Carbon 114 (2017) 334e346

Contents lists available at ScienceDirect

Carbon
journal homepage: www.elsevier.com/locate/carbon

Reinforcement and shape stabilization of phase-change material via

graphene oxide aerogel
Yue Xu, Amy S. Fleischer, Gang Feng*
Department of Mechanical Engineering, Villanova University, Villanova, PA, 19085, USA

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

Article history: Phase change materials (PCMs) are of interest in many applications which may require shape-
Received 10 August 2016 stabilization. In this study, a graphene oxide aerogel (GOxA) reinforced paraffin PCM composite is
Received in revised form developed, effectively reinforcing and shape-stabilizing the paraffin.
22 October 2016
The molecular and diffraction characterizations suggest that the GOxA network potentially affects
Accepted 25 November 2016
paraffin's crystallization. The mechanical characterizations using durometer and nanoindentation show
Available online 28 November 2016
that the composite is 3~7
harder than pure paraffin and maintains significant strength even above
paraffin's melting temperature. Moreover, the composite is much less strain-rate sensitive than paraffin.
The reinforcement via GOxA is much beyond the prediction by the rule-of-mixture, implying a strong
GOxA-paraffin interfacial bonding.
To our best knowledge, this is the first study on the mechanical behavior of paraffin and GOxA-PCM
composite, providing critical insights into their behavior. Additionally, the relationship between the
hardness and durometer index first-ever developed here will enable the quantitative durometer testing
on materials for many other applications at different ambient conditions due to its versatility and
simplicity.
© 2016 Elsevier Ltd. All rights reserved.

1. Introduction [9,16,20e29]. This leads to many potential applications including

Phase change materials (PCMs) store and/or release thermal
energy through the solid-liquid phase transition and exhibit the
advantages of low cost and high energy density, making them a
popular choice for energy storage materials [1e6]. Paraffin is a
high-performance PCM owing to its high latent heat, low super
cooling, and chemical stability; however, its intrinsic low thermal
conductivity can make it difficult to transfer energy effectively into
larger masses, and the possibility of liquid phase leakage can lower
the perceived reliability of the systems [1,2,7e9].
Aerogels are porous materials with extremely low bulk density,
composed of nanoparticles, nanowires, nanotubes, or nanosheets
of oxides [10e12], silicon [12], metals [12e15], and carbon mate-
rials [16e19]. Graphene-based three-dimensional (3D) aerogels
have drawn attention due to their unique properties, including low
density, high porosity, large specific surface area, excellent elec-
trical conductivity and outstanding mechanical properties
* Corresponding author. Mechanical Engineering, Villanova University, 800
Lancaster Ave., Villanova, PA 19085, USA.
E-mail address: gang.feng@villanova.edu (G. Feng).
energy storage [1,9,16,30,31], super-capacitors [20,23], air and
water purification [32,33], and nanocomposites [34].
Recently, much research has focused on the integration of
graphene-based nanomaterials with high thermal conductivities
into PCMs to increase their overall thermal conductivity [35e37]. It
is also known that graphene aerogel (GA) impregnated with PCM
exhibited a rise in thermal conductivity [38].
While the use of nano-inclusions can mitigate the effects of low
thermal conductivity, it is also necessary to address the issue of
liquid leakage. Some methods are available to mitigate this po-
tential leakage, such as encapsulation and shape stabilization
[2,39,40]. Shape stabilization of PCMs occurs through the addition
of supporting materials into the PCM which can hold the liquid
phase in place with the matrix, usually by capillary action. Possible
supporting materials include high density polyethylene (HDPE) [2],
opal [8], graphite [41], carbon nanospheres [40], graphene oxide
(GOx) [3,4,42], graphene aerogel [30,38], exfoliated graphite
nanoplatelets (xGnP) [43], graphite nanoplatelets [5,44], and gra-
phene nanoplatelets [45]. In some cases, large amounts of sup-
porting materials are needed in order to shape stabilize PCMs. For
example, a GO-paraffin composite showed no liquid leakage at
51.7 wt% of GO, but the latent heat dropped by 52% [4]. In the case of

