Journal of Alloys and Compounds 746 (2018) 269e276

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Journal of Alloys and Compounds

journal homepage: http://www.elsevier.com/locate/jalcom

3D printing graphene-aluminum nanocomposites

Zengrong Hu a, *, Feng Chen b, Jiale Xu c, Qiong Nian d, **, Dong Lin e, Changjun Chen f,
Xing Zhu g, Yao Chen f, Min Zhang f
a
School of Rail Transportation, Soochow University, Suzhou, Jiangsu, 215131, China
b
College of Mechanical and Electrical Engineering, Nanjing University of Aeronautics and Astronautics, Nanjing, Jiangsu, 210016, China
c
School of Mechanical Engineering, Jiangsu University, Jiangsu, 212013, China
d
Department of Mechanical Engineering, Arizona State University, Tempe, AZ 85281, USA
e
Department of Industrial and Manufacturing Systems Engineering, Kansas State University, Manhattan, KS 66506, USA
f
College of Mechanical and Electrical Engineering, Soochow University, Suzhou, Jiangsu, 215131, China
g
Testing and Analysis Center, Soochow University, Suzhou, Jiangsu, 215123, China

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

Article history: This report studies the microstructure and property of graphene reinforced aluminum matrix composites
Received 11 December 2017 (Gr-Al) as fabricated by laser 3D printing. Recently, 3D printing was under extensive exploration, while
Received in revised form graphene has been considered as one of the most promising reinforcement fillers for metal matrix
20 February 2018
composites (MMCs) due to its mechanical robustness. Thus, it is of great importance to assess the efficacy
Accepted 22 February 2018
Available online 24 February 2018
of using 3D printing to fabricate the graphene reinforced MMCs. Herein, the mixture of graphene and
aluminum powders was prepared by ball milling with various graphene weight ratios, and then sintered
by the selective laser melting to fabricate bulk Gr-Al composites. Scanning electron microscopy (SEM),
Keywords:
3D printing
transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy
MMCs (XPS), energy dispersive spectrometer (EDS), and Raman spectroscopy were used to characterize the
Graphene microstructures and components of the nanocomposites. The surface and cross-sectional SEM images,
Aluminum XRD patterns, and Raman spectrum verified not only the survival but also the distribution of graphene in
Laser Gr-Al composites. High resolution TEM (HRTEM) images further revealed the co-existence of aluminum,
graphene and aluminum carbide. The Vickers hardness and nano-indentation tests showed the hardness
of the composites was greatly enhanced. Compared with pure aluminum counterpart, the Vickers
hardness of the best composite sample achieves a 75.3% increase. All the experimental results suggest
the efficacy of laser 3D printing technology to fabricate Gr-Al composites.
© 2018 Elsevier B.V. All rights reserved.

1. Introduction
Nowadays, with the technology development in various high-
tech areas, the demand for high-performance materials becomes
more and more pressing. In several fields, such as aerospace and
national defense, metal matrix composite (MMC) has become the
object of favor, and sometimes it is even irreplaceable. The me-
chanical property of most MMCs is dictated by their reinforcement
fillers. The state-of-the-art reinforcements for MMCs include
nitride ceramic (TiN, BN) [1,2], oxide ceramic (Al2O3, SiO2) [3,4],
* Corresponding author.
** Corresponding author.
E-mail addresses: huzengrong@suda.edu.cn (Z. Hu), Qiong.Nian@asu.edu
(Q. Nian).
carbides (TiC, WC) [5,6], and different carbon allotropes [7]. How-
ever, graphene recently has attracted tremendous attentions as the
promising MMCs filler, attribute to its superior mechanical prop-
erty. Numerous works of graphene reinforced MMCs have been
reported, which demonstrates that graphene indeed improves the
mechanical, thermal as well as electrical properties of the com-
posites [8e17].
Among enormous metallic materials, Aluminum and aluminum
alloys are very important in many emerging industrial fields (e.g.,
aeronautics and astronautics field) due to its light weight. Mean-
while, as a major enabling factor for Industry 4.0, metal three-
dimensional (3D) printing, such as powder-based additive
manufacturing (AM) techniques including selective laser sintering
(SLS) and selective laser melting (SLM), are under extensive
exploration [18,19]. In this respect, it is highly desirable to study the
efficacy of the metal 3D printing to fabricate the bulk parts of

