Accepted Manuscript

Aluminum/graphene composites with enhanced heat-dissipation properties by in-situ

reduction of graphene oxide on aluminum particles

Le Zhang, Guangmei Hou, Wei Zhai, Qing Ai, Jinkui Feng, Lin Zhang, Pengchao Si,
Lijie Ci

PII: S0925-8388(18)31107-1
DOI: 10.1016/j.jallcom.2018.03.237
Reference: JALCOM 45467

To appear in: Journal of Alloys and Compounds

Received Date: 6 June 2017

Revised Date: 10 March 2018
Accepted Date: 19 March 2018

Please cite this article as: L. Zhang, G. Hou, W. Zhai, Q. Ai, J. Feng, L. Zhang, P. Si, L. Ci, Aluminum/
graphene composites with enhanced heat-dissipation properties by in-situ reduction of graphene oxide
on aluminum particles, Journal of Alloys and Compounds (2018), doi: 10.1016/j.jallcom.2018.03.237.

This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to
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 ACCEPTED MANUSCRIPT

Aluminum/graphene composites with enhanced heat-dissipation properties by

in-situ reduction of graphene oxide on Aluminum particles

Le Zhang, Guangmei Hou, Wei Zhai, Qing Ai, Jinkui Feng, Lin Zhang,
Pengchao Si*, Lijie Ci*

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SDU& Rice Joint Center for Carbon Nanomaterials, Key Laboratory for Liquid-Solid

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Structural Evolution & Processing of Materials (Ministry of Education), School of

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Materials Science and Engineering, Shandong University, Jinan 250061, China

Corresponding author: Lijie Ci, Pengchao Si

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Email: lci@sdu.edu.cn; pcsi@sdu.edu.cn
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TEL: 86-531-88396169
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Abstract
Aluminum/graphene (Al/G) composites with enhanced heat-dissipation and mechanical
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properties were prepared by the powder metallurgy (P/M) technique. Graphene was first
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uniformly coated on the surface of micro-sized aluminum (Al) powders by an in-situ

reduction reaction of GO and Al. Al/G bulk composites with uniform graphene
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dispersion in Al matrix were fabricated by the simple conventional P/M technique.

Enhancements of 15.4 % in thermal conductivity, 9.1 % in specific heat capacity,
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21.1 % in hardness, and 25.6 % in compressive strength were achieved with only 0.3
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wt.% graphene addition into pure Al.

Key words: Heat-dissipation composites; Aluminum/graphene composites; Graphene
oxide; Reduced Graphene oxide; Powder metallurgy

1. Introduction
Aluminum matrix composites (AMC), with their good thermal and electrical

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conductivity, high tensile strength to weight ratio, high hardness and ductility, have been
attracting great attention in modern industry [1-2]. Other than the common applications
of their mechanical properties, the high thermal conductivity and specific heat capacity
makes AMC widely used heat-dissipation materials in various industrial fields. To
satisfy the increasing demand for required thermal management with higher mechanical

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performance of AMC materials, new reinforcement fillers in Al matrix are in
desperately need.

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Pristine graphene sheets, which are one-atom-thick two-dimensional layers of
sp2-bonded nano-carbon materials, have extraordinary thermal conductivity(~5300

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W/(m*K) [3], high intrinsic strength(~130 GPa) and modulus(~1.0 TPa) [4], high
hardness and low density. These properties make graphene a perfect addictive into

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aluminum matrix. Moreover, the final aluminium/graphene (Al/G) composites are
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supposed to have not only high thermal conductivity but perfect mechanical properties
and machinability.
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Dispersion of graphene in Al matrix is directly affecting the properties of composite.

Almost of the papers about Al/G composites focus mainly on the enhancement of
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mechanical properties, and different graphene dispersion methods have been developed.
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Rather than adding graphene into Al melting liquid directly, Chi-Hoon Jeon et al. [5]
synthesized Al/G composites by friction stir processing (FSP). Graphene oxide (GO)
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was applied directly to the surface of Al matrix in the form of GO/water colloid prior to
FSP and effectively reduced by the heat generated during the process. The thermal
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conductivity of the composite increased by more than 15%. Powder metallurgy (P/M)
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technique, which including shape molding and sintering, has been normally used to
fabricate the bulk samples of Al/G composites [6-12]. Before P/M molding process,
traditional ball-milling method has been widely adopted to mix graphene with
aluminum powders [13-16]. For example, Bartolucci et al. [17] fabricated Al/G
composites by ball-milling, hot isostatic pressing, and hot extrusion. The aluminum
carbide formed during ball-milling lowered the hardness and tensile strength of the

