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-
ture of silanized silicate fillers with an acrylic monomer
matrix, have served clinically as dental restorations for
decades, i.e., filling cavities in teeth, or fixing/joining
crowns to the supporting tooth structure. Extensive
research has been conducted to understand the microstruc-
tural, physical, and mechanical properties of dental resin
composites and, ultimately, to overcome the failure prob-
lems associated with these properties. Recent clinical and
laboratory results have shown that the elastic modulus of
supporting resin composite adhesives has direct influence
on the flexural failure of all-ceramic dental crowns.1–5
This has focused attention on the elastic modulus of resin
composites. Thus, we developed a high elastic modulus
resin composite; reinforced by stiff alumina nanoparticles
rather than the conventional silicate fillers.6 Lee et al.7–10
have demonstrated that fracture in a top brittle layer was
suppressed by substituting higher modulus resin compos-
ites for more compliant ones.
However, other properties also influence the perfor-
mance of resin composite adhesives. In particular, creep
a)
Address all correspondence to this author.
e-mail: illoyd@umd.edu
DOI: 10.1557/JMR.2010.0070
during cyclic loading at oral temperatures causes perma-
nent dimensional changes. This can lead to enhanced
stresses on the tensile surface of brittle crowns that rely
on the support of the composite. Huang et al.11 described a
combined experimental and computational study of con-
tact fatigue mechanisms in sandwich structures, similar to
the layer model of Lawn and co-workers.12 It showed that
stress build-up on the bottom surface of a ceramic crown
may result from several deformation mechanisms includ-
ing viscous deformation of the composite join layers, plas-
tic deformation in dental cement due to ratcheting, and
subcritical crack growth in the ceramic layer. Although
the results from their finite element model suggested that
viscous deformation alone was not sufficient to cause
cracking in the model crown layer, it intensified the
stress.11 Viscous flow was strongly related to temperature,
humidity, and rate and frequency of loading.13,14 Thus, a
static test at room temperature under dry conditions is not
sufficient to understand behavior or model performance in
the mouth. Resistance to fatigue under cyclic loading is an
important characteristic for dental composites. To provide
realistic data for evaluation, fatigue tests should be done in
a wet environment with typical oral temperatures. In addi-
tion, it is important to understand mechanisms that may
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
and other polymer composites are commonly explored
using dynamic mechanical analysis.13,15 It is a good
method to investigate the effects of temperature on be-
havior as it clearly indicates the glass transition tempera-
ture. It is also used to determine the modulus and the
time dependence of the response, the loss tangent, and a
function of external factors such as temperature and
aging time. Our study examined the effect of microstruc-
ture, namely filler loading and filler bonding to the
matrix, on the viscoelastic behavior of our new high
modulus composites.6 We used a new nanoindentation-
based approach developed by Oyen and Cook16–18 to
characterize viscoelastic response to allow us to separate
viscoelastic and plastic contributions to the observed
behavior. This method combines measurement of load–
displacement behavior and development of a viscous-
elastic–plastic (VEP) analytical model with experimentally
determined constants. This approach is unique because
the VEP model has not been previously applied to highly
cross-linked, highly filled thermoset resin composites,
and there has been limited work using nanoindentation
to characterize dental composites. Drummond19 used
low-load nanoindentation to evaluate elastic modulus
and hardness of highly filled dental composites. The
small loads produced small indents and produced large
variations in results because the composites contained
microparticles with a size similar to the indents. This
process allowed differentiation of the properties of fillers
and resin. However, it did not provide information regard-
ing viscoelastic behavior as only one loading/unloading
rate used (10 s/cycle).
II. MATERIALS AND EXPERIMENTAL
PROCEDURE
A. Materials and composition
The resin system was 49.0 mass% bisphenol A glycidyl
methacrylate (Bis-GMA; Esstech, Essington, PA) and
49.0 mass% triethylene glycol dimethacrylate (TEGDMA;
Sigma-Aldrich Inc., St. Louis, MO) with 2.0 mass%
benzoyl peroxide [an aqueous solution of 75% benzoyl
peroxide (BPO; Fisher Scientific, Waltham, MA)] as the
polymerization initiator. Nanosized alumina (NanoTek
Aluminum Oxide, Nanophase Technologies Corporation,
Romeoville, IL) was used as the filler. The manufacturer
characterized this alumina as an equiaxed powder with an
average particle diameter of 47 nm and an overall density
of 3.6 g/cc. Both the manufacturer’s specifications and our
measurements indicated a specific surface area Brunauer–
Emmett–Teller analysis (BET) of 35 m2/g. The BET mea-
surements and scanning electron microscopy of fracture
surfaces6 support the manufacturer’s measurements.
