscillating disk cure meter).
BIMSM/MWNî nanocomposites wit a range in weig t fraction of MWNî were
produced. î ermogravimetric analysis (îGA) was conducted on all samples to verify
t e final material composition and found t e prepared samples to possess a
weig t fraction close to t at blended. îable 1 summarizes t e compositions.
Scanning electron microscopy on freeze-fractured surfaces as well as transmission
electron microscopy (îEM) (Figure 1) revealed good dispersion wit random
distribution
and orientation of MWNîs wit in t e elastomeric matrix.


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Uniaxial tension and uniaxial compression tests were conducted on all
material
compositions. îests were conducted to large strains at constant engineering strain
rate (displacement rate divided by specimen gage lengt ) on a Zwick/Roell Z010
single axis screw mac ine. Specimens were cut from t e 2mm t ick molded plaques.
îensile specimens were rectangular of dimension 60mmx5mm. îwo types of grips
were used. For moderate strains (strains less t an 0.70) tensile grips wit surfaces
designed to test relatively t in compliant polymers were u sed; one surface is
aluminum
and t e mating surface is a polyuret ane. For larger strains (to final failure)

Zwick grip 8122 wit a spring -loaded grip action was used to avoid any sliding
at very large deformation. î e transverse displacement was monitored optically
during extension and t e axial strain was determined assuming incompressibility.
Load-unload-reload tests were conducted to quantify any ysteresis and/or
straininduced

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softening of t e materials. îests were also conducted at different engineering
strain rates to quantify any rate dependence. Some samples were also extended
until failure to examine t e effect of MWNîs on t e tensile stress and strain at
break. Compression specimens were cylinders of nominally 8mm in diameter and
6mm in eig t (accomplis ed by stacking t ree 2mm t ick cylinders). î in îeflon
s eets were placed between t e specimens and t e compression platens to reduce
friction; additionally
a powder composed of PîFE and PE was placed between t e
specimens and t e îeflon s eets. Load-unload-reload tests were conducted. îests
were also performed at different engineering strain rates. îensile and compression
data are reported in terms of true stress (load divided by current deformed
crosssectional
area) and true strain (t e natural logarit m of t e current axial gage lengt
divided by t e initial gage lengt ). Since t e bulk modulus of rubber is substantially
(i.e. 2-3 orders of magnitude greater) t an t e s ear modulus of rubber
t e
deformed cross-sectional area during unia xial tension and compression can be
estimated
from t e measured axial strain assuming incompressibility. A minimum of
at least t ree tests were conducted for eac loading situation; stress -strain curves
were repeatable in all cases and
in t e case of uni axial tension
strain-to-break
measurements were also repeatable for all data sets.
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Uniaxial tension true stress-strain data are s own in Figure 2. Figure 2a
reveals t e
elastomer matrix material to ex ibit a small level of ysteresis (tests at different
strain rates
not s own
revealed negligible strain rate sensitivity); t e stiffness and
t e ysteresis are bot observed to increase wit an increase in MWNî content.
î e ysteresis was furt er quantified t ro ug cyclic load-unload-reload tests
(representative
data are provided in Appendix A) and was found to be a Mullins effect
(see
Mullins (1947
1969)
Mullins and îobin (1954
1965)) w ereby t e ysteresis
was nearly absent after t e first cycle. Figure 2b depicts t e uniaxial tensile data
to large strain up to final failure w ere t e stiffening wit strain is observed to
increase
wit increase in MWNî content and t e strain to failure was also found to
increase wit increase in MWNî content (failure occurre d in t e gage lengt of t e
specimen and was not a grip-induced failure). î e inset of Figure 2b s ows t e initial
modulus as a function of wt% MWNî w ere t e 12.2wt% MWNî -elastomer
composite as a modulus 2.5 times t at of t e neat elastomer.Comparatively
a
similar
weig t fraction of carbon black filler would provide a modulus 1.3 times t at of
t e neat elastomer (e.g.
Bergstrom and Boyce (1999)). î ese data s ow an ability
to substantially increase t e tensile stiffness and retain t e stiffness en ancem ent
during large strain deformation as well as t e ability to increase t e tensile strengt
and t e tensile strain-to-break.

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Uniaxial compressive true stress-true strain data are s own in Figure 3a
revealing
t e same basic trends as observed in t e tensile data. î e overall stiffness and t e
stiffening wit strain are seen to increase wit MWNî content. î e neat elastomer
ex ibits a low level of ysteresis; t e nanocomposite ysteresis increases wit an
increase in MWNî content. î e compressive stress-strain be avior is compared
to t e tensile stress-strain be avior in Figure 3b for t e neat elastomer and for t e
6.1wt% and 12.2wt% MWNî-elastomers. î ese data s ow t e classic differences
seen in elastomer compression vs tension stress-strain data. In an elastomer
t is
difference is attributable to t e evolution in alignment of t e underlying molecular
network wit different states of strain. î e network aligns in a biaxial orientation
w en subjected to uniaxial compression an d aligns in a uniaxial orientation w en
subjected to uniaxial tension. Here
t e MWNîs do not alter t is compression vs
tension dependence of t e stress -strain be avior and
indeed
must also orient wit
deformation as discussed furt er in t e modeling sec tion.


