Time-dependent nanoindentation behavior of high elastic modulus

dental resin composites

Yijun Wang and Isabel K. Lloyda)
University of Maryland, Department of Materials, College Park, Maryland 20742

(Received 24 September 2009; accepted 30 November 2009)

Nanoindentation and the viscous-elastic–plastic (VEP) model developed by Oyen and

Cook for lightly filled thermoplastic polymer composites were used to characterize the
elastic modulus, hardness, and viscoelastic response of a new high elastic modulus dental
resin composite. The VEP model was used because loading rate studies indicated a
viscous component in the loading/unloading response of our highly filled, thermosetting
acrylic resin composites. Increasing the volume fraction of our high modulus filler
increased the elastic modulus and hardness and decreased the viscous response in our
composites. Coupling the filler and resin matrix with a commercial coupling agent like
Metaltite or MPTMS (3-methacryloxypropyltrimethoxysilane) that ionically bonds to the
filler and covalently bonds to the matrix decreases the viscous response and increases the
hardness of the composite. The coupling agents did not affect the elastic modulus. The
ability of the VEP model to predict load–displacement trajectories and the correlation of
the elastic modulus and hardness values determined from the VEP model with those from
the direct continuous stiffness measurement mode nanoindentation measurements indicate
that the VEP model can be extended to highly filled, thermosetting systems. This is
valuable since the potential to predict elastic, plastic, and viscous contributions to
behavior should be valuable in the design and understanding of future highly filled resin
composite systems.

I. INTRODUCTION associated with viscous flow is of concern. Viscous flow

Dental resin composites, routinely composed of a mix- during cyclic loading at oral temperatures causes perma-
ture of silanized silicate fillers with an acrylic monomer nent dimensional changes. This can lead to enhanced
matrix, have served clinically as dental restorations for stresses on the tensile surface of brittle crowns that rely
decades, i.e., filling cavities in teeth, or fixing/joining on the support of the composite. Huang et al.11 described a
crowns to the supporting tooth structure. Extensive combined experimental and computational study of con-
research has been conducted to understand the microstruc- tact fatigue mechanisms in sandwich structures, similar to
tural, physical, and mechanical properties of dental resin the layer model of Lawn and co-workers.12 It showed that
composites and, ultimately, to overcome the failure prob- stress build-up on the bottom surface of a ceramic crown
lems associated with these properties. Recent clinical and may result from several deformation mechanisms includ-
laboratory results have shown that the elastic modulus of ing viscous deformation of the composite join layers, plas-
supporting resin composite adhesives has direct influence tic deformation in dental cement due to ratcheting, and
on the flexural failure of all-ceramic dental crowns.1–5 subcritical crack growth in the ceramic layer. Although
This has focused attention on the elastic modulus of resin the results from their finite element model suggested that
composites. Thus, we developed a high elastic modulus viscous deformation alone was not sufficient to cause
resin composite; reinforced by stiff alumina nanoparticles cracking in the model crown layer, it intensified the
rather than the conventional silicate fillers.6 Lee et al.7–10 stress.11 Viscous flow was strongly related to temperature,
have demonstrated that fracture in a top brittle layer was humidity, and rate and frequency of loading.13,14 Thus, a
suppressed by substituting higher modulus resin compos- static test at room temperature under dry conditions is not
ites for more compliant ones. sufficient to understand behavior or model performance in
However, other properties also influence the perfor- the mouth. Resistance to fatigue under cyclic loading is an
mance of resin composite adhesives. In particular, creep important characteristic for dental composites. To provide
realistic data for evaluation, fatigue tests should be done in
a)
Address all correspondence to this author.
a wet environment with typical oral temperatures. In addi-
e-mail: illoyd@umd.edu tion, it is important to understand mechanisms that may
DOI: 10.1557/JMR.2010.0070 contribute to fatigue, such as viscoelastic deformation.