http://dx.doi.org/10.1016/j.carbon.2016.11.069
0008-6223/© 2016 Elsevier Ltd. All rights reserved.
 Y. Xu et al. / Carbon 114 (2017) 334e346
HDPE PCM [2], the shape-stabilization required at least 25e30 wt%
of HDPE. In this paper instead, the use of graphene oxide aerogel
(GOxA) is explored as both a shape stabilizer and a thermal con-
ductivity enhancer, because its use has been shown to not decrease
the latent heat [38].
Most studies of PCMs have focused on their thermal character-
istics, but their mechanical properties are also vitally important
particularly as related to the shape stabilization behavior. The
mechanical properties of graphene-based and GO-based polymer
composites have been studied, showing improvements in their
strength and modulus [8,46e50] compared to the pure polymer
counterparts. However, to our knowledge, the mechanical proper-
ties and shape stabilization behavior of GOxA-PCM composite have
never been fundamentally studied. A comprehensive fundamental
understanding of the mechanical behavior of GOxA-PCM composite
is thus vitally important to understand the behavior of GOxA alone,
pure paraffin, and the composite.
Typically, mechanical properties of porous 3D carbon aerogels/
networks have been studied through either compression or nano-
indentation tests. Table A1 in Appendix 1 summarizes some of the
recent results, indicating a large discrepancy in the literature
values. For example, for pristine graphene aerogel (GA) with den-
sity less than ~30 mg/cm3, data on strength is in the wide range of
0.2e40 kPa, while the modulus data shows a range of 2e1200 kPa.
In general, by increasing the bonding between carbon nano-
materials, e.g., by noble metal [51] or crosslinking [52], the overall
strength and modulus should increase.
In this work, by infiltrating GOxA with paraffin, a PCM com-
posite with ~5 wt% of GOxA is formed. The mechanical behavior
with respect to both shape stabilization and mechanical properties
will be comprehensively characterized at different strain rates as
well as at a range of temperatures, including above the melting
point of the PCM. While the thermal analysis of this GOxA-PCM
composite is also of interest, it will be left for a future paper in
order to concentrate here on the mechanical characteristics.
To our best knowledge, this is the first study on the fundamental
strain-rate-dependent and temperature-dependent mechanical
behaviors of paraffin and GOxA-PCM composite, providing critical
insights to understand the behavior of graphene-related PCM
composites and their application into the design of high-
performance energy storage PCM composites with high reliability.
2. Material and methods
The graphite powder was purchased from Spectrum Chemical
Manufacturing Corp. The sodium nitrate (NaNO3, high purity grade)
and potassium permanganate (KMnO4, ACS grade) were obtained
from Amresco, Inc. The hydrogen peroxide (H2O2, 29e32% w/w ar.
soln.) and Ethylenediamine (EDA, 99%) were purchased from Alfa
Aesar. Paraffin wax (IGI 1230A) was purchased from International
Group, Inc. All were used in as-purchased conditions.
In general, graphene-based aerogels are prepared by assembling
2D graphene sheets into a 3D porous graphene architectures
through a sol-gel process and subsequently freeze-drying or su-
percritical drying to remove the solvents in the wet gels while
maintaining the shape of the 3D network [20,28]. Here, by
following the method of Hu et al. [20], GOxAs are formed using the
ethylenediamine (EDA) - mediated reduction of GOxs followed by
supercritical CO2 drying. The GOxA-reinforced paraffin composite
is synthesized through infiltrating paraffin into GOxA.
2.1. Synthesis of graphite oxide
The graphite oxide was prepared using a modified Hummers
method [53]. First, 5 g of graphite powder and 2.5 g of sodium
335
nitrate were mixed with 120 ml sulfuric acid in an ice bath under
vigorous stirring for 2 h. 15 g of potassium permanganate was then
slowly added into the system with constant stirring while the
temperature was kept below 20  C. After one hour of stirring, the
temperature of the mixture was raised to 35  C and then the
mixture was stirred overnight for complete oxidation yielding a
thick paste. 150 ml of deionized water (DI water) was added to this
paste gradually and the mixture was heated to 98  C and stirred for
12 h. 500 ml of DI water and 20 ml of hydrogen peroxide were then
added to the mixture. The mixture was then washed with 1 M HCl
solution to remove metal ions. The resultant graphite oxide was
washed with DI water and centrifuged for 20 min at room tem-
perature repeatedly until the pH reached 5e6. Finally it was fully
dried by heating at 65  C for two days.
2.2. Synthesis of graphene oxide aerogel (GOxA)
By following the method of Hu et al. [20], the dried graphite
oxide powder obtained in last section was first re-dispersed into DI
water using a Vibra-cell VC505 ultrasonic processor in order to
form a 3 mg/mL graphene oxide (GOx) suspension. It is critical to
have the right concentration of GOx in the suspension in order to
fabricate GOxA with the lowest possible density [20]. Then, 400 mL
of EDA was added into 100 mL of the GOx suspension. This mixture
was sealed in a glass bottle and heated for 12 h at 90  C in order to
synthesize the graphene oxide hydrogel (GOxH). The obtained
GOxH was immersed in DI water for purification for 3 days. The
purified GOxH was then immersed in acetone for 24 h in order to
fully exchange the water in the GOxH with acetone. The purifica-
tion and water exchange process was performed 6 times for com-
plete solvent exchange. Finally, the acetone-gel was dried using
supercritical drying (Leica EM CPD300) to obtain GOxA.
2.3. Preparation of GOxA-PCM composite
Previous studies have shown great success in forming polymer-
nanoparticle composites by infiltrating polymer into a porous
nanoparticle structure [54,55]. GOxA and paraffin were heated to
80  C (above the melting point of the paraffin) in a vacuum oven.
The GOxA samples were immersed in the melted paraffin which
fully infiltrated into the GOxA samples under vacuum. The com-
posites were then formed after cooling. The GOxA and composite
samples were weighed using a scale (Citizen Scale CY 204 with
0.0001 g resolution) to calculate the weight percent of paraffin. The
GOxA's weight percentage in the composite samples is (5.2±0.51)
wt%.
2.4. Structural and mechanical characterization
The bulk density was calculated based on the weight and the
apparent sample volume. Scanning electron microscope (SEM)
images were produced using a Hitachi S-4800 field emission SEM.
Fourier transform infrared (FTIR) spectra were recorded on a
Nicolet™ iS™10 FT-IR spectrometer. X-Ray diffraction (XRD)
spectra were recorded on a Rigaku Miniflex X-ray Diffractometer
with Cu Ka radiation. The Brunauer-Emmett-Teller (BET) surface
area of GOxA was characterized via a MicroMeritics Gemini VII
2390 Surface Area Analyzer.
The macroscale mechanical properties at different temperatures
were characterized using a Phase II PHT-960 durometer. The nano/
microscale mechanical properties at different strain rates at room
1
Throughout this paper, the Dx in the form of “x±Dx” always refers to the
standard deviation of quantity x.
336 Y. Xu et al. / Carbon 114 (2017) 334e346
temperature were studied using nanoindentation. The detailed
procedures and conditions for durometer and nanoindentation
testing will be discussed in the related sections later.
3. Results and discussion
3.1. Morphology and crystal structure characterization of graphene
oxide aerogel
Images of the GOx suspension, GOxH and GOxA are shown in
Fig. 1. The GOxH showed some volume shrinkage after self-
assembly (Fig. 1aeb), although this shrinkage is minor compared
to other chemical reduction methods [20]. Fig. 1bec show that the
GOxH shrank roughly by 1/3 after the supercritical CO2 drying and
kept the 3D structure nicely.
The GOxAs' density r ranges from 17 to 36 mg/cm3 based on 5
samples. The GOxAs' specific surface area (AS) is determined as high
as 476 m2/g. If we assume spherical pores and neglect the gra-
phene's thickness, 3/(rAS) [56] is an estimate for the average pore
size r, i.e., 0.17e0.37 mm, which is roughly consistent with the SEM
results (Fig. 2a).
Fig. 2a shows a SEM image of GOxA, implying interconnected
0.2e1 mm pores formed by thin layers of GOx sheets. Fig. 2bec
show the SEM images of the as-synthesized and polished surfaces
of GOxA-PCM composite, showing complete infiltration without
observable voids.
The oxidation of graphite into GOx and the reduction of GOx
into GOxA were investigated using FTIR, as shown in Fig. 3. No
significant peaks were found for graphite, which is consistent with
previous work [57,58]. The FTIR spectrum of GOx indicates
absorption bands of eOH at 3000-3500 cm1, COOH at 1721 cm1,
CeOH at 1355 cm1, and alkoxy CeOeC at 1047 cm1, which is
similar to the GOx spectrum obtained in Han et al.’s work [59]. The
spectrum of GOx also shows a peak at 1588 cm1, representing the
skeletal vibrations from unoxidized graphitic domains [60,61]. The
GOx's carbonyl COOH peak at 1721 cm1 is not shown in GOxA's
spectrum, confirming the partial reduction of GOx. The GOx's OeH
stretching peak at 3000-3500 cm1 and alkoxy CeOeC peak at
1047 cm1 are not shown in GOxA's spectrum, again confirming the
partial reduction of GOx [57,62]. In addition, the GOxA's spectrum
shows the epoxy CeOeC peak at 1209 cm1 and the C]C peak at
1568 cm1, indicating an interaction between graphene sheets and
carbohydrates as well as the assembly of GOx sheets into 3D
structures [20].
3.2. Structure characterization of paraffin and GOxA-PCM
composite
To investigate the effect of embedding GOxA into paraffin on the
Fig. 1. Optical images of (a) GOx dispersion, (b) GOxH, and (c) GOxA. (A colour version of this figure can be viewed online.)
microstructure and crystal phases, FTIR spectra and XRD patterns of
pure paraffin and GOxA-PCM composite were measured as in Fig. 4.
Fig. 4a shows the FTIR spectra of the GOxA-PCM composite
and paraffin. The GOxA-PCM FTIR spectrum is almost the super-
imposition of the spectra of GOxA alone and pure paraffin, with
the addition of three new peaks as shown. The spectra of both
paraffin and GOxA-PCM show the 2915 cm1 and 2848 cm1 CeH
stretching peaks [63], the 1462 cm1 and 1377 cm1 CeH
bending peaks [64,65], as well as the 719 cm1 CeH rocking peak
that can be seen only in long chain alkanes. The new peaks in the
1800 - 2500 cm1 range appear only for the GOxA-PCM com-
posite, implying new chemical bonding(s) in the GOxA-PCM
composite, most likely at the GOxA-PCM interface. For example,
the new peak at 2156 cm1 may correspond to C^C stretching
[64,65]. Further analysis on the new peaks and possible associ-
ated new phase(s) will be left as future work.
Fig. 4b shows the XRD patterns of the GOxA-PCM composite and
paraffin. Except for the new peak labeled, the GOxA-PCM com-
posite's XRD is almost identical to that of pure paraffin, suggesting
that embedding GOxA into paraffin does not significantly change
the crystallization of paraffin. Here, the XRD pattern of paraffin
corresponds to the orthorhombic structure [66]. Due to GOxA's
extremely low density, GOxA alone will not generate significantly
sharp peaks; in fact, previous studies indicate a weak and broad
peak at around 25 for GOxA [9,26]. Fig. 4b also indicates one new
peak at ~37.05 for the composite, corresponding to a plane spacing
of 2.43 Å, implying that a potentially new phase may exist in the
composite, most likely at the GOxA-PCM interface. A study on the
exact structure of this potentially new phase will be left as future
work.
We also measured the XRD peak broadening to analyze any
microstructure changes in the paraffin matrix due to embedding
GOxA into paraffin, such as the grain-size change [67,68] and/or the
crystal-defect density change [68,69]. As shown in Supplementary
Fig. S1b and Table S1, the peak widths (Full-widths-at-half-
maximum) of one typical peak (q ¼ 10.7 ) for both the paraffin and
GOxA-PCM are in fact identical (¼0.414 ). The same peak width
implies that the microstructure (grain-size and crystal-defect
density) has no significant difference between pure paraffin and
the paraffin-matrix in the composite.
Thus, based on the above analysis of FTIR and XRD, a potentially
new phase and/or bonding condition at the graphene-paraffin
interface may be generated by embedding graphene into paraffin.
3.3. Shape stabilization and mechanical characterization
As shown in Supplementary Fig. S2, the GOxA-PCM composite
maintains its original shape even above the melting temperature
without any leakage of liquid paraffin from the system, proving
 Y. Xu et al. / Carbon 114 (2017) 334e346
Fig. 2. SEM images of GOxA and GOxA-PCM. (a) GOxA (a single graphene oxide sheet in the center). GOxA-PCM composite in the (b) as-infiltrated and (c) polished conditions.
Fig. 3. FTIR spectra of graphite, GOx and GOxA. (A colour version of this figure can be
viewed online.)
excellent shape stabilization. In order to quantitatively analyze the
fundamental mechanism of shape stabilization and investigate the
effect of embedding GOxA network into GOxA-PCM composite, we
have mechanically tested paraffin, GOxA, and GOxA-PCM at the
macroscale (at different temperatures) using a durometer and at
the nano/microscale using nanoindentation at different strain rates.
3.3.1. Macroscale mechanical characterization using durometer at
different temperatures
3.3.1.1. Durometer testing at different temperatures. Paraffin, GOxA
and GOxA-PCM were mechanically characterized using a digital
Shore-A durometer at different temperatures. The durometer test is
one common technique for simple, quick and semi-quantitative
evaluation of materials' resistance to penetration, i.e., hardness.
The durometer hardness D is standardized by ASTM D 2240 [70].
One most common durometer scale is Shore A, designated here as
Fig. 4. (a) FTIR spectra of GOxA, paraffin and GOxA-PCM composite. (b) XRD patterns of paraffin and GOxA-PCM composite. (A colour version of this figure can be viewed online.)
337
DSA, appropriate for many common materials from rubber band
with DSA z25 to shoe heel with DSA z80. For elastomeric materials,
durometer hardness D can be correlated to the modulus E roughly
by a power-law relationship [71]. However, this correlation cannot
be easily established in case of plastic indentation, because the
durometer intrinsically tests hardness instead of modulus.
Samples of paraffin, GOxA and GOxA-PCM which were 8 mm in
diameter and 10 mm high were prepared for durometer testing
using a Phase II PHT-960 digital Shore-A durometer. Paraffin and
GOxA-PCM samples were tested at different temperatures in the
range of 22  Ce67  C. The samples were directly put in a water bath
and the sample temperature T was recorded using an E-type ther-
mocouple through a digital OMEGA HH509 thermometer. The dry
GOxA samples were tested only at 22  C. The DSA readings for all
three materials changed with time after increasing the pressing
time, indicating strain rate dependence. For consistency, the DSA
values were read ~3 s after applying the load.
Fig. 5a shows DSA vs. T for all materials. The GOxA-PCM com-
posite is significantly harder than pure paraffin at all temperatures,
implying a significant reinforcement effect from embedding GOxA
into the paraffin. It should be mentioned that the standard devia-
tion in measured DSA for all samples over all temperatures is small
(0.4e1.0) which ensures sample uniformity and durometer con-
sistency. It is interesting that GOxA-PCM's DSA reaches a plateau at
10.2 ± 0.7 for T > Tm ¼ 55.4  C (paraffin's melting temperature),
indicating a significant hardness for T > Tm and hence significant
shape stabilization. GOxA-PCM's DSA at T > Tm matches well with
the hardness (DSA ¼ 13.5 ± 0.8) of dry GOxA alone at 22  C, implying
that the GOxA-PCM composite's hardness at T > Tm is due to the
support from GOxA network alone as the paraffin is fully melted.
3.3.1.2. Method for quantitative analysis of Shore-A durometer
testing. DSA is a hardness index, which cannot be directly compared
to the hardness measured by other techniques, such as nano-
indentation. Therefore, in order to have a more quantitative
338 Y. Xu et al. / Carbon 114 (2017) 334e346
Fig. 5. (a) Durometer Shore A hardness DSA vs. testing temperature T. (b) Hardness H (calculated from DSA based on Eq. (5)) vs. T. Here, paraffin's Tm (¼55.4  C) and the GOxA's
properties at 22  C are also plotted. (c) The correlation of H and DSA based on Eq. (5). (A colour version of this figure can be viewed online.)
comparison, based on the mechanics of the durometer, we derive,
for the first time in the literature, a methodology to correlate DSA to
hardness, H. Here, H is commonly defined as the mean pressure
under an indenter. For an axi-symmetric indenter, we have
H ¼ P=A and A ¼ pa2c ;
where P is the indentation contact load (e.g., in Newton, or N), A is
the projected contact area (e.g., in mm2), and ac is the contact radius
(e.g., in mm).
As illustrated in Fig. 5c, the durometer test is essentially an
indentation test using a truncated axi-symmetric flat punch tip
[70,71], and the contact force P and indentation depth h are related
to the Shore-A durometer reading DSA by Ref. [70],
P ¼ 0:55 þ 0:075DSA ; in N;
h ¼ 2:5  0:025DSA ; in mm:
For an Shore-A durometer, the radius a of the cylindrical trun-
cated flat punch tip at a distance x from the tip end is [70] (see
Fig. 5c),

corresponding values (6.27 ± 0.4 MPa and 15.7 ± 0.3 MPa, respec-
0:395 þ x tan 17:5 x  1:74mm
a¼ ; in mm:
0:635 x > 1:74mm
When indenting a material with a high ratio of E to H with E/
H > ~40 [72e74], the indentation contact depth hc can be well
estimated by the indentation depth h. Consequently, as shown in
Fig. 5c, the contact radius ac in Eq. (1) can be estimated by the
physical radius a of the indenter tip at the contact boundary. Thus,
by replacing x in Eq. (4) by h, the final equation to correlate DSA to H,
is given in Eq. (5).
 