The surface of alumina filler was modified by two
types of coupling agents. One was Metaltite (Tokuyama
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Corp., Tokyo, Japan), a dental primer used to improve
adhesion between resins and ceramics. Metaltite con-
tains 6-methacryloyloxyhexyl 2-thiouracil-5-carboxylate
(MTU-6) in an ethanol solution. Metaltite-treated filler
had 3 mass% of Metaltite applied to the surface before
mixing with the monomer solution. After treatment, the
filler particles were washed with ethanol to remove redun-
dant or unbonded coupling agent. The dried powder was
then gradually added into the monomer solution.
The second coupling agent was 3-methacryloxypro-
pyltrimethoxysilane (MPTMS; Sigma-Aldrich). It is a
silanizing agent commonly used to provide a chemical
bond between silicate fillers and an organic matrix. The
alumina was silanized in a rotary evaporator by mixing it
with MPTMS in cyclohexane with n-propylamine as a
catalyst in a 90
C water bath until dry. The dried powder
was then added to the monomer solution.
In both cases, the mixture of filler and monomer were
cured in an oven at 120
C for about 6 h. The detailed
fabrication procedure and microstructural characteriza-
tion are described elsewhere.6 These studies indicated
that the alumina nanoparticles were well dispersed with
the composite. The compositions of the specimens eval-
uated in this study are listed in Table I.
B. Nanoindentation testing
A Nano Indenter XP (MTS Nano Instruments, Oak
Ridge, TN) with a standard Berkovich diamond tip was
used for the nanoindentation tests. The Nano Indenter
instrument is located in a clean room of Class 10,000
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-
imize effects from minor processing variations. How-
ever, 2–3 additional samples of each composition were
fabricated and the same tests were repeated on them to
verify behavioral characteristics and reproducibility.
Cross-linked composites were cut, ground, and polished
to a 0.5- or 1-mm diamond finish to provide a flat and
parallel surface for testing.
The tests to characterize the viscoelasticity of the
composites were performed at room temperature in the
load-control mode of the machine. A triangle-wave
loading–unloading cycle was applied, as shown in Fig. 1.
The test time was equally divided between loading and
unloading. Total test times were 30, 100, or 300 s. The
TABLE I. Sample composition and abbreviation.
Sample design Coupling agents Filler vol%
PR Pure resin None 0
UT Untreated None 46.6
MT Phosphate coupled Metaltite 47.0
SA Silane coupled MPTMS 57.6
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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
FIG. 4. Comparison of the samples in Table I in terms of maximum
penetration depths at loading time of 300 s, left coordinate, and dis-
placement shifts between 30 and 300 rise times, right coordinate. The
maximum load is 300 mN.
elastic–plastic behavior.17 In the 300 s curve for PR, the
maximum penetration occurred after the load maximum
was reached and the unloading slope was negative at the
beginning of the unloading curve. This is characteristic
of a strong viscous response.17 A monomer system such
as Bis-GMA and TEGDMA that produces thermoset
polymers with a highly cross-linked network, would
be expected to exhibit less viscous flow derived from
the rearrangement and sliding of polymer chains than
a thermoplastic polymer because the neighboring
chains are usually cross-linked. However, since uncross-
linked polymer segments exist, viscous flow from re-
arrangement and sliding of uncross-linked segments is
possible. Thus, even for thermoset polymers, a viscous
response is not unexpected.
Comparing the behaviors of PR and UT in Fig. 2, UT
exhibits less displacement at maximum load on the load-
ing–unloading curves for loading at different rates indi-
cated by D. This indicates there was less viscous flow in
the alumina reinforced composite UT. This is attributed
to the decrease in the organic fraction of the alumina/
resin composite where flow could occur. However, even
with only about 45 vol% polymer, the organic fraction in
UT still plays an important role, as indicted by the vis-
cous response.
In polymer composites, the interfacial region between
the filler surface and the point in the polymer matrix where
the matrix exhibits bulk behavior is often treated as a
phase.21 This means that the composite can be treated as
if it has three phases, inorganic filler, organic matrix, and
the interfacial region. The properties in the interfacial
region are primarily controlled by the contact between the
filler and the polymer. This contact then influences the
properties of the composite.22,23 We hypothesize that at
least some of the viscous flow observed in our filled com-
posites resulted from flow in the interfacial region
between the filler and bulk polymer. Enhancing the bond-
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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
the time-dependent behavior observed for uncoupled
composites. Similar behavior was observed for compos-
ites with silanized filler. The coupling agents in this
study were chosen since they were capable of reacting
with the hydroxyl groups on the surface of the filler and
copolymerizing with the methacrylate vinyl group in the
resin matrix.24 This type of bonding between the filler
and matrix is much stronger than the hydrogen bonding
or van de Waals forces that connect the untreated filler to
the matrix. Thus, when stress is applied, movement in the
interfacial region of the coupled composite is impeded.