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 Y. Wang et al.: Time-dependent nanoindentation behavior of high elastic modulus dental resin composites

The viscoelastic properties of dental resin composites Corp., Tokyo, Japan), a dental primer used to improve
and other polymer composites are commonly explored adhesion between resins and ceramics. Metaltite con-
using dynamic mechanical analysis.13,15 It is a good tains 6-methacryloyloxyhexyl 2-thiouracil-5-carboxylate
method to investigate the effects of temperature on be- (MTU-6) in an ethanol solution. Metaltite-treated filler
havior as it clearly indicates the glass transition tempera- had 3 mass% of Metaltite applied to the surface before
ture. It is also used to determine the modulus and the mixing with the monomer solution. After treatment, the
time dependence of the response, the loss tangent, and a filler particles were washed with ethanol to remove redun-
function of external factors such as temperature and dant or unbonded coupling agent. The dried powder was
aging time. Our study examined the effect of microstruc- then gradually added into the monomer solution.
ture, namely filler loading and filler bonding to the The second coupling agent was 3-methacryloxypro-
matrix, on the viscoelastic behavior of our new high pyltrimethoxysilane (MPTMS; Sigma-Aldrich). It is a
modulus composites.6 We used a new nanoindentation- silanizing agent commonly used to provide a chemical
based approach developed by Oyen and Cook16–18 to bond between silicate fillers and an organic matrix. The
characterize viscoelastic response to allow us to separate alumina was silanized in a rotary evaporator by mixing it
viscoelastic and plastic contributions to the observed with MPTMS in cyclohexane with n-propylamine as a
behavior. This method combines measurement of load– catalyst in a 90
C water bath until dry. The dried powder
displacement behavior and development of a viscous- was then added to the monomer solution.
elastic–plastic (VEP) analytical model with experimentally In both cases, the mixture of filler and monomer were
determined constants. This approach is unique because cured in an oven at 120
C for about 6 h. The detailed
the VEP model has not been previously applied to highly fabrication procedure and microstructural characteriza-
cross-linked, highly filled thermoset resin composites, tion are described elsewhere.6 These studies indicated
and there has been limited work using nanoindentation that the alumina nanoparticles were well dispersed with
to characterize dental composites. Drummond19 used the composite. The compositions of the specimens eval-
low-load nanoindentation to evaluate elastic modulus uated in this study are listed in Table I.
and hardness of highly filled dental composites. The
small loads produced small indents and produced large B. Nanoindentation testing
variations in results because the composites contained
microparticles with a size similar to the indents. This A Nano Indenter XP (MTS Nano Instruments, Oak
process allowed differentiation of the properties of fillers Ridge, TN) with a standard Berkovich diamond tip was
and resin. However, it did not provide information regard- used for the nanoindentation tests. The Nano Indenter
ing viscoelastic behavior as only one loading/unloading instrument is located in a clean room of Class 10,000
rate used (10 s/cycle). with 24  0.25
C temperature control and 40 %  5%
relative humidity control. All the results presented for a
given composition were done on a single sample to min-
II. MATERIALS AND EXPERIMENTAL
imize effects from minor processing variations. How-
PROCEDURE
ever, 2–3 additional samples of each composition were
A. Materials and composition fabricated and the same tests were repeated on them to
The resin system was 49.0 mass% bisphenol A glycidyl verify behavioral characteristics and reproducibility.
methacrylate (Bis-GMA; Esstech, Essington, PA) and Cross-linked composites were cut, ground, and polished
49.0 mass% triethylene glycol dimethacrylate (TEGDMA; to a 0.5- or 1-mm diamond finish to provide a flat and
Sigma-Aldrich Inc., St. Louis, MO) with 2.0 mass% parallel surface for testing.
benzoyl peroxide [an aqueous solution of 75% benzoyl The tests to characterize the viscoelasticity of the
peroxide (BPO; Fisher Scientific, Waltham, MA)] as the composites were performed at room temperature in the
polymerization initiator. Nanosized alumina (NanoTek load-control mode of the machine. A triangle-wave
Aluminum Oxide, Nanophase Technologies Corporation, loading–unloading cycle was applied, as shown in Fig. 1.
Romeoville, IL) was used as the filler. The manufacturer The test time was equally divided between loading and
characterized this alumina as an equiaxed powder with an unloading. Total test times were 30, 100, or 300 s. The
average particle diameter of 47 nm and an overall density
of 3.6 g/cc. Both the manufacturer’s specifications and our TABLE I. Sample composition and abbreviation.
measurements indicated a specific surface area Brunauer–
Sample design Coupling agents Filler vol%
Emmett–Teller analysis (BET) of 35 m2/g. The BET mea-
surements and scanning electron microscopy of fracture PR Pure resin None 0
surfaces6 support the manufacturer’s measurements. UT Untreated None 46.6
MT Phosphate coupled Metaltite 47.0
The surface of alumina filler was modified by two SA Silane coupled MPTMS 57.6
types of coupling agents. One was Metaltite (Tokuyama