0:55 þ 0:075DSA
H¼ MPa; where a
pa2
8
>
< 0:635 mm DSA < 70
   
¼ DSA (5)
>
: 0:395 þ 2:5 1  tan 17:5 mm DSA  70 :
(1) 100
Fig. 5d shows the plot of H vs. DSA, which demonstrates a tran-
sition at DSA ¼ 70 due to the truncated cone part of the tip (see
Fig. 5c). For DSA<70, Eq. (5) is simply H ¼ 0.434 þ 0.059DSA (MPa),
i.e., a linear correlation (DSA<70). It should be noted that, as advised
by ASTM D 2240, the absolute value of DSA is reliable and compa-
rable between durometers only in the range of DSA ¼ 20e90 [70]
due to the relatively large manufacturing tolerance requirement
of durometers (see Fig. 5c) [70].
(2)
3.3.1.3. Quantitative analysis of durometer testing for GOxA, paraffin,
and GOxA-PCM samples. With this correlation in Eq. (5), the DSA
(3)
values in Fig. 5a can be correlated to H and replotted vs. T as in
Fig. 5b. Fig. 5a and b shows same qualitative trends as discussed
before. Fig. 5b shows that, at room temperature, the hardnesses of
paraffin and GOxA-PCM based on durometer are 6.06 ± 0.4 MPa
and 11.3 ± 0.8 MPa, respectively. These results match well with the
(4) tively) based on nanoindentation as discussed below. Here, based
on nanoindentation data, the modulus to hardness ratio E/H are 177
and 71 for paraffin and GOxA-PCM, respectively, i.e., both are larger
than 40, so Eq. (5) can be used. This newly developed correlation
methodology described by Eq. (5) enables us to quantitatively
analyze the durometer measurements, provided the aforemen-
tioned key assumptions are satisfied (E/H > 40 and DSA ¼ 20e90).
Fig. 5b also indicates that H ¼ 1.23 ± 0.3 MPa for dry GOxA at
22  C and H ¼ 1.04 ± 0.3 MPa at T > Tm, again proving excellent
 Y. Xu et al. / Carbon 114 (2017) 334e346
shape stabilization capability. It should be noted that the GOxA
hardness (H ¼ 1.23 ± 0.3 MPa) based on durometer measurements
is much higher than the hardness (H ¼ 238e400Pa) resulting from
the nanoindentation measurements discussed later. There may be
three major reasons for this difference: (1) for dry GOxA,
DSA ¼ 13.5 < 20, so the absolute value of DSA is not reliable; (2) the
indentation method is known to overestimate hardness of porous
materials due to indentation induced densification effect [75,76],
and here, GOxA is highly porous so that the densification effect is
very large; and (3) for rapid compression of porous materials in air,
the air pressure built-up because of air trapping in the pores
dominates the effective compression load [77,78]. Here, we believe
the 2nd and 3rd factors may be the dominant ones. In fact, the
readings of durometer measurement were ~3 s for ~2.2 mm
penetration, while the flat punch nanoindentation tests took about
4e10 min for ~ 7 mm, so the compression/compaction effect under
durometer is probably about 300 times larger than that under
nanoindenter (the densification (2nd) factor), and the durometer
tip moved about five orders of magnitude faster than nanoindenter
tip (the built-up air pressure (3rd) factor). In fact, when the
durometer was sitting on GOxA, its DSA kept rapidly dropping from
~18 to ~13.5, i.e., ~25%, within ~3s, and then, many GOxA samples
would catastrophically break (similar to the case of GOxA nano-
indentation as discussed later). Thus, it is difficult to evaluate the
further DSA change (after 3s). On the other hand, for paraffin and
GOxA-PCM samples, after an initial 5e10% dropping within 1s~2s,
their values of DSA quickly stabilized.
Nevertheless, at room temperature, even considering the
perhaps overestimated value (H ¼ 1.23 ± 0.3 MPa) for GOxA, the
H ¼ 11.3 ± 0.8 MPa of GOxA-PCM composite is still significantly
larger than the sum of H ¼ 6.06 ± 0.4 MPa of paraffin and
H ¼ 1.23 ± 0.3 MPa for GOxA, quantitatively. This reinforcement of
embedding GOxA into paraffin is much beyond the prediction by
the rule-of-mixture, implying a strong bonding between GOxA and
paraffin. Based on the FTIR, XRD, and mechanical characterization,
since the microstructure of paraffin-matrix is the same as pure
paraffin (as implied by the same XRD peak broadening (see
Fig. S1b)), we hypothesize that a potentially new paraffin inter-
phase is created at the surface of graphene oxide (GOx) sheet. This
potentially new phase may act as a bonding agent (through prob-
ably physical bonding, covalent bonding, hydrogen bonding, and/or
van der Waals bonding) to bond the GOx sheet and the rest of the
paraffin matrix. A study on the exact nature of the bonding would
be left for a future work.
More importantly, the GOxA-PCM composite is much harder
than pure paraffin at all temperatures and maintains significant
strength even at temperatures much higher than paraffin's melting
temperature. Therefore, this composite shows strong shape stabi-
lization capability.
3.3.2. Nano/microscale characterization
A Keysight™ Nano Indenter™ G200, with two indenter heads:
(1) XP and (2) Advance Dynamics Contact Module (DCM II) heads,
was used to perform the nanoindentation tests. The XP head has a
higher load capacity, while the DCM II head has a higher load res-
olution. The continuous stiffness measurement (CSM) technique
was implemented throughout each test [79e81], with a constant
harmonic frequency (50 Hz for XP and 75 Hz for DCM II heads) and
harmonic displacement of 1.5 nm for both heads.
Due to GOxA's extremely low hardness and modulus, the GOxA
was tested using two large flat punch indenters: (1) a 456 mm-
diameter diamond circular punch in DCM II, and (2) a 2 mm-
diameter steel circular punch in XP head. The tests on GOxA were
run with a constant load-rate-to-load-ratio of 0.05s1. Prior to any
indentation, the nanoindenter was stabilized to a thermal drift rate
339
of <0.05 nm/s.
All tests on paraffin and GOxA-PCM were performed using a
diamond Berkovich indenter in the XP head. As demonstrated later,
paraffin and GOxA-PCM are strain-rate dependent, which to our
best knowledge has not been previously studied. Also, as discussed
in Appendix 2, the GOxA-PCM composite can be effectively treated
well as a homogeneous material for analyzing the indentation
results.
For a coherent and concise discussion, the general nano-
indentation technique is summarized in Appendix 2, and a new
technique of multiple-strain-rate nanoindentation characterization
is first-ever developed and presented in Appendix 3.
3.3.2.1. Nano/microscale multiple-strain-rate characterization of
paraffin and GOxA-PCM. A nanoindenter can control load P and
continuously measure the indentation displacement h. The inden-
tation strain rate ε_ is defined as the displacement-rate-to-
displacement-ratio (_ε ¼ h=hz _ _
P=2P) [82,83]. A multiple-strain-rate
indentation method is used in this study: for one indentation, it
has three sequentially decreasing strain rates (P=P¼2_ _ ε0 , 0:2_ε0 , and
0:02_ε0 ) during a single loading (see Fig. 6a). The methodology for
multiple-strain-rate nanoindentation characterization is developed
and discussed in Appendix 3 in detail.
Fig. 6a shows the typical load-time (P-t) curves for the two sets
of three-strain-rate indentation. One ε_ 0 is equal to 0.05 s1 and the
other is equal to 0.0025s1; this corresponds to six preset strain
_
rates, i.e., P=P¼ (0.025, 0.25, 0.5, 2.5, 5, 50)
10e3 se1.
Fig. 6b shows the indentation load-displacement (P-h) curves of
paraffin and GOxA-PCM. Here, for clear comparison, only one
typical P-h curve is shown for each loading condition for each
_
material. Fig. 6b suggests a transition at P=Pz0.005s 1
: at faster
rates, paraffin (black-dash) behaves almost the same as GOxA-PCM
(red-dash); at slower rates, paraffin's curve (black-solid) is much
lower. In fact, the 20-fold strain-rate drop induces a minimal
behavior change for GOxA-PCM (red-dash / red-solid), while
inducing a drastic drop for paraffin (black-dash / black-solid).
Thus, paraffin's strain rate dependency is qualitatively much
more pronounced, especially at slower rates (P=P<~0.005s_ 1
).
As discussed in Appendix 3, the quantitative characterization of
strain-rate dependence requires the steady state (SS) condition,
corresponding to ε_ ¼ P=2P _ (see Eq. (A9)). Fig. 6ced show the
measured strain rates (_ε ¼ h=h) _ _
and P=P vs. h for GOxA-PCM and
paraffin, respectively, corresponding to the loading schedules in
Fig. 6a. The black curves in Fig. 6ced imply that the instrumental
control of P=P _ is very accurate at the intended values (P=P¼2_ _ ε0 ,
0:2_ε0 , and 0:02_ε0 ) for both samples; in fact, the complete transition
time between any two preset rates is only 0.01e1.0 s (not shown
here).
On the other hand, the red curves in Fig. 6c show that each
responded strain rate needs significant time to reach its steady-
state (SS) value (P=2P),_ suggesting the viscoelasticity nature of
GOxA-PCM. The red curves in Fig. 6d demonstrate that, for pure
paraffin, the strain rates reach the SS for the three larger values of
_ but not for the three smaller ones. The comparison of Fig. 6ced
P=P
shows that pure paraffin needs much longer time to achieve SS,
indicating that paraffin is much more viscous compared to GOxA-
_
PCM, especially at slower loading rates (P=P<~0.005s 1
).
3.3.2.2. Analysis of strain-rate-dependent hardness for paraffin and
GOxA-PCM. Fig. 7 shows the CSM modulus E and hardness H (see
Appendix 2 for general nanoindentation technique) vs. the
_
measured strain rate (_ε ¼ h=h) as labeled individually. Here the sub-
scripts show the materials and calculation method: “OP” designates
the Oliver-Pharr (OP) method, and “True” designates the true
hardness method as described later. It may be surprising that, while
340
Fig. 6. (a) Load-time (P-t) curves for the two sets (_ε0 ¼ 0.05 s1 and 0.0025s1) of three-strain-rate testing. (b) Load-displacement (P-h) curves of paraffin and GOxA-PCM cor-