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composite. Another powder mixing method were explored at the same time, Latief et al.
[6] dispersed exfoliated graphite nanoplatelets (xGnP) in acetone then added the
aluminum particles, followed by the P/M technique to prepare composites. The
compressive strength and hardness increased with increasing the amount of xGnP and
the sintering temperature. Similarly, Liu et al. [7] coated colloidal graphene oxide (GO)

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onto aluminum powder particles by mechanical stirring then reduced GO to graphene
via thermal annealing. Wang et al. [8] developed a method to first adsorb GO sheets

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onto polyvinyl alcohol (PVA) - treated Al flakes and then reduced GO by rapid heating

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to a high temperature. Li et al. [11-12] fabricated GO/Al composite flakes based on the
mechanism of electrostatic interaction between GO and Al flakes, which was followed
by thermal annealing to reduce GO.

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All in all, dispersion and interfacial reactions are two important factors that can affect
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the properties of final samples. Graphene is easy to agglomerate in molten aluminum
liquid and the reaction temperature of aluminum liquid is usually so high that some
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negative interfacial reactions may occur. By comparison, P/M technique is the better
method to shape the sample and realize the homogeneous distribution of graphene. As
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for ball-milling mixing method, it cannot make sure the uniform distribution of
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graphene on each particle and some interfacial reactions may occur, too. In general,
there are two main methods to fabricate graphene coated aluminum powders in liquid
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phase. The first is directly mixing graphene solution and aluminum powders. However,
The nonuniform distribution of graphene in powders impedes the development of this
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method. The second is mixing GO solution and aluminum powder, then, GO was
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reduced to graphene at high temperature. Finally, The coated powders are shaped into
bulk by P/M technique.
Our investigation aimed at realizing the uniform dispersion of graphene in Al matrix
and fabricating bulk composites with high thermal conductivity and perfect mechanical
properties by the application of GO with P/M technique. Previous investigations have
indicated that the existence of carbonyl and carboxyl groups on GO sheet make it

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strongly hydrophilic, which allows GO to readily disperse in water and form more
stable solution than pristine graphene [18]. What’s more, GO can be fabricated easily by
inexpensive graphite powder [19]. Previous reports have also indicated that GO can be
directly reduced by active metals like aluminum without any additional reducing agents
in acidic solution [20-21]. From the above, GO is the better starting coating material. In

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this study, we found that graphene can be well dispersed into Al particles by in-situ
reducing GO onto the surfaces of aluminum particles. The P/M technique was further

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employed to fabricate the Al/G composites with much enhanced heat-dissipation and

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mechanical properties at a very low graphene loading of 0.1-0.3 wt.%.

2. Experimental procedure

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Pure aluminum powders with an average particle diameter of ~10 µ m were used in this
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study. GO solution was synthesized according to the modified Hummers method [22]
from expandable graphite. KMnO4 ( 15 g ) and NaNO3 ( 2.5 g ) were dispersed in
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H2SO4 (115 ml) in an ice bath under continual stirring. Expandable graphite (2.5 g) was
added and completely dispersed. The mixed slurry was maintained at 273 K for 24 h.
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Then, the mixture was heated to 308 K and kept for 30 min with constant stirring. The
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temperature was slowly increased to 373 K and the mixture was diluted to 500 ml by
adding DI water drop by drop at the same time. The suspension was then maintained at
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371 K for another 15 min with constant stirring. 5 ml 30% H2O2 was added into the
mixture, which was then diluted with 3000 ml HCl solution (5 %) to remove metal ions.
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The final GO product was rinsed with DI water for several times.
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GO solution was diluted to 0.2 mg/ml with DI water and dispersed by ultrasonic
treatment for 30 min before used. The pH value of the prepared GO solution was around
4.0. Composites with 0.1 wt.%, 0.2 wt.% and 0.3 wt.% GO were prepared by adding 20
g of Al powders into 100 ml, 200 ml and 300 ml of the diluted GO solution, respectively.
The mixtures were stirred until the solution became colorless and transparent (Fig. 1a).
Our following results indicated that GO was in-situ reduced to graphene on the surfaces

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of Al particles. The reaction time was about 5 min, 40 min and 60 min, respectively.
Afterwards the as-prepared graphene coated Al powders were transferred into ethanol.
Magnetic stirring was then started and continued for another 3 min. Then graphene
coated Al powders were filtered and vacuum dried for 8h at 50 ℃. 17 g Al/G powders
were weighed and cold compressed at the pressure of 200 MPa in a stainless steel mold

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with a diameter of 40 mm. The bulk samples (ɸ40×5 mm) were then sintered at 600℃
for 5 h in Ar atmosphere. To make a comparison, a pure Al bulk sample was also

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prepared in the same manner.