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 Y. Wang et al.: Time-dependent nanoindentation behavior of high elastic modulus dental resin composites

FIG. 1. Schematic plot of triangle wave of loading–unloading with

maximum load, Pmax. The Pmax is 300 mN and the tMax is 30, 100, or
300 s.
FIG. 2. Instrumented indentation load (P)-displacement (h) traces for
peak load, Pmax, was 300 mN for all tests. The maximum PR (pure resin) and UT (untreated) by Berkovich indentation, plotted
with hollow symbols and filled symbols, respectively. Triangle-wave
load was chosen to produce indentations that would be
loading using a rise time of 15, 50, and 150 s for each indentation is
representative of bulk behavior in the stiffest, highest vol- shown with triangles, circles, and stars, respectively. The difference in
ume fraction filler composites. The load–displacement maximum displacement as a function of loading rate is characterized
traces were recorded for further analysis. The difference by D.
in maximum displacement as a function of loading rate for
each sample type, Dtype, was noted because it is a visual
indicator of viscoelastic response.
Samples were also tested using the continuous stiff-
ness measurement (CSM) mode. Here, a small, high fre-
quency oscillation of the force signal is used to obtain the
elastic modulus\and hardness of the composites directly.
Indents were made at the center of the specimens and
spaced far enough apart (>300 mm) to avoid interaction
with each other. Nine indents were made on each sample.
The maximum load, Pmax, was about 2 N and the
resulting medians were about 50 mm. They were large
enough to ensure the modulus and hardness were repre-
sentative of bulk behavior rather than local composition
and microstructure. The elastic modulus, E, and hard-
ness, H, versus penetration depth, were directly taken
from the machine’s software. The analysis was based on
the methods developed by Oliver and Pharr.20
FIG. 3. Instrumented indentation load (P)-displacement (h) traces for
UT (untreated) and MT (phosphate coupled) by Berkovich indenta-
III. EXPERIMENTAL RESULTS AND DISCUSSION tion, plotted with hollow symbols and filled symbols, respectively.
Triangle-wave loading using a rise time of 15, 50, and 150 s for each
Figures 2–4 illustrate representative load–displacement indentation is shown with triangles, circles, and stars, respectively.
behavior for our composites as a function of loading rate.
While the curves represent experiments on individual
samples, the behavior is representative of measurements and 150 s, half of the total testing time. Thus, due to the
on at least three composite samples with the same compo- fixed peak load, 300 mN, the load–displacement
sition. The fillers were well dispersed in all the samples response of indentation was tested at three rates, 20, 6,
and the peak loads were large enough to produce indenta- and 2 mN s1. The time-dependent behavior was pro-
tions that represented bulk behavior rather than the behav- nounced for both samples. For the unfilled resin, PR, the
ior of just the filler or just the resin matrix.6 penetration depth at peak load varied with the time to
Figure 2 shows the load–displacement curves of two reach peak load. Figure 2 shows that PR exhibited an
samples, pure resin (PR) and untreated (UT), indicated increased maximum displacement into the sample with
by hollow symbols and filled symbols, respectively. For increasing rise time. In the 30-s loading–unloading
each sample, from left to right, the rise time was 15, 50, curve, the indentation fingerprint was similar to pure

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 Y. Wang et al.: Time-dependent nanoindentation behavior of high elastic modulus dental resin composites