responding to the loading schedules in (a). (c) P=P
_ and strain rate (_ε ¼ h=h) vs. h plots for GOxA-PCM and (d) that for paraffin. (A colour version of this figure can be viewed online.)
the CSM hardnesses of paraffin and GOxA-PCM are strain rate
dependent, their CSM moduli are apparently independent of strain-
rate across almost four orders of magnitude (105~101s1). This
can be understood by the known fact that the CSM modulus is
indeed the dynamic modulus and function of CSM harmonic fre-
quency [84] (constant 50 Hz for all tests). The CSM hardness rep-
resents the indentation mean pressure related to the current quasi-
static strain rate.
It may be also surprising to see that, GOxA-PCM's Oliver-Pharr
(OP) modulus (1.111 ± 0.032 GPa) is about 40% lower than that
Fig. 7. CSM modulus E and hardness H vs. strain rate for GOxA-PCM and paraffin. (A
colour version of this figure can be viewed online.)
Y. Xu et al. / Carbon 114 (2017) 334e346
_
(1.570 ± 0.066 GPa) of pure-paraffin. This appears to contradict the
known fact that graphene-reinforced organic materials are nor-
mally stiffer than the pure matrix counterparts [85,86]. Since the
GOxA-PCM composite sample is very compact without any signif-
icant porosity (see Fig. 2c), we believe that this apparent contra-
diction may be explained by the significant indentation pile-up on
paraffin, which is discussed in Appendix 4. It is worth to note that
(see Appendix 4), the highly irregular indent shape for pure paraffin
is first-ever observed for any homogeneous materials, probably due
to the underlying uneven plastic flow and local back-flow after
unloading of crystalline paraffin. As discussed in Appendix 5, we
could calculate the true hardness HTrue-Paraffin free of pile-up effect
for paraffin using a revised Joslin-Oliver method [87]. Here, since
the indentations on GOxA-PCM show no pile-up (see Appendix
Fig. A1a), the Oliver-Pharr hardness HOP-GOxA-PCM is directly used
for the true hardness of GOxA-PCM.
In Fig. 7, the HOP-GOxA-PCM curve plot two sets of hardness data for
GOxA-PCM: (1) the squares are the results obtained by averaging
over the six steady-states (SSs), and (2) the dense small triangles
are all individual data. We see a good match between the two sets
of data. This match implies that, when the indentation transits from
one SS to the sequential SS, the deformation is still in a quasi-steady
state (QSS) (instead of in a transient state). Therefore, the hardness
results are effectively steady-state results.
In Fig. 7, the HTrue-Paraffin curve also plots two data sets for
paraffin: (1) the squares of averaging over the three steady-states
(SSs) and the tails of the three slower loadings, and (2) the dense
individual data. This good matching between the two sets again
 Y. Xu et al. / Carbon 114 (2017) 334e346
implies that all indentation data are effectively steady-state results.
Moreover, Supplementary Figs. S3aeS3b show that, compared to
paraffin, GOxA-PCM has much better indentation data consistency
and is a material with better-defined solid behavior (instead of
viscous behavior).
By comparing paraffin (HTrue-paraffin) and GOxA-PCM (HOP-GOxA-
PCM) in Fig. 7, GOxA-PCM is always much harder than pure paraffin,
and the difference increases by decreasing the strain rate. For
example, the composite is 2.7
and 6.7
harder at ε_ ¼ 0.05s1 and
104s1, respectively, suggesting a strong reinforcement effect due
to the GOxA.
Fig. 7 also indicates that the two materials are strain rate
dependent as expected for organic materials. In this log-log plot of
HOP-GOxA-PCM vs. ε_ , the slope (i.e., the strain-rate sensitivity m) is
nicely a constant (~0.15) for all ε_ , corresponding to a constant
power-law exponent n z 6.7 for GOxA-PCM (see Appendix 3).
However, for paraffin, by increasing ε_ from ~104 to ~101, m de-
creases from ~0.45 to ~0.19, i.e., n increases from 2.2 to 5.2.
Consequently, the change of n suggests that, the deformation
mechanism for pure paraffin might transit from the molecule
diffusion (n < 3) at small strain rate to dislocation motion (n > 3) at
large strain rates (see Appendix 3). However, due to the space
limitation, the investigation of deformation mechanism of paraffin
and GOxA-PCM will be left for future work.
Thus, compared to paraffin, GOxA-PCM has a smaller m, and
hence is much less strain-rate sensitive, especially at smaller strain
rates. That is to say, by reinforcing paraffin using GOxA, the hard-
ness (strength) of the composite is not only much higher but also
more stable against strain rate change, especially at smaller strain
rates, which is critical for practical applications. For example, based
on Fig. 7 and Table 1, under a 0.27 MPa compression stress, it takes
paraffin only 3 h to deform 10% but would take GOxA-PCM almost
two centuries. Thus, the shape stabilization capability of GOxA-
PCM is drastically increased compared to pure paraffin.
Thus, in summary, the paraffin is largely reinforced and shape
stabilized by the GOxA-network. In the following, similar to the
discussion based on durometer testing, we want to show that this
reinforcement cannot be explained by the rule-of-mixture,
implying a strong bonding between GOxA and paraffin.
3.3.2.3. Nano/microscale characterization of graphene oxide aerogel
(GOxA) alone. In order to test the mechanical properties of GOxA
alone using nanoindentation, two large circular flat punch in-
denters were used: a 2 mm-diameter steel tip and a 456 mm-
diameter diamond tip. Here, for any flat punch indenter, the contact
area A is a known constant, and the hardness H and modulus E can
be determined using Eq. (A1)e(A3) in Appendix 2. Here, the contact
radius ac is known.
As demonstrated later, since GOxA's modulus E (75e400 kPa) is
6e7 orders of magnitude lower than that (1045 GPa for diamond or
200 GPa for steel) of indenters, Eq. (A3) can be nicely applied.
Equations A1 and A3 indicate that, when a cylindrical flat punch
indenter (of constant ac) is used, H and E are simply proportional to
P and S, respectively. Here, to use Eq. (A3), GOxA's n can be esti-
mated to be ~0.2 [88]. Also, for highly porous materials, the
Table 1
The duration L10 for 10% accumulative strain for paraffin and GOxA-PCM under two
values of uniaxial stress su (See Appendix 3 and Eq. (A10) for the discussion).
Material su (MPa) ε_ u (s1) L10 Duration to 10% strain
Paraffin 1.67 5.4
103 19 s
GOxA-PCM 1.67 2.7
106 8.8 h
Paraffin 0.27 9.0
106 3h
GOxA-PCM 0.27 ~1.8
1011 ~190 year
341
constraint factor, i.e., the ratio of H to strength s, is ~1.0 instead of
~3.0 [89].
Even when using the large flat punch indenters which are much
bigger than the pore size (0.2~1 mm as shown in Fig. 2a), it is still
very challenging to perform stable nanoindentations on GOxA due
to its extremely high porosity and extremely low mechanical
properties. Fig. 8 shows the H and E calculated by Eq. (A1) and Eq.
(A3) vs. indentation depth h, for two typical indentations (one
indentation for each tip). It should be noted that when h reaches
around 7 mm, both indentations become unstable, and the GOxA
under the indenters were catastrophically collapsed, which
generated large circular holes matching with the flat punch shapes
(see Supplementary Fig. S6).
During the stable stages of indentations as shown in Fig. 8, for
both tips, while H (fP) increases continuously and monotonically, E
(fS) interestingly steps up on multiple plateaus of ~2 mm steps.
Since 2 mm is around the upper bound of pore size (see Fig. 2a), each
step-up between E plateaus may be associated with collectively
crushing each effective-supporting layer of pores. The increase of H
and E with increasing h may be because indentation technique is
known to overestimate H and E due to the densification effect for
porous materials [75,76]. On the other hand, the increase of E in
plateau steps (instead of continuously increasing as for H) may be
due to that the CSM stiffness S is much more sensitive to the
stiffness of the local supporting densified structure. Also, while the
values of H (black symbols) match fairly well using the two tips, the
values of E (red symbols) deviate about 4 times between the two
tips, probably due to the high heterogeneous local fluctuation in the
highly porous GOxA structure as well as the way of how the
structure was densified under each indenter.
Due to the densification effect, Fig. 8 can be used to estimate the
upper bounds of E and H for GOxA alone. Table 2 lists the E and H
values at the middle of plateaus based on the number of supporting
layers collectively penetrated. Moreover, after penetrating the 3rd
collective layer, the GOxA under indentation was catastrophically
collapsed, so that the E and H values at the 3rd-layer penetration
provides the upper-bound estimates for GOxA's modulus and fail-
ure strength sf (noting H/s z 1.0 as aforementioned [89]), i.e.,
E z 75e389 kPa and sf z H z 238e400 Pa for GOxA alone. These
values fall in the ranges for GOxA alone based on previous studies
(see Appendix Table A1): 2e1200 kPa for modulus and
200e40000Pa for hardness.
However, Fig. 7 demonstrates that the GOxA-PCM is at least 2.7
times harder than pure paraffin whose hardness is in the range of
Fig. 8. H and E calculated by Eq. (A1) and Eq. (A3) vs. h, for two typical indentations on
GOxA (one for each tip). Here, because the intrinsic noise of XP head (2 mm tip) is
much higher, the associated E data was smoothened and plotted on the background of
the original unaltered data. (A colour version of this figure can be viewed online.)
342 Y. Xu et al. / Carbon 114 (2017) 334e346

Table 2
The E and H values at the middle of plateaus based on Fig. 8 and the number of layers collectively penetrated.