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The morphology of powders and fracture surfaces of block samples were performed by
field-emission scanning electron microscopy (FE-SEM, HitachiSU-70) . The images of
interface bonding between graphene and Al particle and the lattice structure of graphene

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were obtained by transmission electron microscope (JEM-2100). Raman spectra were
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recorded by Renishaw inVia micro-Raman spectrometer with 632 nm laser as the
excitation source. X-ray diffraction (XRD) patterns were acquired on a Rigaku Dmaxrc
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diffractometer with Ni filtered Cu Kα radiation (V= 50KV, I= 100 mA) at a scanning

rate of 10˚/min. Thermal conductivity and specific heat capacity at 20 ℃ were measured
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by a laser thermal conductance instrument (NETZSCH LFA 457 MicroFlash®).

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Differential scanning calorimeter (NETZSCH DSC 404) measurement was carried out
to measure the change of the specific heat capacity of pure Al and 0.3 wt.% Al/G
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composite from 50 ℃ to 745 ℃. Vickers hardness tests were performed on the samples
with a 25 g weight. Compression resistance properties were carried out on
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an universal testing machine at room temperature.

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3. Results and discussion

Due to the rich oxygen related groups on GO (Fig. 1b), they can be well dispersed in the
form of single or few layers in the DI water with the concentration of 0.2 mg/ml. The
weak acid solution with the pH value of 4.0 helped to remove the thin aluminum oxide
layers on the surfaces of Al powders first. Then, H+ can easily form complexes with the
oxygen-related groups on GO sheets. A dehydration process occurred and the positively

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charged GO sheets received electrons from Al atoms [20]. GO sheets were then in-situ
reduced on the surface of Al particles and coated around their surfaces. Through this
simple process, we can easily realized the homogeneous mixing thin layer graphene
together with Al powders.
However, a spontaneous hydrolysis reaction would occur between Al particles and DI

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water due to the removal of the aluminum oxide layers and high surface energy of the
small particle size [23], and Al(OH)3, as the reaction products, will form on the surface

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of Al particles. Pure Al powders (Fig. 1c) are spherical shape and their surface was

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smooth. On the contrary, the surface of DI water-dried graphene coated Al particle (Fig.
1d) looked rather rough with some irregular shaped aggregations appeared, which was
identified to be Al(OH)3. Al(OH)3, as a result, became Al2O3 during sintering process,

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which would decrease the purity and thermal conductivity of Al/G bulk samples. We
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found that the hydrolysis reactions mainly occurred during the 8 hours’ drying process
at the higher temperature of 50 ℃ in the very watery environment. In order to avoid this
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side reaction, Al/G particles were first immediately washed by absolute ethyl alcohol
(alcohol-dried powders) after the coating process to remove extra water before drying.
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As shown in Fig. 1e, the surface morphology of alcohol-dried graphene coated Al

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powder was similar to pure Al powder, indicating nearly no side reaction occurred
during the graphene coating process.
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Graphene sheets can also be easily observed when they bridged two Al particles, as
shown in Fig. 1f. However, it was hard to discern graphene sheets on the surface of
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individual particles by SEM images (Fig. 1e) due to the atomic thin feature of the
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reduce GO and their tightly coating on the surface. And the tight connection was shown
in the TEM image (FIG. 2a), which indicated there was no gap between graphene and Al
particle. Raman spectrum (Fig. 3a, rGO before sintering), which was acquired on the
surfaces of randomly selected single particles, indicated the existence of graphene
(reduced GO). Another SEM image of the fracture surface of the bulk sample was adopt
to indicate the existence of graphene after sintering (Fig. 3c). The red arrows pointed to

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graphene in this image. To make it more persuasive, energy spectroscopy analysis was
also adopt to prove the existence of graphene (Fig. 3d, 3e and 3f). The element of C
existed with rather high content. In fact, Raman signals (Fig. 3a, rGO after sintering)
were acquired on the fracture surfaces of the bulk sample, which indicated that there
still existed graphene. The Raman spectrum of dried GO (Fig. 3a) was also acquired to

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make a comparison. Both of the Raman spectra of the reduced GO on Al and pristine
GO exhibit G (~1597 cm-1) and D (~1327 cm-1) bands. As shown in Fig. 3a, the D/G

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intensity ratio of reduced GO (1.13) was increased compared with that of GO (0.84),

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which suggested the structural change due to the removing of functional groups [24].
What’s more, the TEM image (Fig. 2b) also showed the obvious lattice structure of
reduced GO.

