Polymer Testing 41 (2015) 1e6

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Polymer Testing
journal homepage: www.elsevier.com/locate/polytest

Short communication: test method

Effects of experimental variables on PMMA nano-indentation

measurements
Tao Jin a, Xiaoyan Niu b, Gesheng Xiao a, Zhihua Wang a, Zhiwei Zhou c,
Guozheng Yuan a, Xuefeng Shu a, *
a
Institute of Applied Mechanics and Biomedical Engineering, Taiyuan University of Technology, Taiyuan, 030024, China
b
College of Civil Engineering, Hebei University, Baoding, 071002, China
c
State Key Laboratory of Frozen Soil Engineering, Cold and Arid Regions Environmental and Engineering Research Institute,
Chinese Academy of Sciences, Lanzhou, 730000, China

a r t i c l e i n f o a b s t r a c t

Article history: This work aims to investigate the effects of experimental variables on nano-indentation
Received 18 August 2014 measurements on PMMA. A wide range of conditions, including different load levels,
Accepted 21 September 2014 loading rates, holding times and unloading rates were employed to examine the sensitivity
Available online 28 September 2014
of nano-indentation measurements to the selected experimental variables. The test results
indicate that the elastic modulus and hardness of PMMA are approximately load-level
Keywords:
invariant. However, they are sensitive to the loading rate, holding time and unloading
Nano-indentation
rate. Both elastic modulus and hardness increase with increasing loading rate, while
Experimental variables
PMMA
increasing holding time leads to decreasing elastic modulus and hardness. Moreover, the
unloading rate has almost no obvious effect on the hardness of PMMA, while the opposite
is true for elastic modulus.
2014 Elsevier Ltd. All rights reserved.

1. Introduction have been reported to describe nano-indentation tests. H

PMMA is an important material which has been widely
used as a material for engineering components in the
aircraft and automotive industries [1e3]. The design of
these engineering components requires an overall under-
standing of the mechanical properties of PMMA. Many re-
ports have been undertaken to measure the elastic and
time-dependent mechanical responses of PMMA [1e6].
Nano-indentation is typically applied to study nano-scale
mechanical response and provides accurate continuous
measurements of the indentation load (P) and penetration
depth (h). By numerical calculation of the loadedisplace-
ment curves, the mechanical properties, Young's modulus
and hardness, can be obtained [7]. Many investigations
* Corresponding author. Tel./fax: 86 351 6014455.
E-mail address: shuxuefeng@tyut.edu.cn (X. Shu).
Chakraborty [3] et al. studied the tribological behavior of
multifunctional ZnO/PMMA nano-composite through
nano-indentation tests. L He et al. [8] investigated the
elastic modulus and stressestrain response of human
enamel by nano-indentation. The nano-mechanical char-
acteristics of polycarbonate (PC) polymer were investigated
by nano-indentation [9].
However, nano-indentation measurements always vary
with changing loading conditions. In addition, the accuracy
of the measurements greatly affects the reliability of the
subsequent data analysis. Accordingly, better understand-
ing of the effects of experimental variables on PMMA nano-
indentation measurements is required. A number of authors
have reported the sensitivity of nano-indentation mea-
surements to the loading conditions. ML Oyen [5] found that
a material with substantial time-dependent deformation in
the experimental time frame exhibited some effects of both
load level and ramp time on modulus values. YC Lin [7]

http://dx.doi.org/10.1016/j.polymertesting.2014.09.015
0142-9418/ 2014 Elsevier Ltd. All rights reserved.
2 T. Jin et al. / Polymer Testing 41 (2015) 1e6