Indenter Layer# penetrated h at the middle of plateau (mm) E (kPa) H (Pa)

2 mm tip 1st ~1.0 143 43

456 mm tip 1st ~1.0 30 30
2 mm tip 2nd ~4.0 289 200
456 mm tip 2nd ~4.0 52 144
2 mm tip 3rd ~6.0 389 400
456 mm tip 3rd ~6.0 75 238

0.85e6 MPa, while GOxA-PCM is almost four orders of magnitude Acknowledgements

harder than GOxA alone. Thus, the reinforcement due to GOxA in
paraffin is drastically higher than the prediction of the rule-of-
mixture, indicating a strong bonding between GOxA and paraffin.
This is qualitatively consistent with the aforementioned results
based on durometer tests.
4. Conclusions
A 5 wt% graphene oxide aerogel (GOxA) reinforced paraffin-PCM
composite is developed. The composite maintains its original shape
above melting temperature of the PCM and to hold the molten
paraffin without any leakage, indicating superior shape
stabilization.
The X-ray diffraction and Fourier transform infrared (FTIR)
The authors appreciate the support of the National Science
Foundation (CBET-1235769). Any opinions, findings, and conclu-
sions or recommendations expressed in this material are those of
the author(s) and do not necessarily reflect the views of the Na-
tional Science Foundation. We thank Nancy Peltier in Biology
Department at Villanova for her help with the supercritical CO2
drying. We also appreciate the comprehensive comments and
constructive suggestions from the reviewers of this paper.
Appendix 1. Literature survey on the mechanical properties
of porous 3D carbon aerogels/networks.

Table A1
The mechanical properties of porous 3D carbon aerogels/networks.

Materials Processing/Material condition Density (mg/cm3) Strength s (kPa) Modulus E (kPa)

GA [20] Pristine 3e5 0.2e3 (decreasing with more testing cycles) 10e16
25  C ammonia treated GA [90] Ammonia treatment, but closer to pristine ~16 0.3 2
90  C ammonia treated GA [90] Ammonia treatment, further reinforced ~16 0.7 4.8
3D self-assembly of GO [51] Nobel-metal and glucose assistance ~30 42 260
CNT-graphene hybrid aerogel [91] Acid-treated CNT 32 30 (at 3% strain) 1200
CNT-graphene hybrid aerogel [91] Pristine CNT 41 70 (at 3% strain) 2900
GA [26] Pristine 30.9 40 1200
GA [26] Pristine 47.6 150 2800
GA [26] Pristine 96.1 660 6200
Graphene Assembly [52] Covalently cross-link GO 80e100 10000 51000

spectra imply a potentially new phase at the GOxA-paraffin inter- Appendix 2. Nanoindentation characterization
face in the composite. Durometer testing indicates that the com-
posite is much harder than paraffin at both room temperature and Generally, nanoindentation can be used to determine the
elevated temperatures and maintains significant strength above hardness H and modulus E of the indented material using Eqs.
paraffin's melting temperature. Nanoindentation testing shows (A1)e(A3) [79,92,93].
that the composite is 3e7
times harder and less strain-rate sen-
sitive than paraffin, especially at smaller strain rates. Thus, the P P
H¼ ¼ ; (A1)
composite is not only much harder but also much more stable A pa2c
against strain rate change, which is critical for practical applica-
tions. Furthermore, the durometer and nanoindentation tests both
S 1 1  n2 1  n2i
quantitatively indicate that the reinforcement of paraffin in GOxA is Er ¼ ; where ¼ þ ; (A2)
2ac Er E Ei
beyond the prediction by the rule-of-mixture, implying a strong
GOxA-PCM interfacial bonding.
To our best knowledge, this is the first study on the fundamental   S
E ¼ 1  n2 if Ei > > E; (A3)
mechanical behavior of paraffin and GOxA-PCM composite at 2ac
different temperatures and different strain rates, providing critical
insights into their behaviors. The relationship between the hard- where P is the indentation load; A and ac are the contact area and
ness and durometer index first-ever developed here will enable the radius, respectively. S is the contact stiffness. Er is the reduced
quantitative durometer testing on materials for many other appli- modulus as defined in Eq. (A2), where E and n are the modulus and
cations at different ambient conditions (e.g., temperatures and Poisson's ratio of the indented material, while Ei and ni are the
probably chemical environments) due to its versatile and simple quantities of the indenter.
nature. A nanoindenter can control P and continuously measure the
indentation displacement h. With the continuous stiffness mea-
surement (CSM) technique [79,92,93], a nanoindenter can also
 Y. Xu et al. / Carbon 114 (2017) 334e346
continuously measure S.
For flat homogenous materials without pile-up, the Oliver-Pharr
method can be used to determine the contact radius ac through P, h,
S using Eqs. (A4) and (A5) [79,92,93].
P
hc ¼ h  0:75 ; (A4)
S where A' and B' are fitting parameters.
Ac ¼ pa2c ¼ f ðhc Þ; (A5)
where hc is the contact depth. Here, Eq. (A5) is called area function,
which can be calibrated using standard materials with known
moduli or directly determined by visualizing the indenter shape
using microscopy [79,92,93].
It should be noted that the measured indentation properties
(modulus or hardness) are due to the average responses from the
indentation-deformed volume (plastic zone) [72,73,89]. Based on
Johnson's expanding cavity model, the plastic zone is normally
estimated by a hemisphere with a diameter 1~2
of the contact
diameter d [72,73,89].
As shown in Fig. 2a, 1.0 mm would be a good estimate for the
upper bound of the pore-size in GOxA and hence used as the
characteristic microstructure length scale (lu) in the GOxA-PCM
composite. Our indentation results shown in Fig. 7 are always
from h > 5 mm, namely, h > 5lu. More importantly, for a Berkovich
indenter, the contact diameter d z 7h > 35 mm. Thus, any h > 5 mm
indentation corresponds to a plastic zone with diameter >35 mm,
i.e., >35lu.
Thus, the indented material in the GOxA-PCM composite can be
effectively treated well as a homogeneous material for the results in
Fig. 7.
Appendix 3. Multi-strain-rate characterization using
nanoindentation
For strain-rate-dependent materials, their strengths depend on
not only the strain rate but also the deformation history. For
example, after instantaneously applying a constant strain rate (_εu ),
the required stress would transiently change and finally reach to a
constant steady-state (SS) value. Thus, only at the steady-state, a
strain rate can be uniquely correlated to the applied stress, namely
flow strength (s). In order to quantitatively study the strain-rate-
dependence, the mechanical properties should be measured at
the steady state (SS).
A phenomenological power-law relationship is commonly used
to describe the strain-rate dependence of flow strength at the SS,
ε_ u ¼ Asn or alternatively s ¼ B_εm
u; (A6)
where ε_ u and s are the strain rate and stress during a uniaxial
testing at the SS; n, m, A and B are fitting parameters, while m is
called the strain rate sensitivity, and n (¼1/m) is called the power-
law exponent. The value of n normally correlates to the deforma-
tion mechanism, e.g., for crystals, n < 3 normally indicates diffusive
deformation, while n > 3 normally indicates dislocational defor-
mation [94].
The indentation strain rate ε_ is defined as the displacement-
_ 10 B0 1=m
rate-to-displacement-ratio (_ε ¼ h=h) [82,83]. Due to the strong
strain gradient and stress concentration under indentation, the
equivalent uniaxial strain ε_ u z0:09_ε [95], while s zH/3 [96,97].
Thus, Eq. (A6) can be revised to [94].
Hn
ε_ ¼ A ; alternatively H ¼ 3
0:09m B_εm ;
0:09
3n
Or simply,
343
ε_ ¼ A0 H n ;
alternatively
H ¼ B0 ε_ m (A7)
Nanoindenter intrinsically controls P (instead of h). Thus, it is
much convenient to directly control the loading rate to alter the
strain rate. For a self-similar indenter (e.g., a perfect Berkovich or
conical indenter) indenting a homogeneous material, by neglecting
indentation size effect [98,99], the contact area A is proportional to
h2. Thus, A ¼ Ch2, where C is a constant related to indenter geom-
etry. By differentiating H¼P/A ¼ P/(Ch2), we have [100].
dH dP dh h_ P_ H_
¼  2 ; i:e; 2_ε ¼ 2 ¼  ; (A8)
H P h h P H
.
2_ε ¼ P_ P if H_ ¼ 0: (A9)
Because a constant H (z3s) is expected for a material during a
steady state deformation, based on Eq. (A9), we have 2_ε ¼ P=P. _
Therefore, a constant ε_ test can be approximated by running con-
stant load-rate-to-load-ratio P=P _ (¼2_ε) [100], i.e., exponentially
increasing the load.
However, in practice, an indentation with one slow strain rate
(104~105s1) would take multiple days. Consequently, a constant
thermal drift rate - a key assumption for quantitative indentation
analysis - may not be valid [101]. Therefore, a multiple-strain-rate
indentation technique is developed here, particularly with three
sequentially decreasing strain rates (P=P¼2__ ε0 , 0:2_ε0 , and 0:02_ε0 )
during a single loading (see Fig. 6a) to minimize its duration (<4 h).
The loading portion at each strain rate lasts about 1/3 of the
maximum depth. Two sets of three-strain-rate indentations were
performed with ε_ 0 equals 0.05 s1 and 2.5
103s1 (see Fig. 6a) in
this study, corresponding to six preset strain rates, i.e., (0.025, 0.25,
0.5, 2.5, 5, 50)
103 s1 .
An interesting and practical observation should be mentioned:
the deformation during each entire three-strain-rate indentation is
almost always at either the steady state (SS) or quasi-steady state
(QSS). This is because the slow and smooth hardness change during
the transition between each pair of preset strain rates. This has
been demonstrated for both paraffin and GOxA-PCM composite.
The SS (and QSS) deformation during the entire multi-strain-rate
testing provides a significant benefit: the SS (and QSS) ε_ (in Eq.
(A7)) spans continuously over a wide range (see Fig. 7) instead of
only the preset values (e.g., 3 strain rates for each three-strain-rate
testing).
It may also be important in practical considerations to predict
the life L of a stressed structural part made of strain-rate sensitive
material. We may define the expected life L10 under a constant
uniaxial stress su as the duration for reaching a preset critical cu-
mulative strain εc, say 10% (i.e., εc ¼ 0.1), due to the corresponding
steady-state strain rate ε_ u . Noticing that L10 ¼ εc =_εu ¼ 0:1=_εu , based
on Eq. (A7), we have
 