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Metallographic photos and scanning electron microscopy (SEM) images of pure
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aluminum and Al/G composites with different graphene contents were shown in Fig. 4.
Due to the uniform and tight coating of graphene on Al particles, graphene sheets were
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expected to mainly exist at the boundaries between two adjacent Al crystallines in the
Al/G composite. The uniform distribution of graphene within the Al matrix was
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expected to contribute to the property enhancement of the composites. However, the

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metallographic photos (Fig. 4a-d) showed that there existed a large amounts of pores
inside the bulk samples after pressureless sintering, and the pore contents increased as
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graphene contents increased. This was ascribed to the fact that graphene layers at the
boundaries impeded the diffusion of aluminum atoms during the sintering process.
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Similarly, SEM images of fracture surfaces (Fig. 4e-h) indicated some of the aluminum
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crystallines still maintained their spherical structures of Al/G powder. In fact, with a
high melting temperature of above 3000 ℃, graphene had a low tendency to bond with
pure aluminum [11]. In order to determine the stability of graphene in Al matrix after
sintering, Raman signals (Fig. 3a, rGO after sintering) were acquired on the fracture
surfaces of the bulk sample, which indicated that there still existed graphene. The D/G
intensity ratio increased to 1.15, indicating graphene was further reduced after sintering.

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The bulk samples were cut and polished to get a smooth surface for X-ray diffraction
(XRD) test. The patterns (Fig. 3b) indicate all of the samples had aluminum peaks at
38.6° (1 1 1), 44.8° (2 0 0), 65.2° (2 2 0), 78.3° (3 1 1), and 82.4° (2 2 2). No diffraction
peaks of aluminum oxide or carbide were observed, which indicates there was nearly no
reaction between graphene and Al at the sintering temperature.

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Archimedes principle was employed to measure the density of these samples. The
measured densities (1.132 g/cm3 for pure Al, 1.128 g/cm3 for 0.1 wt.% Al/G composite,

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1.125 g/cm3 for 0.2 wt.% Al/G composite, and 1.124 g/cm3 for 0.3 wt.% Al/G composite)

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were rather low and decreased with the increased addition of graphene. In fact, uniform
dispersion of nano-size porosity would improve the heat dissipation capacity of the bulk
composites [25]. The higher density Al/G composites with lower porosity and better

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properties were expected by a following a hot-pressing or an extrusion processing.
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Thermal conductivity values of all these samples at 20 ℃ (Fig. 5a) were 143 W/(m*K),
154 W/(m*K), 159 W/(m*K), and 165 W/(m*K) for pure Al, 0.1 wt.% Al/G composite,
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0.2 wt.% Al/G composite, and 0.3 wt.% Al/G composite, respectively. The factors
having effect on the thermal conductivity of the Al/G composite include the quality of
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both graphene and Al, dispersibility of graphene in Al matrix, and thermal resistance of
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the interfaces between graphene and Al matrix. With the extremely high intrinsic
thermal conductivity over 5000 W/(m*K) [26], the addition of graphene can enhance
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the conductivity in a composite. In our case, 15% increase of thermal conductivity with
only 0.3 wt.% graphene addition can be ascribed to not only the excellent thermal
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properties of graphene, but also to the tight interface between graphene and Al matrix
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due to the in-situ reduction and coating process. Moreover, we expected an more
increment of thermal conductivity if the composite can be further densified since the
porosity may increase the thermal resistance of the composites.
The specific heat capacity of these samples at 20 ℃ based on the thermal conductivity
measurement were calculated. As with thermal conductivity (Fig. 5a), the specific heat
capacity (0.905 J/g/K, 0.921 J/g/K, 0.928 J/g/K, and 0.987 J/g/K, for pure Al, 0.1 wt.%

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Al/G composite, 0.2 wt.% Al/G composite, and 0.3 wt.% Al/G composite, respectively)
gradually increased with the addition of graphene. The higher specific heat capacity
meant the enhancement of thermal energy storage, indicating the increased rate of the
body cooling or heating [27]. Materials with a higher specific heat capacity can absorb
more heat from the heat resource with the same temperature increasing. Therefore, Al/G

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composites are suitable for thermal dissipation application due to its increased specific
heat capacity. The result of DSC (Fig. 5b) indicated that the specific heat capacity of 0.3

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wt. % Al/G composite was larger than that of pure Al before melting.