explained the effects of holding time on nano-hardness of Indentation tests-4 were performed at xed peak force
brittle and ductile materials. The above research reveals that (Pmax 30mN), loading time (tL 300s), and 
holding time
the load level, ramp time and holding time of an indentation (tH 10s) with varying unloading rates (Pu Pmax/tL, 0.2,
indeed affect the measurement of elastic modulus or hard- 0.3, 0.4, 0.6, 1.2, 2, and 3mN/s). This gave unloading times of
ness. Evidently, understanding of the effects of the time tL 150, 100, 75, 50, 25, 15, and 10s, respectively.
frame is necessary to suitably explain the variation in PMMA Each test was performed at room temperature and
nano-indentation measurements under the different load repeated three-four times. The mean values of elastic
conditions. Hence, in the present paper, an overall exami- modulus and hardness were used for the following
nation was undertaken to study the effects of experimental discussion.
variables on PMMA nano-indentation measurements over a Many details about analysis of indentation test results
wide range of the variables. are given elsewhere [10e12]. Based on load-control nano-
indentation, the contact stiffness S can be obtained from
the unloading stage of the load-depth curve. The function
2. Experiment procedure
P ah  hf m (1) is used to t the unloading curve, where
a and m are the tting parameters, h is the indentation
Nano-indentation tests were performed using a Nano-
depth and hf is the residual depth. Usually, the upper
indenter G200 test system produced by Agilent Technolo-
portion of the unloading data is tted by using the least
gies. A triangular pyramid Berkovich diamond indenter was
squares method. Hence, the contact stiffness S can be
employed. The material tested in this investigation was 5-
computed by [10]:
mm thick sheet of PMMA (poly methyl methacrylate). The
Plexiglas G PMMA sheet is produced through a traditional

dP  m1
cell cast method, and thus no molecular chain orientation S am hmax  hf (2)
dh h hmax
exists in the as-cast sheet. In order to study the sensitivity
of PMMA to experimental variables in nano-indentation For a perfect Berkovich diamond indenter, the projected
measurements, a load-control method was employed contact area is:
(Fig. 1). Four experimental protocols were employed in the
load-control indentation tests: Ac 24:56h2c (3)
Indentation tests-1 performed at xed loading time
(tL 10s), holding time (tH 10s), and unloading time where hc is the contact depth and can be calculated by:
(tU 10s) but with varying peak loads (Pmax 10, 30, 50, 70,
P
100 mN). hc h  (4)
S
Indentation tests-2 were performed at xed peak force
(Pmax 30mN), holding time (tH 10s), and unloading time where 0.75 is a constant for the Berkovich indenter, S is
(tU 10s) with varying loading rates (P Pmax/tL, 0.0375, the contact stiffness.
0.06, 0.1, 0.15, 0.3, 0.6, 1, and 3mN/s). This gave loading The hardness is dened by:
times of tL 800, 500, 300, 200, 100, 50, 30, and 10s,
respectively. P
H (5)
Indentation tests-3 were performed at xed peak force Ac
(Pmax 30mN), loading time (tL 10s), and unloading time where P is the contact load. The elastic modulus of the
(tU 10s) with varying holding time (tH 10, 25, 50, 75, indented material is obtained from the following equation
100, 150, 200, 300, 500, 800, and 1000s). [10]:

1 1  n2 1  n2i
(6)
Er E Ei
where Ei, ni are the modulus and Poisson's ratio of the
indenter tip (diamond), E, n are the modulus and Poisson's
ratio of the indented material and Er is the reduced elastic
modulus. Sneddon's stiffness equation provides the foun-
dational relationship between reduced elastic modulus (Er),
S, and contact area (Ac):
p
p S
Er p (7)
2b Ac
where b 1.034 is the shape constant of Berkovich tip.

3. Results and discussion

Fig. 1. Schematic loadetime (Pet) curve for indentation tests; labels dene
Fig. 2 shows the indentation elastic modulus and
the peak force (Pmax), loading time (tL), holding time(tH), and unloading hardness of PMMA as a function of the peak load. Both the
time(tU), all of which were varied in the current tests. elastic modulus and hardness values are approximately
 T. Jin et al. / Polymer Testing 41 (2015) 1e6 3

Fig. 2. Indentation elastic modulus and hardness of PMMA as a function of

peak force.