This indicates that the stress applied to the composites is
more effectively transferred to the stronger and stiffer
filler when the filler is coupled to the matrix.
Figure 4 compares the maximum penetration depth for
a loading time of 300 s and the displacement, D, for the
samples in Table I. As you move from left to right in
Fig. 4, D decreases indicating that viscous flow decreases
as filler is added and the filler is coupled to the matrix.
Both increased filler fraction and coupling the filler to
the matrix attenuate polymer mobility and thus decrease
viscous flow by confining uncross-linked polymer seg-
ments near the filler and cross-linking the treated filler
into the matrix. Figure 4 also shows that MT, the coupled
sample has a smaller displacement depth than UT, the
uncoupled sample, at the same loading rate and filler
fraction. This implies that the coupled samples have
higher hardness than uncoupled composites.
Dental resin adhesive composites are used in a
demanding oral environment, i.e., aqueous conditions
with varying pH, temperature variations, and over-
stresses. Thus, a strong bond between filler and polymer
is desirable to protect against degradation or swelling
induced by the intrusion of saliva and acids along the
interface between filler and polymer. A strong bond is
also necessary to minimize the effect of temperature
variation on viscous flow in the polymeric matrix.
Finally, a strong filler-matrix bond has the potential to
reduce the change of dimensions in resin composites
associated with viscous flow or creep under long-term
cyclic loading in the mouth. Thus, increasing 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
are plotted with hollow symbols. The simulated {P, h}
responses from the VEP model are indicated with
dashed, dotted, and solid lines for the 30, 100, and 300 s
tests, respectively. The 300 s data were used to determine
the P and h from the model so the model curve overlays
the data almost exactly. The loading and unloading
curves predicted by the VEP model fit the100 s data well
indicating that the model provides a good prediction for
the deformation behavior of the composite. The fit is not
as good for the 30 s test. This may be explained by
Deborah number effect, i.e., the apparent time constant
describing material flow behavior varies with the obser-
vation time of the test.16 Briefly, this is related to the fact
that there are multiple flow mechanisms involved during
the loading–unloading event and they have different time
constants. Thus, when the loading–unloading time changes;
the contribution from each mechanism changes as well.
In a heavily particle-filled system like ours, with limited
numbers of tests, it is hard for the simple VEP model to
predict accurate load–displacement response for each
potential deformation mechanism. However, it should
be noted that for longer rise times, additional, slower
mechanisms such as the matrix flowing past and then
breaking free from a particle are likely to be involved and
they may contribute more to the displacement. In other
words, as the observation time increases, the slower flow
mechanisms contribute more to overall displacement. In
this study, the parameters used for prediction were
extracted from a single 300 s test, thus the parameters in
the VEP model represented displacements from each
mechanism active during the 300 s test. However, when
rise time is shorter, some deformation mechanisms will
not be active, so that using load and deformation parame-
ters derived from the 300 s test would tend to over-predict
displacement as was observed for loading the 30 s curve.
Thus, the VEP model is limited by both its simplicity and
the nature of flow with multiple time constants. Using a
single time constant model, it is hard to predict mechanical
behavior that stems from multiple mechanisms with dif-
ferent time scales. It was also found by Cook and Oyen16
that the VEP model did not provide a good fit to the data
for extreme cases. In their study, the model fitting to the
data for very long rise times was poor. Thus, further work
to include time constants for mechanisms operative at
different time scales would enhance the predictive capa-
bility of the model.
TABLE II. E, H, and t of various resin composites.
Samples PR
E (GPa) 4.7 (4.6)
H (GPa) 0.97 (0.244)
t (s) 156
Filler fraction (vol%) 0 46.6
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C. Mechanical properties derived from the VEP
model
In the VEP model, fitting and simulation give a way to
estimate the mechanical properties of the composite, i.e.,
E, H, and t. In Table II, the VEP inferred elastic modulus
matches well with data obtained from direct nanoinden-
tation tests.6 This gives confidence in the other mechan-
ical properties derived from the data using the VEP
model. The similarity of the elastic modulus determined
from the VEP model and direct nanoindentation measure-
ments in conjunction with the fit of the data to the 100 s
tests indicate that the VEP model can be used with highly
filled highly cross-linked network polymer composites.