ing between the filler and matrix by a coupling agent will

decrease this part of the viscous response.
In Fig. 3 the load–displacement behavior of UT is
compared with MT, a similarly filled sample (46.6 and
47 vol% filler, respectively) where the filler was coupled
to the matrix. Both were tested by the same procedure.
Note that MT has a smaller maximum displacement at all
loading rates and a smaller D. This indicates that the
composite with the Metaltite-treated filler, MT, had less
viscous flow. Because both of the composites have the
same volume fraction of filler and matrix, this supports
the hypothesis that the flow between the filler and the
matrix as well as deformation in the matrix contribute to
FIG. 4. Comparison of the samples in Table I in terms of maximum the time-dependent behavior observed for uncoupled
penetration depths at loading time of 300 s, left coordinate, and dis- composites. Similar behavior was observed for compos-
placement shifts between 30 and 300 rise times, right coordinate. The ites with silanized filler. The coupling agents in this
maximum load is 300 mN.
study were chosen since they were capable of reacting
with the hydroxyl groups on the surface of the filler and
elastic–plastic behavior.17 In the 300 s curve for PR, the copolymerizing with the methacrylate vinyl group in the
maximum penetration occurred after the load maximum resin matrix.24 This type of bonding between the filler
was reached and the unloading slope was negative at the and matrix is much stronger than the hydrogen bonding
beginning of the unloading curve. This is characteristic or van de Waals forces that connect the untreated filler to
of a strong viscous response.17 A monomer system such the matrix. Thus, when stress is applied, movement in the
as Bis-GMA and TEGDMA that produces thermoset interfacial region of the coupled composite is impeded.
polymers with a highly cross-linked network, would This indicates that the stress applied to the composites is
be expected to exhibit less viscous flow derived from more effectively transferred to the stronger and stiffer
the rearrangement and sliding of polymer chains than filler when the filler is coupled to the matrix.
a thermoplastic polymer because the neighboring Figure 4 compares the maximum penetration depth for
chains are usually cross-linked. However, since uncross- a loading time of 300 s and the displacement, D, for the
linked polymer segments exist, viscous flow from re- samples in Table I. As you move from left to right in
arrangement and sliding of uncross-linked segments is Fig. 4, D decreases indicating that viscous flow decreases
possible. Thus, even for thermoset polymers, a viscous as filler is added and the filler is coupled to the matrix.
response is not unexpected. Both increased filler fraction and coupling the filler to
Comparing the behaviors of PR and UT in Fig. 2, UT the matrix attenuate polymer mobility and thus decrease
exhibits less displacement at maximum load on the load- viscous flow by confining uncross-linked polymer seg-
ing–unloading curves for loading at different rates indi- ments near the filler and cross-linking the treated filler
cated by D. This indicates there was less viscous flow in into the matrix. Figure 4 also shows that MT, the coupled
the alumina reinforced composite UT. This is attributed sample has a smaller displacement depth than UT, the
to the decrease in the organic fraction of the alumina/ uncoupled sample, at the same loading rate and filler
resin composite where flow could occur. However, even fraction. This implies that the coupled samples have
with only about 45 vol% polymer, the organic fraction in higher hardness than uncoupled composites.
UT still plays an important role, as indicted by the vis- Dental resin adhesive composites are used in a
cous response. demanding oral environment, i.e., aqueous conditions
In polymer composites, the interfacial region between with varying pH, temperature variations, and over-
the filler surface and the point in the polymer matrix where stresses. Thus, a strong bond between filler and polymer
the matrix exhibits bulk behavior is often treated as a is desirable to protect against degradation or swelling
phase.21 This means that the composite can be treated as induced by the intrusion of saliva and acids along the
if it has three phases, inorganic filler, organic matrix, and interface between filler and polymer. A strong bond is
the interfacial region. The properties in the interfacial also necessary to minimize the effect of temperature
region are primarily controlled by the contact between the variation on viscous flow in the polymeric matrix.
filler and the polymer. This contact then influences the Finally, a strong filler-matrix bond has the potential to
properties of the composite.22,23 We hypothesize that at reduce the change of dimensions in resin composites
least some of the viscous flow observed in our filled com- associated with viscous flow or creep under long-term
posites resulted from flow in the interfacial region cyclic loading in the mouth. Thus, increasing bond
between the filler and bulk polymer. Enhancing the bond- strength should decrease the risk of restoration failure

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 Y. Wang et al.: Time-dependent nanoindentation behavior of high elastic modulus dental resin composites

due to loss of support from resin composite adhesives. On unloading,

Further experiments are needed to confirm that coupling
P ¼ Pmax ð2  t=tR Þ; tR  t  2tR : ð7Þ
agents minimize composite degradation and creep under
oral conditions. By substituting the load, P, from Eq. (6) into Eqs. (2),
(3), and (4), the total displacement on loading is
IV. VISCOUS-ELASTIC–PLASTIC MODEL

Pmax t 1=2
A. VEP model introduction hR ðtÞ ¼ hE þ hP þ hV ¼
a2 E tR
The complexity of microstructure of polymer compos-