L10 ¼ : (A10)
9 3su
Here, B' and m can be found experimentally by fitting H vs. ε_
0
using H ¼ B ε_ m (see Fig. 7). For example, for HOP-GOxA-PCM shown in
Fig. 7, the fitting parameters are B’ ¼ 23.35 MPa and m ¼ 0.15, and
hence L10 e6.0
109 s z 190 year for su ¼ 0.27 MPa based on Eq.
(A10). L10 for paraffin and GOxA-PCM under two values of su are
listed in Table 1.
344
Appendix 4. Irregular localized pile-ups around each
indentation on Paraffin
Fig. A1a shows the optical image of a typical indent on GOxA-
PCM, displaying flat indent surfaces and straight edges without
pile-up. Thus, we expect that the Oliver-Pharr method can be used
to determine the modulus and hardness well for GOxA-PCM
composite. On the contrary, Fig. A1b shows a typical indent on
paraffin with bumpy indent surfaces and wavy indent edges, which
is the case for every indentation on paraffin (also see the SEM image
in Supplementary Fig. S4). To our best knowledge, this highly
irregular indent shape is first-ever observed for any homogeneous
materials. This is probably due to the underlying uneven plastic
flow and local back-flow (resulted from the residual stress field in
the permanent indent) after unloading of crystalline paraffin.
The investigation of this surprising irregular indentation plas-
ticity of paraffin is not the focus of this paper and hence will be left
for a future work. Preliminary investigation using ex-situ optical
microscopy on post-indentation morphology shows that the indent
irregularity happens almost spontaneously (within 2 s); thus, the
recrystallization of paraffin crystal in the indented area may be
ruled out as the key reason as it requires diffusion.
Fig. A1. Optical images of (a) a typical 30 mm-deep indent on GOxA-PCM and (b) one on paraffin. (c) and (d) The magnified optical images of the boxed region in (b), where the focal
depths are (c) 0 mm and (d) 8 mm, respectively, showing two large ~8 mm-tall localized pile-ups.
Due to the uneven plastic flow, Fig. A1b-A1d interestingly
indicate multiple localized pile-ups (instead of the common form of
single pile-up [93,102]) on each indent edge. For example, Fig. A1b-
A1d show that, an edge of a 30 mm indentation has two large
~8 mm-tall localized pile-ups which did not exist prior to the
indentation (not shown here). Moreover, in order to further
confirm the existence of pile-ups for paraffin, additional in-
dentations were done using a 300 mm sapphire spherical indenter
(see Supplementary Fig. S5). Those indents clearly show multiple
localized pile-ups. Unfortunately, as shown in Fig. A1b and
Supplementary S4, it is very difficult to have a precise estimate for
the indent area due to the strong indent irregularity, and more
importantly, the indent may be altered significantly from the con-
tact under load due to the possible aforementioned plastic back-
flow (see Fig. A1b and Supplementary S4).
Appendix 5. Calculation of true hardness free of the pile-up
effect for paraffin
As discussed in Appendix 4, significant pile-ups are observed
around each indentation on paraffin. The Oliver-Pharr method
based on Eq. (A4) assumes no pile-up, and it underestimates the
contact depth hc and hence the contact area A in case of indentation
Y. Xu et al. / Carbon 114 (2017) 334e346
pile-up [79,92,93]. In order to determine the true hardness free of
the pile-up effect, it is essential to determine the true contact area
A. Two existing methods to correct for the pile-up effect are (1)
estimate A at the maximum indentation depth by directly
measuring the residual indent's area using an appropriate micro-
scopy [103,104], and (2) a revised Joslin-Oliver method [87] as
discussed below.
Unfortunately, it is very difficult to have a precise estimate for
the indent area due to the strong indent irregularity and possible
plastic back-flow. Therefore, we could use a revised Joslin-Oliver
method [87] (see Eq. (A11)) to estimate the true hardness HTrue
free of the pile-up effect, provided we know the true modulus ETrue.
2 H
ETrue OP
HTrue ¼ 2
; (A11)
EOP
where HOP and EOP are the Oliver-Pharr hardness and modulus,
respectively. Here, as aforementioned, the GOxA-PCM is expected
to be slightly stiffer than the paraffin, and the GOxA-PCM com-
posite's Oliver-Pharr modulus (EOP-GOxA-PCM ¼ 1.111 ± 0.032 GPa in
Fig. 7) would be free of pile-up effect, which could be a good upper
bound estimate for paraffin's true modulus, i.e., ETrue-paraffin
z1.111 GPa. Thus, Eq. (A11) can be used to calculate HTrue-paraffin (a
good upper bound) as plotted in Fig. 7.
Appendix A. Supplementary data
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.carbon.2016.11.069.
References
[1] J.F. Li, W. Lu, Y.B. Zeng, Z.P. Luo, Simultaneous enhancement of latent heat
and thermal conductivity of docosane-based phase change material in the
presence of spongy graphene, Sol. Energy Mater. Sol. Cells 128 (0) (2014)
48e51.
[2] R. Ehid, A.S. Fleischer, Development and characterization of paraffin-based
shape stabilized energy storage materials, Energy Convers. Manag. 53 (1)
(2012) 84e91.
[3] G.-Q. Qi, C.-L. Liang, R.-Y. Bao, Z.-Y. Liu, W. Yang, B.-H. Xie, M.-B. Yang,
Polyethylene glycol based shape-stabilized phase change material for ther-
mal energy storage with ultra-low content of graphene oxide, Sol. Energy
Mater. Sol. Cells 123 (2014) 171e177.
[4] M. Mehrali, S.T. Latibari, M. Mehrali, H.S.C. Metselaar, M. Silakhori, Shape-
stabilized phase change materials with high thermal conductivity based on
paraffin/graphene oxide composite, Energy Convers. Manag. 67 (0) (2013)
275e282.
[5] J.-L. Zeng, S.-H. Zheng, S.-B. Yu, F.-R. Zhu, J. Gan, L. Zhu, Z.-L. Xiao, X.-Y. Zhu,
Z. Zhu, L.-X. Sun, Z. Cao, Preparation and thermal properties of palmitic acid/
 Y. Xu et al. / Carbon 114 (2017) 334e346
polyaniline/exfoliated graphite nanoplatelets form-stable phase change
materials, Appl. Energy 115 (2014) 603e609.
[6] M.M. Farid, A.M. Khudhair, S.A.K. Razack, S. Al-Hallaj, A review on phase
change energy storage: materials and applications, Energy Convers. Manag.
45 (9e10) (2004) 1597e1615.
[7] M. Xiao, B. Feng, K. Gong, Preparation and performance of shape stabilized
phase change thermal storage materials with high thermal conductivity,
Energy Convers. Manag. 43 (1) (2002) 103e108.
[8] M.-Y. Shen, T.-Y. Chang, T.-H. Hsieh, Y.-L. Li, C.-L. Chiang, H. Yang, M.-C. Yip,
Mechanical properties and tensile fatigue of graphene nanoplatelets rein-
forced polymer nanocomposites, J. Nanomater. 2013 (2013) 9.
[9] Y. Zhong, M. Zhou, F. Huang, T. Lin, D. Wan, Effect of graphene aerogel on
thermal behavior of phase change materials for thermal management, Sol.
Energy Mater. Sol. Cells 113 (0) (2013) 195e200.
[10] T.F. Baumann, A.E. Gash, S.C. Chinn, A.M. Sawvel, R.S. Maxwell, J.H. Satcher,
Synthesis of high-surface-area alumina aerogels without the use of alkoxide
precursors, Chem. Mater. 17 (2) (2005) 395e401.
[11] M. Moner-Girona, A. Roig, E. Molins, J. Llibre, Sol-gel route to direct forma-
tion of silica aerogel microparticles using supercritical solvents, J. Sol-Gel Sci.
Technol. 26 (1) (2003) 645e649.
[12] S.M. Jung, H.Y. Jung, M.S. Dresselhaus, Y.J. Jung, J. Kong, A facile route for 3D
aerogels from nanostructured 1D and 2D materials, Sci. Rep. 2 (2012) 849.
[13] Y. Tang, K.L. Yeo, Y. Chen, L.W. Yap, W. Xiong, W. Cheng, Ultralow-density
copper nanowire aerogel monoliths with tunable mechanical and electrical
properties, J. Mater. Chem. A 1 (23) (2013) 6723e6726.
[14] S.M. Jung, D.J. Preston, H.Y. Jung, Z. Deng, E.N. Wang, J. Kong, Porous Cu
nanowire aerosponges from one-step assembly and their applications in
heat dissipation, Adv. Mater. 28 (7) (2016) 1413e1419.
[15] W. He, G. Li, S. Zhang, Y. Wei, J. Wang, Q. Li, X. Zhang, Polypyrrole/silver
coaxial nanowire aero-sponges for temperature-independent stress sensing
and stress-triggered joule heating, ACS Nano 9 (4) (2015) 4244e4251.
[16] A. Mikhalchan, Z. Fan, T.Q. Tran, P. Liu, V.B.C. Tan, T.-E. Tay, H.M. Duong,
Continuous and scalable fabrication and multifunctional properties of carbon
nanotube aerogels from the floating catalyst method, Carbon 102 (2016)
409e418.
[17] T. Horikawa, J.i. Hayashi, K. Muroyama, Size control and characterization of