load-level constant for PMMA. Therefore, the peak load

almost has no effect on the indentation measurements of
PMMA. Hence, further load-control indentation tests were
performed by controlling the xed peak force
(Pmax 30mN).
As Fig. 3 (a) shows, the indentation elastic modulus and
hardness of PMMA increase with increasing loading rate.
At a lower loading rate, the ramp time (tR) is longer so that
the viscous deformation is largely exhausted during the
loading and there is only a small degree of creep response,
as shown in Fig. 3 (b). Furthermore, the larger indentation
depth leads to a bigger contact area (Ac). Hence, a lower
loading rate corresponds to a lower elastic modulus and
hardness. On the other hand, the deformation rate is
higher at a high loading rate. Therefore, the ramp time of
loading is too short to exhaust the viscous deformation so
that the indentation depth decreases as the loading rate
increases, especially at high loading rate. Furthermore, at a
high loading rate, more viscous deformation will be
accumulated after loading, transforming into larger creep
deformation during the holding stage, as plotted in Fig. 3
(b). Fig. 3 (c) presents the relationship between creep
strain rate and holding time under different loading rates.
The indentation creep strain rate can be calculated as
[13,14]:

 1 dh
(8)
h dt
where h is the instantaneous indentation depth and t is
time. This result indicates that the indentation creep strain
rate at the initial holding stage decreases with decreasing Fig. 3. Indentation elastic modulus and hardness of PMMA as a function of
loading rate (a); Loading depth and holding time depth as a function of
loading rate. At a higher loading rate, the creep strain rate loading rate (b); Creep strain rate during the holding stage under different
drops quickly at the beginning of the holding stage and loading rates (c).
then stabilises, which shows the primary and secondary
creep. Conversely, the creep strain rate is stable during the
entire holding time at a lower loading rate, indicating the This phenomenon results from the viscous deformation. A
secondary creep occurs before the holding stage. Addi- higher loading rate results in a smaller ramp time. There-
tionally, Fig. 3 (c) indicates that the steady creep was ob- fore, more accumulated viscous deformation needs to be
tained at the initial holding stage under a loading rate of released during the holding stage, which results in a higher
0.15mN/s, with a strain rate of approximately 0.0025s1. creep strain rate at the initial holding stage. In addition,
4 T. Jin et al. / Polymer Testing 41 (2015) 1e6
when the loading rate is under 1mN/s, the uctuation in
elastic modulus caused by the loading rate reaches 60.8%.
However, the viscous deformation cannot be released fully
when the loading rate exceeds 1mN/s. The elastic modulus
acts as a constant under this loading condition.
Fig. 4 (a) shows the elastic modulus and hardness
plotted as a function of the holding time. The observed
elastic modulus and hardness were largely dependent on
holding time for PMMA. For constant load and loading rate,
increasing the holding time reduces the elastic modulus
and hardness. Both elastic modulus and hardness contin-
ually declined as the holding time increased, but the rate of
decline decreased, as expected. Similar behavior was also
observed by Conte  et al. [15]. This phenomenon results
from the creep deformation. Viscosity resistance of the
molecule chains or polymers results in no balance being
established between stress and strain. In addition, creep is
caused by the motion of molecule chains under stress. For
long holding times, creep is largely exhausted during the
long holding time, resulting in a smaller recovery of elastic
strain during unloading. Accordingly, a smaller unloading
elastic modulus for the long holding time is obtained. Fig. 4
(b) shows the relationship between holding time and the
creep depth during nano-indentation. It is obvious that the
Fig. 4. Indentation elastic modulus and hardness of PMMA as a function of
holding time (a); The relationship between creep depth and holding time
(b).
depth of penetration by creep during the holding stage
increases with the hold time during nano-indentation. In
addition, a deeper indentation depth leads to a larger
contact area which results in a smaller hardness, as plotted
in Fig. 4 (a).
The indentation elastic modulus and hardness of PMMA
as a function of unloading rate are plotted in Fig. 5 (a). It can