1=2
Pmax t 1=2 2 Pmax t3
ites makes it challenging to identify the mechanisms of þ þ : ð8Þ
fracture or deformation associated with viscous flow quan- a1 HtR 3 a2 E t2 tR
titatively. In our study, the VEP developed by Cook and And similarly, the total displacement on unloading is
co-workers16 was used to analyze the nanoindentation data " #1=2
and infer the elastic, plastic, and viscoelastic properties Pmax ð2  t=tR Þ
(time scale for viscous flow) of our composites. This h ðtÞ ¼ hE þ hP þ hV ¼
U
a2 E 
information can then be used to understand deformation
! !1=2
mechanisms in our highly filled resin composites.
Pmax 2tR Pmax
Their model is described below. It consists of three þ þ
elements: elastic, plastic, and viscous responses, a1 H 3t a2 E
connected in a pseudo-Maxell series.17,20 The total dis-
 ½2  ð2  t=tR Þ3=2  : ð9Þ
placement of the indenter is the sum of individual dis-
placement elements, By means of fitting the experimental {h, t} trajectory
h ¼ hE þ hP þ hV ; ð1Þ of one of the tests into Eqs. (8) and (9), the parameters
in the equations, such as E, H, and t can be extracted.
where hE, hP, and hV are the elastic, plastic, and viscous These parameters may then be used to predict the load–
displacements, respectively. For each element, consider- displacement curves for other tests under different load-
ing the indentation conditions and pyramidal geometry, ing rates.
the load–displacement is subjected to quadratic relation-
ships instead of conventional linear ones.17,20 Thus, the
constitutive responses of load–displacement for each ele- B. Fitting and simulations
ment are Figure 5 shows a representative example of using the
PE ¼ a2 E h2E ; ð2Þ parameters derived from fitting the 300 s curve to fit the

PP ¼ a1 Hh2P ; ð3Þ

PV ¼ a2 E t2 ðdhV =dtÞ2 ; ð4Þ

where PE, PP, and PV are loads associated with elastic,
plastic, and viscous responses, E* is the indentation mod-
ulus given by E ¼ E=ð1  n2 Þ, n is the Poisson ratio,
H is the true hardness, t is the time constant for viscous
flow, and a1 and a2 are indenter geometry constants
given by a1 = ptan2c for an assumed rigid conical
indenter of effective included angle 2c and a2 =
ptanc/2b.16
The load is common to all elements,16
P ¼ PE ¼ PP ¼ PV : ð5Þ
For triangle-wave loads, on loading the load is
expressed as FIG. 5. Instrumented indentation load (P)-displacement (h) traces of
MT were displayed with hollow triangles, circles, and stars according
P ¼ Pmax ðt=tR Þ; 0  t  tR ; ð6Þ to various rise time. The predictions were made using the VEP model
for various observation times, 30, 100, and 300 s, plotted with dashed,
where t is the time, tR is the rise time to reach peak load, dotted, and solid lines, respectively. The parameters used in the model
Pmax. were extracted by fitting unloading curve of 300 s test.

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 Y. Wang et al.: Time-dependent nanoindentation behavior of high elastic modulus dental resin composites