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î e tensile and compression stress vs strain data were furt er reduced to

plots
of strain energy density vs axial strain. Figure 4 s ows t e strain energy density
results for all material compositions for uniaxial tension (Figure 4a) and uniaxial
compression (Figure 4b). î is data is t en once again reduced to provide a plot of
t e strain energy contribution of t e MWNîs
´

to t e composite be avior.
Here
we assume a simple rule of mixtures approac giving:

´  ´
  
´ or ´
  ´

 ´  

Ñ

W ere ´ is t e strain energy density of t e composite
´ is t e strain energy
density
of t e elastomer
and f is t e volume fraction of t e MWNîs. Figure 5 depicts ´

vs. axial strain for uniaxial tension (Figure 5a) and for uniaxial compression
(Figure 5b) as obtained by reducing t e data for all compositions. Note t at
t e curves obtained from eac composition are nearly coincident for t e tensile
data as well as for t e compression data and t us reflect t e unit contribution of
t e MWNîs to t e deformation be avior of t e composite. î e coincidence of
t ese data supports t e use of equation 2 as a surprisingly good first approximation
to assess and model t e contribution of MWNîs to t e composite be avior.
î is form of t e reduced data will be s own to be instrumental in constructing t e
microstructurally-informed constitutive model for t ese nanocomposites .
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Our experimental results indicate t at t e strain energy density
´
of t e

MWNîelastomer composites under consideration can be decomposed into a
contribution from t e elastomer
´
and a contribution from t e MWNîs
´


using t e simple rule of mixtures approac given earlie r in equation (1). î is
representation
is p ysically realistic for t is case of a low to modest volume fraction of wavy
(bent) fibers distributed wit in a compliant elastomeric matrix
w ere t e fibers
will essentially deform wit t e matrix
unbending and rotating wit t e imposed
deformation. î e wavy fibers offer little disturbance to t e basic deformation field
of t e elastomer (in ot er words
t ere is not a significant amplification of strain in
t e matrix) and ence t e elastomer deformation can be d irectly described by t e
macroscopic deformation gradient.


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î e BIMSM elastomer is a crosslinked molecular network and was found to

ex ibit
little time-dependence. î e Mullins effect (quantified in t e data presented in
Appendix A) is small and can be modelled using t e Qi and Boyce (2004) model

but t is effect is neglected in t is paper in order to more clearly focus on t e primary
contributions of t e MWNîs to t e mec anical be avior. Hence
t e matrix
is approximated as yperelastic and modeled using t e A -B eig t-c ain network
model of rubber elasticity. î e A -B model represents a random isotropic molecular
network as eig t c ains emanating from a central junction point to t e corners of a
cube; t e cube is taken to b e aligned wit t e principal axes of stretc . In t is
representation

eac c ain stretc es by t e root mean square of t e imposed stretc and also rotates
towards t e axis(es) of maximum principal stretc (es) (Figure 6). î us
t e eig t-
c ain model captures t e essence of t e p ysics of deformation of an isotropic
random network as verified by
its ability to predict t e stress-strain be avior of an elastomer under different states
of strain. î e strain energy function for a compressible version of t e eig t -c ain
model (see
Bisc off et al. (2001)) is given by:

 
´       
#  %& "
'
   !" $
W ere

  ()* + , -   ./* 0! -   ()* + , -
 

W ere ()* is t e inverseLangevin function wit

(    123  
0
"  ./4 and %& is t e bulck modulus.
î e Cauc y stress is t en obtained by differetiating ´
giving:

' 789 789 => @

5  < or 5   ?A <
 G  %& "

6 7 :; 76 46 BCDEF

î e material properties were fit to t e BIMSMtensile data
giving  

HI!JKLM and   $HH ; t e bulk modulus was taken to be 3GPa. î e model fit is
s own to
capture t e tensile be avior in Figure 7. As is well known
elastomeric stress -strain
be avior is strongly dependent on t e state of imposed deformation (see
for
example

îreloar (1975)
Arruda and Boyce (1993))
w ere t e greatest contrast is seen in
comparisons of uniaxial tension to uniaxial compression (or
alternatively
uniaxial
tension and equibiaxial tension). î e model prediction of t e uniaxial compressio n
be avior based on its fit to t e tensile data is also s own in Figure 7
demonstrating
t e ability of t e model to capture t e matrix be avior. î e small discrepancy
between model prediction and experiment is most likely due to our neglecting t e
small amount of ysteresis and Mullins effect (see Appendix A) ex ibited by t is
material. However
for purposes of examining t e effect of CNîs on t e uniaxial
tension and compression be avior
t is discrepancy is small.

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