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The Vickers method was used to measure the hardness values of pure Al and Al/G
samples. The measurements were repeated 15 times for each sample and averaged. As
shown in Fig. 6a, the hardness values were 43.1±2.5 HV, 49.2±2.5 HV, 50.7±1.2 HV,

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and 52.2±1.9 HV for pure Al, 0.1 wt.% Al/G composite, 0.2 wt.% Al/G composite, and
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0.3 wt.% Al/G composite, respectively. The 0.3 wt. % Al/G composite showed an
hardness increasement of 21.1% over pure Al sample. The improvement of hardness
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values can be explained by the following equation [11]:

Hc = Hm fm+Hr fr
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In the equation, Hc is the hardness of the whole composites, Hm is the hardness of

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matrix
(Al), Hr is the hardness of reinforcement (graphene), fm and fr are the volume fraction of
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matrix and graphene, respectively.

Compressive stress-strain curves with different graphene contents were given in Fig. 6b.
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The compressive strength increased with the increase of graphene content. The
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compressive strength were 207 MPa, 232 MPa, 249 MPa, and 260 MPa for pure Al, 0.1
wt.% Al/G composite, 0.2 wt.% Al/G composite, and 0.3 wt.% Al/G composite,
respectively (Fig. 6c). The addition of graphene of only 0.1-0.3 wt.% can enhance the
compressive strength by 12.1~25.6%, indicating the excellent reinforcement effect of
graphene for Al and other metallic materials. The improvement of compressive strength
can be explained by the following equation [11]:

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σc = σm fm+σr fr
σc, σm, and σr is the strength of the composites, Al matrix, and graphene, fm and fr are the
volume fraction of Al and graphene, respectively. The reinforcement of the compressive
properties was mainly ascribed to the graphene at the boundaries prevented the
movement of the dislocations with the mechanism of dispersion strengthening.

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Moreover, the compressive strain was higher with higher graphene addition, which was
possibly due to the flexibility feature and the lubricating effect of graphene at

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boundaries.

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4. Conclusions
In summary, aluminum and graphene composites with enhanced thermal and

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mechanical properties were fabricated by the P/M technique. Graphene sheets were well
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dispersed in the Al matrix by using a special in-situ GO reduction and coating on Al
particles in the aqueous solution. Even though Al/G composites fabricated by simple
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compress and sintering in this work had a lower density with high porosity, our
preliminary results demonstrated that graphene can be a suitable candidate in Al
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composites for the enhancement of thermal conductivity, specific heat capacity and
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mechanical properties. The composites had potential for heat-management applications

in electronic devices. For structural applications in the area of automobile, aerospace,
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we believe a further forming process such as hot or cold extrusion can be applied to
increase the density of the composites and obtain their better mechanical properties.
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Acknowledgements
The authors gratefully acknowledge the support of 1000 Talent Plan program (No.
31270086963030); Key Research Plan of Shandong Province (2015GGE27286);
Independent Innovation Foundation of Shandong University; The Young Scholars
Program of Shandong University (2016WLJH03); Shandong Provincial Science and
Technology Major Project (2015ZDZX11008).

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thermal management applications in nanoelectronic circuits, Applied Physics Letters. 92
(2008) 151911.
[27] E. Pop, V. Varshney, A.K. Roy, Thermal properties of graphene: Fundamentals and
applications, MRS bulletin. 37 (2012) 1273-1281.

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Fig. 1: (a) photograph of solution before and after reaction; SEM images of (b) GO sheet,
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(c) pure Al powder, (d) DI water-dried graphene coated Al powder, and (e, f)
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alcohol-dried graphene coated Al powder.

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Fig. 2: TEM images of (a) interface bonding between graphene and Al particle , and
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(b) lattice structure of reduced GO.
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Fig. 3: (a) Raman spectra of GO, reduced GO before/after sintering; and (b) XRD patterns

of pure Al and graphene/Al composites；(c) SEM image of graphene on the fracture

surface; (d), (e) and (f) Energy spectroscopy analysis on the fracture surface.
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Fig. 4: Metallographic photos and SEM images of (a, e) pure aluminum, and composites
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with (b, f) 0.1 wt. % graphene , (c, g) 0.2 wt. % graphene and (d, h) 0.3 wt. % graphene.
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Fig. 5: (a) Thermal conductivity and specific heat capacity at 20 , (b) specific heat
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capacity at 50~745 .
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Fig. 6: (a) Vickers hardness, (b) compressive stress-strain curve , and (c) compressive

strength of pure Al and graphene/Al composite with different contents.

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Highlights

Dispersion of graphene in aluminum matrix by in-situ reduction of graphene

oxide on aluminum particles.

Alcohol washing was adopted to avoid the hydrolysis reaction of aluminum and

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guarantee the purity of the composites.

Enhancement of heat-dissipation and mechanical properties by adding graphene

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into aluminum matix.

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