spherical carbon aerogel particles from resorcinoleformaldehyde resin,
Carbon 42 (1) (2004) 169e175.
[18] M.A. Worsley, J.H. Satcher, T.F. Baumann, Synthesis and characterization of
monolithic carbon aerogel nanocomposites containing double-walled carbon
nanotubes, Langmuir 24 (17) (2008) 9763e9766.
[19] T.Q. Tran, Z. Fan, P. Liu, H.M. Duong, Advanced morphology-controlled
manufacturing of carbon nanotube fibers, thin films and aerogels from aer-
ogel technique, in: Asia Pacific Confederation of Chemical Engineering
Congress 2015, Melbourne: Engineers Australia, 2015, pp. 2444e2451.
[20] H. Hu, Z. Zhao, W. Wan, Y. Gogotsi, J. Qiu, Ultralight and highly compressible
graphene aerogels, Adv. Mater. 25 (15) (2013) 2219e2223.
[21] L. Qiu, D. Liu, Y. Wang, C. Cheng, K. Zhou, J. Ding, V.-T. Truong, D. Li, Me-
chanically robust, electrically conductive and stimuli-responsive binary
network hydrogels enabled by superelastic graphene aerogels, Adv. Mater.
26 (20) (2014) 3333e3337.
[22] Y. Xu, K. Sheng, C. Li, G. Shi, Self-assembled graphene hydrogel via a one-step
hydrothermal process, ACS Nano 4 (7) (2010) 4324e4330.
[23] K. Zhang, L.L. Zhang, X.S. Zhao, J. Wu, Graphene/polyaniline nanofiber
composites as supercapacitor electrodes, Chem. Mater. 22 (4) (2010)
1392e1401.
[24] G. Tang, Z.-G. Jiang, X. Li, H.-B. Zhang, A. Dasari, Z.-Z. Yu, Three dimensional
graphene aerogels and their electrically conductive composites, Carbon 77
(0) (2014) 592e599.
[25] Y. Qian, I.M. Ismail, A. Stein, Ultralight, high-surface-area, multifunctional
graphene-based aerogels from self-assembly of graphene oxide and resol,
Carbon 68 (0) (2014) 221e231.
[26] X. Zhang, Z. Sui, B. Xu, S. Yue, Y. Luo, W. Zhan, B. Liu, Mechanically strong and
highly conductive graphene aerogel and its use as electrodes for electro-
chemical power sources, J. Mater. Chem. 21 (18) (2011) 6494e6497.
[27] M.A. Worsley, P.J. Pauzauskie, T.Y. Olson, J. Biener, J.H. Satcher, T.F. Baumann,
Synthesis of graphene aerogel with high electrical conductivity, J. Am. Chem.
Soc. 132 (40) (2010) 14067e14069.
[28] M.B. Lim, M. Hu, S. Manandhar, A. Sakshaug, A. Strong, L. Riley,
P.J. Pauzauskie, Ultrafast solegel synthesis of graphene aerogel materials,
Carbon 95 (2015) 616e624.
[29] H. Huang, P. Chen, X. Zhang, Y. Lu, W. Zhan, Edge-to-edge assembled gra-
phene oxide aerogels with outstanding mechanical performance and su-
perhigh chemical activity, Small 9 (8) (2013) 1397e1404.
[30] S. Ye, Q. Zhang, D. Hu, J. Feng, Core-shell-like structured graphene aerogel
encapsulating paraffin: shape-stable phase change material for thermal en-
ergy storage, J. Mater. Chem. A 3 (7) (2015) 4018e4025.
[31] S.T. Nguyen, H.T. Nguyen, A. Rinaldi, N.P.V. Nguyen, Z. Fan, H.M. Duong,
Morphology control and thermal stability of binderless-graphene aerogels
from graphite for energy storage applications, Colloids Surfaces A Phys-
icochem. Eng. Aspects 414 (0) (2012) 352e358.
[32] J. Liang, Z. Cai, L. Li, L. Guo, J. Geng, Scalable and facile preparation of gra-
phene aerogel for air purification, RSC Adv. 4 (10) (2014) 4843e4847.
[33] Q. Fang, B. Chen, Self-assembly of graphene oxide aerogels by layered double
hydroxides cross-linking and their application in water purification, J. Mater.
345
Chem. A 2 (23) (2014) 8941e8951.
[34] F. Irin, S. Das, F.O. Atore, M.J. Green, Ultralow percolation threshold in aerogel
and cryogel templated composites, Langmuir 29 (36) (2013) 11449e11456.
[35] R.J. Warzoha, A.S. Fleischer, Effect of graphene layer thickness and me-
chanical compliance on interfacial heat flow and thermal conduction in
solideliquid phase change materials, ACS Appl. Mater. Interfaces 6 (15)
(2014) 12868e12876.
[36] R.J. Warzoha, R.M. Weigand, A.S. Fleischer, Temperature-dependent thermal
properties of a paraffin phase change material embedded with herringbone
style graphite nanofibers, Appl. Energy 137 (2015) 716e725.
[37] R.J. Warzoha, A.S. Fleischer, Effect of carbon nanotube interfacial geometry
on thermal transport in solideliquid phase change materials, Appl. Energy
154 (2015) 271e276.
[38] J. Yang, E. Zhang, X. Li, Y. Zhang, J. Qu, Z.-Z. Yu, Cellulose/graphene aerogel
supported phase change composites with high thermal conductivity and
good shape stability for thermal energy storage, Carbon 98 (2016) 50e57.
[39] S. Tahan Latibari, M. Mehrali, M. Mehrali, T.M. Indra Mahlia, H.S. Cornelis
Metselaar, Synthesis, characterization and thermal properties of nano-
encapsulated phase change materials via solegel method, Energy 61 (2013)
664e672.
[40] M. Mehrali, S. Tahan Latibari, M. Mehrali, T.M.I. Mahlia, H.S. Cornelis Met-
selaar, Effect of carbon nanospheres on shape stabilization and thermal
behavior of phase change materials for thermal energy storage, Energy
Convers. Manag. 88 (2014) 206e213.
[41] Z. Zhang, X. Fang, Study on paraffin/expanded graphite composite phase
change thermal energy storage material, Energy Convers. Manag. 47 (3)
(2006) 303e310.
[42] Z. Sun, W. Kong, S. Zheng, R.L. Frost, Study on preparation and thermal en-
ergy storage properties of binary paraffin blends/opal shape-stabilized phase
change materials, Sol. Energy Mater. Sol. Cells 117 (0) (2013) 400e407.
[43] J.-N. Shi, M.-D. Ger, Y.-M. Liu, Y.-C. Fan, N.-T. Wen, C.-K. Lin, N.-W. Pu,
Improving the thermal conductivity and shape-stabilization of phase change
materials using nanographite additives, Carbon 51 (2013) 365e372.
[44] S. Wi, J. Seo, S.-G. Jeong, S.J. Chang, Y. Kang, S. Kim, Thermal properties of
shape-stabilized phase change materials using fatty acid ester and exfoliated
graphite nanoplatelets for saving energy in buildings, Sol. Energy Mater. Sol.
Cells 143 (2015) 168e173.
[45] M. Mehrali, S.T. Latibari, M. Mehrali, T.M. Indra Mahlia, H.S. Cornelis Met-
selaar, M.S. Naghavi, E. Sadeghinezhad, A.R. Akhiani, Preparation and char-
acterization of palmitic acid/graphene nanoplatelets composite with
remarkable thermal conductivity as a novel shape-stabilized phase change
material, Appl. Therm. Eng. 61 (2) (2013) 633e640.
[46] X. Zhao, Q. Zhang, D. Chen, P. Lu, Enhanced mechanical properties of
graphene-based poly(vinyl alcohol) composites, Macromolecules 43 (5)
(2010) 2357e2363.
[47] C.-C. Ji, M.-W. Xu, S.-J. Bao, C.-J. Cai, Z.-J. Lu, H. Chai, F. Yang, H. Wei, Self-
assembly of three-dimensional interconnected graphene-based aerogels and
its application in supercapacitors, J. Colloid Interface Sci. 407 (0) (2013)
416e424.
[48] J.A. King, D.R. Klimek, I. Miskioglu, G.M. Odegard, Mechanical properties of
graphene nanoplatelet/epoxy composites, J. Appl. Polym. Sci. 128 (6) (2013)
4217e4223.
[49] N. Norhakim, S.H. Ahmad, C.H. Chia, N.M. Huang, Mechanical and thermal
properties of graphene oxide filled epoxy nanocomposites, Sains Malays. 43
(4) (2014) 603e609.
[50] D. Cai, M. Song, A simple route to enhance the interface between graphite
oxide nanoplatelets and a semi-crystalline polymer for stress transfer,
Nanotechnology 20 (31) (2009) 315708.
[51] Z. Tang, S. Shen, J. Zhuang, X. Wang, Noble-metal-promoted three-
dimensional macroassembly of single-layered graphene oxide, Angew.
Chem. Int. Ed. 49 (27) (2010) 4603e4607.
[52] M.A. Worsley, S.O. Kucheyev, H.E. Mason, M.D. Merrill, B.P. Mayer, J. Lewicki,
C.A. Valdez, M.E. Suss, M. Stadermann, P.J. Pauzauskie, J.H. Satcher, J. Biener,
T.F. Baumann, Mechanically robust 3D graphene macroassembly with high
surface area, Chem. Commun. 48 (67) (2012) 8428e8430.
[53] W.S. Hummers, R.E. Offeman, Preparation of graphitic oxide, J. Am. Chem.
Soc. 80 (6) (1958) 1339.
[54] Y.-R. Huang, Y. Jiang, J.L. Hor, R. Gupta, L. Zhang, K.J. Stebe, G. Feng,
K.T. Turner, D. Lee, Polymer nanocomposite films with extremely high
nanoparticle loadings via capillary rise infiltration (CaRI), Nanoscale 7 (2)
(2015) 798e805.
[55] Y. Cho, S.Y. Lee, L. Ellerthorpe, G. Feng, G. Lin, G. Wu, J. Yin, S. Yang, Elas-
toplastic inverse opals as power-free mechanochromic sensors for force
recording, Adv. Funct. Mater. 25 (38) (2015) 6041e6049.
[56] S. Lowell, J.E. Shields, M.A. Thomas, M. Thommes, Characterization of Porous
Solids and Powders: Surface Area, Pore Size and Density, Springer Science &
Business Media, 2012.