be observed that the hardness is almost unloading rate
independent. However, the elastic modulus is sensitive to
the unloading rate. It decreases as the unloading rate in-
creases. The viscous deformation can be used to explain the
unloading rate dependence of elastic modulus. For PMMA,
viscous deformation occurs throughout the indentation
process. At a lower unloading rate, the indentation depth
continues to increase after the holding stage, causing a
bulge and negative unloading stiffness in the unloading
curve [16,17]. It is obvious that the bulge phenomenon is
sensitive to unloading rate. A lower unloading rate more
easily causes the bulge phenomenon. However, at a
higher unloading rate, the recovery of elastic strain during
unloading is larger than that under a lower unloading rate.
As shown in Fig. 5 (b), the slope of the unloading curve
Fig. 5. Indentation elastic modulus and hardness of PMMA as a function of
unloading rate (a); Nanoindentation unloading curves for PMMA under
different unloading rates (b) (In order to enable a better visual comparison,
some curves are parallelly moved).
 T. Jin et al. / Polymer Testing 41 (2015) 1e6
increases with the decreasing unloading rate. Hence, a
lower unloading rate corresponds to a higher unloading
elastic modulus.
It is obvious that the testing time frame has great ef-
fects on the nano-indentation measurements of PMMA.
Furthermore, the time dependence of PMMA results from
viscous deformation, as mentioned above. However, the
viscous deformation occurs throughout the indentation
process. Therefore, it is necessary to analyze the effects of
tI (tL tH) on the PMMA nano-indentation measurements.
In order to analyze the effects of tI and avoid the effects of
unloading rate, the results of Test-2 are selected to
compare with those of Test-3, which have the same tI.
Fig. 6 shows the experimentally measured elastic
modulus, hardness and displacement of PMMA through
Test-2 and Test-3 plotted against tI. Both the elastic
modulus and hardness decrease with increasing tI, as
expected. Because the increasing tI leads to increasing
indentation depth, it results in the reduction of elastic
modulus and hardness. However, for the same tI, the
elastic modulus measured by Test-2 is completely
consistent with that measured by Test-3, which is
confusing. For example, when tI 60s, the loading time. tL
and holding time tH are 50s and 10s in Test-2 while they
are 10s and 50s in Test-3. Therefore, it is easy to infer that
the elastic modulus measured by Test-2 will be smaller
than that measured by Test-3. Unfortunately, we have no
Fig. 6. Experimentally measured elastic modulus, hardness, and displacement of PMMA through Test-2 and Test-3, respectively, as a function of tI.
5
explanation of this interesting phenomenon and further
study is being undertaken. On the contrary, the hardness
measured by Test-2 is smaller then that measured by
Test-3 and the difference decreases with tI increases, as
expected.
4. Conclusions
A wide range of experimental conditions have been
employed to examine the sensitivity of the elastic modulus
and hardness of PMMA to the selected experimental vari-
ables. Both the elastic modulus and hardness are load-level
independent. The elastic modulus is sensitive to the
loading-rate, holding time and unloading-rate. The elastic
modulus is found to decrease as the holding time or
unloading-rate increases. However, the elastic modulus
increases with increasing loading-rate. The hardness of
PMMA exhibits increased values with increasing loading-
rate. However, the hardness decreases as the holding
time increases. Furthermore, the hardness exhibits
unloading rate independence. Viscous deformation can
explain the effects of experimental variables on PMMA
nano-indentation measurements. In addition, a minimum
loading time of 200s is required for obtaining steady creep
at the initial holding stage during indentation. Moreover, a
high unloading rate is needed to acquire reasonable nano-
indentation measurements.
6 T. Jin et al. / Polymer Testing 41 (2015) 1e6
Acknowledgements
This work is supported by the Natural Science Founda-
tion of China (Grant Nos. 11172195 and 11172196), Post-
graduate Excellent Innovation Project of Shanxi Province
(No. 20133038), Program for New Century Excellent Talents
in University, and the Top Young Academic Leaders of
Higher Learning Institutions of Shanxi. The nancial con-
tributions are gratefully acknowledged.
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