This is significant since the model was derived for ther-
moplastic polymers or composites with low filler loading
and has not been applied to highly filled systems.16,25
The VEP calculated hardness (true hardness) data
were much greater than those obtained from direct tests.
This issue has been discussed in the literature. In the
VEP model, the total irreversible deformation consists
of two parts: plastic and viscous deformation. The true
hardness from the model is based on the plastic deforma-
tion, viscous deformation is excluded. In the direct CSM
mode tests, the total irreversible deformation determined
the hardness. Thus, the hardness values were lower since
they included both plastic and viscous deformation.
Other researchers have reported the same finding.25 This
means that it is important to specify what is meant by
hardness when the VEP model is used.
The numbers within brackets are E and H obtained
from direct testing by nanoindentation. The numbers
without brackets are the values E and H obtained from
VEP modeling (the H is also called true hardness).
The ability to separate the plastic and viscous contri-
butions to the observed displacement provides a way to
estimate the relaxation time for viscous flow in resin
composites. This is important because the relaxation time
provides insight into the coupling between the filler and
the resin matrix. The relaxation times, t, are presented in
Table II. For PR, the t was about 156 s so the unloading
times (15, 50, and 150 s) corresponded to about 1/10, 1/3,
and 1/1 of t. For sample SA, the t was about 420 s, so the
unloading times correspond to about 1/28, 1/8.4, and
1/2.8 of t. Thus, viscous flow would not play as dominant
a role in behavior for SA because the time constant
is much longer than the test period indicating that the
UT MT SA
21.0 (20.4) 22.1 (21.5) 31.5 (31.2)
2.50 (0.753) 3.27 (0.934) 5.68 (1.340)
259 331 420
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-
nificantly to the observed deformation. From a practical
viewpoint, increased relaxation time should correlate with
decreased creep and thus better long-term performance.
In our experiments the relaxation time increased as the
volume fraction of inorganic filler increased and with the
addition of effective coupling agents. For particle-filled
composites with a similar degree of cross-linking, it
makes sense that relaxation time would increase and
viscous flow would decrease as the volume fraction of
filler is increased, because filler particles (i) decrease the
volume of polymer present to exhibit viscous flow; and
(ii) filler particles tend to interfere with the viscous flow
of the polymer. Coupling agents bond the filler particles
to the matrix. Thus, the addition of effective coupling
agents should decrease viscous flow and increase relaxa-
tion time compared to composites with similar filler frac-
tions but no coupling agent or a less effective agent.
Comparing UT and MT in Table II shows that the relax-
ation time was increased by more than 20% when
Metaltite was used as a coupling indicating that it was
effective in bonding the filler to the resin matrix.
V. CONCLUSIONS
The time-dependent response of dental resin compos-
ites has the potential to affect the performance of com-
posite adhesives under long-term cyclic loading so that
developing a quantitative measure for it and an under-
standing of the factors that contribute to it is important.
Our studies of nanoindentation behavior as a function of
loading rate showed that the time-dependent response of
our resin composites was affected by filler loading and
coupling agents. Specifically, when filler volume frac-
tion was increased or the bond between the filler and
matrix was enhanced by an effective coupling agent,
viscous flow decreased substantially as indicated by the
relaxation time and the shift in maximum penetration as a
function of test duration. In addition, our work validated
the VEP model of Cook et al.16 for highly filled, heavily
cross-linked resin matrix composites. In particular, the
VEP model was able to predict load–displacement trajec-
tories and the value of E calculated from the VEP model
was consistent with those from the direct CSM mode
nanoindentation measurements. The time constant for
viscous behavior predicted by the VEP approach and the
potential to deconvolute the elastic, plastic, and viscous
contributions from the load–displacement curves should
be valuable for the design and understanding of future
highly filled resin composite systems.
ACKNOWLEDGMENTS
We would like to acknowledge Dr. Robert Cook, Dr.
Brian Lawn, Dr. Sanjit Bhowmick, and Lin-Sien Lum of
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National Institute of Standards and Technology (NIST)
for their helpful discussions and use of their equipment.
We also thank Prof. Van Thompson of New York Uni-
versity for helpful discussions. Financial support was
provided by National Institutes of Health (NIH) Grant
NIDCR PO1 DE10976. This work was done in partial
fulfillment of dissertation requirements for Yijun Wang.
We also thank ESSTECH for donating BisGMA for the
initial materials studies.
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