[57] L. Zhang, G. Chen, M.N. Hedhili, H. Zhang, P. Wang, Three-dimensional as-
semblies of graphene prepared by a novel chemical reduction-induced self-
assembly method, Nanoscale 4 (22) (2012) 7038e7045.
[58] R. Kumar, M. Mamlouk, K. Scott, A graphite oxide paper polymer electrolyte
for direct methanol fuel cells, Int. J. Electrochem. 2011 (2011) 7.
[59] D. Han, L. Yan, Supramolecular hydrogel of chitosan in the presence of gra-
phene oxide nanosheets as 2D cross-linkers, ACS Sustain. Chem. Eng. 2 (2)
(2014) 296e300.
346 Y. Xu et al. / Carbon 114 (2017) 334e346
[60] E.-Y. Choi, T.H. Han, J. Hong, J.E. Kim, S.H. Lee, H.W. Kim, S.O. Kim, Non-
covalent functionalization of graphene with end-functional polymers,
J. Mater. Chem. 20 (10) (2010) 1907e1912.
[61] N.G. Sahoo, H. Bao, Y. Pan, M. Pal, M. Kakran, H.K.F. Cheng, L. Li, L.P. Tan,
Functionalized carbon nanomaterials as nanocarriers for loading and de-
livery of a poorly water-soluble anticancer drug: a comparative study, Chem.
Commun. 47 (18) (2011) 5235e5237.
[62] M. Chen, C. Zhang, X. Li, L. Zhang, Y. Ma, L. Zhang, X. Xu, F. Xia, W. Wang,
J. Gao, A one-step method for reduction and self-assembling of graphene
oxide into reduced graphene oxide aerogels, J. Mater. Chem. A 1 (8) (2013)
2869e2877.
[63] N. Shukla, C. Liu, P.M. Jones, D. Weller, FTIR study of surfactant bonding to
FePt nanoparticles, J. Magnetism Magnetic Mater. 266 (1e2) (2003)
178e184.
[64] J. Coates, Interpretation of Infrared Spectra, a Practical Approach, Encyclo-
pedia of Analytical Chemistry, John Wiley & Sons, Ltd, 2006.
[65] G. Hollis, D.R. Davies, T.M. Johnson, L.G. Wade, Organic Chemistry, in:
L.G. Wade Jr (Ed.), Test Item File, sixth ed., Pearson Prentice Hall, Upper
Saddle River, N.J, 2006.
[66] G.M. Miha ly Freund, Paraffin Products: Properties, Technologies, Applica-
tions, 1982.
[67] R. Yogamalar, R. Srinivasan, A. Vinu, K. Ariga, A.C. Bose, X-ray peak broad-
ening analysis in ZnO nanoparticles, Solid State Commun. 149 (43e44)
(2009) 1919e1923.
[68] Y.H. Zhao, X.Z. Liao, Z. Jin, R.Z. Valiev, Y.T. Zhu, Microstructures and me-
chanical properties of ultrafine grained 7075 Al alloy processed by ECAP and
their evolutions during annealing, Acta Mater. 52 (15) (2004) 4589e4599.
[69] T. Ungar, A. Borbely, The effect of dislocation contrast on x-ray line broad-
ening: a new approach to line profile analysis, Appl. Phys. Lett. 69 (21)
(1996) 3173e3175.
[70] T.K. Gupta, B.P. Singh, R.K. Tripathi, S.R. Dhakate, V.N. Singh, O.S. Panwar,
R.B. Mathur, Superior nano-mechanical properties of reduced graphene ox-
ide reinforced polyurethane composites, RSC Adv. 5 (22) (2015)
16921e16930.
[71] H.J. Qi, K. Joyce, M.C. Boyce, Durometer hardness and the stress-strain
behavior of elastomeric materials, Rubber Chem. Technol. 76 (2) (2003)
419e435.
[72] G. Feng, S. Qu, Y. Huang, W.D. Nix, An analytical expression for the stress
field around an elastoplastic indentation/contact, Acta Mater. 55 (9) (2007)
2929e2938.
[73] G. Feng, S. Qu, Y. Huang, W.D. Nix, A quantitative analysis for the stress field
around an elastoplastic indentation/contact, J. Mater. Res. 24 (3) (2009)
704e718.
[74] G. Feng, The Application of Contact Mechanics in the Study of Nano-
indentation, 2006.
[75] K. Vanstreels, C. Wu, M. Gonzalez, D. Schneider, D. Gidley, P. Verdonck,
M.R. Baklanov, Effect of pore structure of nanometer scale porous films on
the measured elastic modulus, Langmuir 29 (38) (2013) 12025e12035.
s, C. Yacou, M. Verdier, R. Dendievel, A. Ayral, Mechanical properties
[76] D. Jauffre
of hierarchical porous silica thin films: experimental characterization by
nanoindentation and Finite Element modeling, Microporous Mesoporous
Mater. 140 (1e3) (2011) 120e129.
[77] B. Barabadi, R. Nathan, K.-p. Jen, Q. Wu, On the characterization of lifting
forces during the rapid compaction of deformable porous media, J. Heat
Transf. 131 (10) (2009) 101006.
[78] R. Crawford, R. Nathan, L. Wang, Q. Wu, Experimental study on the lift
generation inside a random synthetic porous layer under rapid compaction,
Exp. Therm. Fluid Sci. 36 (2012) 205e216.
[79] W.C. Oliver, G.M. Pharr, Measurement of hardness and elastic modulus by
instrumented indentation: advances in understanding and refinements to
methodology, J. Mater. Res. 19 (01) (2004) 3e20.
[80] X. Li, B. Bhushan, A review of nanoindentation continuous stiffness
measurement technique and its applications, Mater. Charact. 48 (1) (2002)
11e36.
[81] J. Hay, P. Agee, E. Herbert, Continuous stiffness measurement during
instrumented indentation testing, Exp. Tech. 34 (3) (2010) 86e94.
[82] B.N. Lucas, W.C. Oliver, Indentation power-law creep of high-purity indium,
Metallurgical Mater. Trans. A 30 (3) (1999) 601e610.
[83] J.M. Wheeler, V. Maier, K. Durst, M. Go€ken, J. Michler, Activation parameters
for deformation of ultrafine-grained aluminium as determined by indenta-
tion strain rate jumps at elevated temperature, Mater. Sci. Eng. A 585 (2013)
108e113.
[84] E.G. Herbert, W.C. Oliver, G.M. Pharr, Nanoindentation and the dynamic
characterization of viscoelastic solids, J. Phys. D Appl. Phys. 41 (7) (2008)
074021.
[85] M. Bhattacharya, Polymer nanocompositesda comparison between carbon
nanotubes, graphene, and clay as nanofillers, Materials 9 (4) (2016) 262.
[86] J. Du, H.-M. Cheng, The fabrication, properties, and uses of graphene/polymer
composites, Macromol. Chem. Phys. 213 (10e11) (2012) 1060e1077.
[87] G. Feng, W.D. Nix, Indentation size effect in MgO, Scr. Mater. 51 (6) (2004)
599e603.
[88] N. Bheekhun, A.R. Abu Talib, M.R. Hassan, Aerogels in aerospace: an over-
view, Adv. Mater. Sci. Eng. 2013 (2013) 18.
[89] K.L. Johnson, Contact Mechanics, Cambridge University Press, 1985.
[90] Z. Han, Z. Tang, P. Li, G. Yang, Q. Zheng, J. Yang, Ammonia solution
strengthened three-dimensional macro-porous graphene aerogel, Nanoscale
5 (12) (2013) 5462e5467.
[91] Z. Sui, Q. Meng, X. Zhang, R. Ma, B. Cao, Green synthesis of carbon nanotube-
graphene hybrid aerogels and their use as versatile agents for water purifi-
cation, J. Mater. Chem. 22 (18) (2012) 8767e8771.
[92] K.O. Kese, Z.C. Li, B. Bergman, Method to account for true contact area in
soda-lime glass during nanoindentation with the Berkovich tip, Mater. Sci.
Eng. A 404 (1e2) (2005) 1e8.
[93] J.D. Gale, A. Achuthan, The effect of work-hardening and pile-up on nano-
indentation measurements, J. Mater. Sci. 49 (14) (2014) 5066e5075.
[94] G. Feng, A.H.W. Ngan, Creep and strain burst in indium and aluminium
during nanoindentation, Scr. Mater. 45 (8) (2001) 971e976.
[95] W.H. Poisl, W.C. Oliver, B.D. Fabes, The relationship between indentation and
uniaxial creep in amorphous selenium, J. Mater. Res. 10 (08) (1995)
2024e2032.
[96] P. Zhang, S.X. Li, Z.F. Zhang, General relationship between strength and
hardness, Mater. Sci. Eng. A 529 (2011) 62e73.
[97] D. Tabor, The Hardness of Metals, Oxford University Press, 2000.
[98] W.D. Nix, H. Gao, Indentation size effects in crystalline materials: a law for
strain gradient plasticity, J. Mech. Phys. Solids 46 (3) (1998) 411e425.
[99] G.M. Pharr, E.G. Herbert, Y. Gao, The indentation size effect: a critical ex-
amination of experimental observations and mechanistic interpretations,
Annu. Rev. Mater. Res. 40 (1) (2010) 271e292.
[100] B.N. Lucas, W.C. Oliver, Indentation power-law creep of high-purity indium,
Metallurgical Mater. Trans. A 30(3) 601e610.
[101] V. Maier, K. Durst, J. Mueller, B. Backes, H.W. Ho € ppel, M. Go€ken, Nano-
indentation strain-rate jump tests for determining the local strain-rate
sensitivity in nanocrystalline Ni and ultrafine-grained Al, J. Mater. Res. 26
(11) (2011) 1421e1430.
[102] A. Pakzad, J. Simonsen, R.S. Yassar, Elastic properties of thin poly(vinyl
alcohol)ecellulose nanocrystal membranes, Nanotechnology 23 (8) (2012)
085706.
[103] N.X. Randall, Direct measurement of residual contact area and volume
during the nanoindentation of coated materials as an alternative method of
calculating hardness, Philos. Mag. A 82 (10) (2002) 1883e1892.
[104] L. Charleux, V. Keryvin, M. Nivard, J.P. Guin, J.C. Sanglebœuf, Y. Yokoyama,
A method for measuring the contact area in instrumented indentation
testing by tip scanning probe microscopy imaging, Acta Mater. 70 (2014)
249e258.