30 and 100 s curves. Here, the experimental data for MT C. Mechanical properties derived from the VEP
are plotted with hollow symbols. The simulated {P, h} model
responses from the VEP model are indicated with In the VEP model, fitting and simulation give a way to
dashed, dotted, and solid lines for the 30, 100, and 300 s estimate the mechanical properties of the composite, i.e.,
tests, respectively. The 300 s data were used to determine E, H, and t. In Table II, the VEP inferred elastic modulus
the P and h from the model so the model curve overlays matches well with data obtained from direct nanoinden-
the data almost exactly. The loading and unloading tation tests.6 This gives confidence in the other mechan-
curves predicted by the VEP model fit the100 s data well ical properties derived from the data using the VEP
indicating that the model provides a good prediction for model. The similarity of the elastic modulus determined
the deformation behavior of the composite. The fit is not from the VEP model and direct nanoindentation measure-
as good for the 30 s test. This may be explained by ments in conjunction with the fit of the data to the 100 s
Deborah number effect, i.e., the apparent time constant tests indicate that the VEP model can be used with highly
describing material flow behavior varies with the obser- filled highly cross-linked network polymer composites.
vation time of the test.16 Briefly, this is related to the fact This is significant since the model was derived for ther-
that there are multiple flow mechanisms involved during moplastic polymers or composites with low filler loading
the loading–unloading event and they have different time and has not been applied to highly filled systems.16,25
constants. Thus, when the loading–unloading time changes; The VEP calculated hardness (true hardness) data
the contribution from each mechanism changes as well. were much greater than those obtained from direct tests.
In a heavily particle-filled system like ours, with limited This issue has been discussed in the literature. In the
numbers of tests, it is hard for the simple VEP model to VEP model, the total irreversible deformation consists
predict accurate load–displacement response for each of two parts: plastic and viscous deformation. The true
potential deformation mechanism. However, it should hardness from the model is based on the plastic deforma-
be noted that for longer rise times, additional, slower tion, viscous deformation is excluded. In the direct CSM
mechanisms such as the matrix flowing past and then mode tests, the total irreversible deformation determined
breaking free from a particle are likely to be involved and the hardness. Thus, the hardness values were lower since
they may contribute more to the displacement. In other they included both plastic and viscous deformation.
words, as the observation time increases, the slower flow Other researchers have reported the same finding.25 This
mechanisms contribute more to overall displacement. In means that it is important to specify what is meant by
this study, the parameters used for prediction were hardness when the VEP model is used.
extracted from a single 300 s test, thus the parameters in The numbers within brackets are E and H obtained
the VEP model represented displacements from each from direct testing by nanoindentation. The numbers
mechanism active during the 300 s test. However, when without brackets are the values E and H obtained from
rise time is shorter, some deformation mechanisms will VEP modeling (the H is also called true hardness).
not be active, so that using load and deformation parame- The ability to separate the plastic and viscous contri-
ters derived from the 300 s test would tend to over-predict butions to the observed displacement provides a way to
displacement as was observed for loading the 30 s curve. estimate the relaxation time for viscous flow in resin
Thus, the VEP model is limited by both its simplicity and composites. This is important because the relaxation time
the nature of flow with multiple time constants. Using a provides insight into the coupling between the filler and
single time constant model, it is hard to predict mechanical the resin matrix. The relaxation times, t, are presented in
behavior that stems from multiple mechanisms with dif- Table II. For PR, the t was about 156 s so the unloading
ferent time scales. It was also found by Cook and Oyen16 times (15, 50, and 150 s) corresponded to about 1/10, 1/3,
that the VEP model did not provide a good fit to the data and 1/1 of t. For sample SA, the t was about 420 s, so the
for extreme cases. In their study, the model fitting to the unloading times correspond to about 1/28, 1/8.4, and
data for very long rise times was poor. Thus, further work 1/2.8 of t. Thus, viscous flow would not play as dominant
to include time constants for mechanisms operative at a role in behavior for SA because the time constant
different time scales would enhance the predictive capa- is much longer than the test period indicating that the
bility of the model.

TABLE II. E, H, and t of various resin composites.

Samples PR UT MT SA
E (GPa) 4.7 (4.6) 21.0 (20.4) 22.1 (21.5) 31.5 (31.2)
H (GPa) 0.97 (0.244) 2.50 (0.753) 3.27 (0.934) 5.68 (1.340)
t (s) 156 259 331 420
Filler fraction (vol%) 0 46.6 47.0 57.6

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 Y. Wang et al.: Time-dependent nanoindentation behavior of high elastic modulus dental resin composites

viscous flow mechanisms are too slow to contribute sig- National Institute of Standards and Technology (NIST)
nificantly to the observed deformation. From a practical for their helpful discussions and use of their equipment.
viewpoint, increased relaxation time should correlate with We also thank Prof. Van Thompson of New York Uni-
decreased creep and thus better long-term performance. versity for helpful discussions. Financial support was
In our experiments the relaxation time increased as the provided by National Institutes of Health (NIH) Grant
volume fraction of inorganic filler increased and with the NIDCR PO1 DE10976. This work was done in partial
addition of effective coupling agents. For particle-filled fulfillment of dissertation requirements for Yijun Wang.
composites with a similar degree of cross-linking, it We also thank ESSTECH for donating BisGMA for the
makes sense that relaxation time would increase and initial materials studies.
viscous flow would decrease as the volume fraction of
filler is increased, because filler particles (i) decrease the
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ACKNOWLEDGMENTS of elasticity of resin-based materials. Dent. Mater. 18, 64 (2002).
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We would like to acknowledge Dr. Robert Cook, Dr. ical properties measurement of polymeric materials. Int. J. Mater.
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