https://doi.org/10.1016/j.jallcom.2018.02.272
0925-8388/© 2018 Elsevier B.V. All rights reserved.
270 Z. Hu et al. / Journal of Alloys and Compounds 746 (2018) 269e276
aluminum matrix composites.
Herein, 3D printing graphene reinforced aluminum matrix
nanocomposites were fabricated by the SLM technology. Mechan-
ical ball milling as an effective method to disperse graphene in
matrix metal powder [10,13,20e25], was used to prepare the
mixture of graphene and aluminum powders. Bulk composite
material was successfully printed by a modified SLM process for the
first time.
2. Experiments
2.1. Materials
The Al powders (99.5%, average diameter ~30 mm, Tianjin
Chemical Reagent Co. Ltd, China), and multi-layer graphene sheets
(<5 layers, Nanjing Kefu Nanotech Inc., China), were used for ball
milling first, and then 3D printing by SLM processing. The Al
powders and graphene sheets were mixed together by planetary
ball mill (speed 200 r/min, 2 h, stainless steel ball, 84 mm, stainless
jar). The ratio of ball to powder was 5:1, and ball milled without
protection gas. Pure aluminum powder and three kinds of mixed
powders were prepared: Al, -0.5 wt % Gr-Al, 1 wt % Gr-Al, and 2.5 wt
% Gr-Al, as shown in Fig. 1aed. It can be observed from Fig. 1 that
when graphene contain ratio was low, graphene sheets were
mostly absorbed on the aluminum particles surface, and when the
graphene ratio was become higher, separated graphene sheets
were easily find on the SEM image, as shown in Fig. 1d.
2.2. Samples preparing
The ball milled mixture was preset on an Al 6061 substrate of
60 mm  80 mm  6 mm. Then, laser beam was scanning a square
area of 5 mm  5 mm, then put another layer of the mixture and
laser melting it again. Repeat it to realize the laser 3D printing
process, as shown in Fig. 2. The powder bed preparing system was
homemade. It was simple and need long time to fabricating a
sample; however it has the greatest advantage of low cost. An SD-
Fig. 1. SEM images of (a) Al, (b) 0.5 wt % Gr-Al, (c) 1 wt % Gr-Al, and (d) 2.5 wt % Gr-Al mixture.
MD300 Nd:YAG millisecond pulse laser system (wave length
1064 nm, pulse duration 0.1e20 ms, max frequency 50 Hz, max
average power 300 W, spot diameter 0.2 mm, focal length of
focusing lenses 75 mm) was used to performer the laser melting
process at the frequency of 25 Hz, pulse duration 2.5 ms, scanning
speed 3 mm/s, and laser power of 90 W. The powder bed preparing
system was located on a numerical controlled (NC) x-y stage. And a
copper pipe which kept suitable position with the laser beam was
blowing argon (Ar) gas (15 L/min) to protect the samples from
oxidation and nitride during laser fabricating process. Fig. 3 shows
the 3D printing Gr-Al samples.
2.3. Microstructure characterization
A Rigaku UltimaⅣ Miltipurpose X-Ray diffraction system was
used to detect the material composite with Cu-Ka source. A Hitachi
S-4700 Field emission SEM and Hitachi SU5000 were used to study
the surface morphology and cross-sectional microstructures. The
Raman spectra were obtained by a HORIBA LabRAM HR800 Raman
spectrometer (HORIBA Jobin Yvon, NJ, USA). A 632.8 nm He-Ne
laser was focused by an Olympus 50  objective (MPLN50x,
Olympus America) as an excitation source, at the center of the
sample placed in an open air environment at room temperature.
The instrument has a spectral uncertainty of 0.27 cm 1 and peak
fitting uncertainty of 0.02e0.07 cm 1. A TenuPol-5 twin-jet elec-
tropolishing system was used to prepare TEM samples via twin-jet
electropolishing methods. Microstructure images were obtained by
the FEI Tecnai G-20 system, which operated at 200 keV.
2.4. Mechanical property testing
The micro-hardness of samples was measured by HXD-1000TM/
LCD (Shanghai optical instrument factory, Shanghai, China) micro-
hardness instrument with 100 g load and 10 s holding time. The
nanomechanical properties of laser 3D-printing Gr-Al samples
were measured by Agilent Nano indenter G200. The metallographic
polishing machine was used to polish the samples surfaces by
 Z. Hu et al. / Journal of Alloys and Compounds 746 (2018) 269e276
Fig. 2. Schematic diagram of laser 3D printing graphene aluminum process.
Fig. 3. Laser 3D printing Gr-Al samples.
removing a very thin layer in order to get fine and flat surface for
the micro-hardness measuring. All the tests were carried out at
room temperature and in a laboratory environment.
3. Results and discussion
The surface morphologies of pure Al and Gr-Al with different
graphene weight ratio were similar to each other, as shown in
Fig. 4aed. As observed from these SEM images, the entire sample
surface has a rather flat morphology, without continued pore area.
This indicates the laser 3D printing process was effective to fabri-
cate high quality composite material. However, as the graphene
weight ratio increasing, the Gr-Al samples surface show slightly
different morphology, i.e., rugged location and particle-like area.
This may ascribe to that the mixed graphene flakes would be in-
clined to connect the matrix material together as well as agglom-
erated together by itself, along with its weight ratio increasing.
XRD patterns, as shown in Fig. 5a revealed that the structure of
the Gr-Al samples mainly consisted of graphene and Al. The C (002)
peak at 2q degree of 26.3 can be obviously observed, well index to
crystalline structure of carbon allotropes. The composites only
contain graphene and Al originally, thereby it is intuitively derived
that graphene was still kept in the composites after laser 3D
printing process.
Other peaks can be also found easily at 2q degree of about 38.5 ,
44.7, 65 , 78.2 , and 82.4 . They are well indexed to Al (111), (200),
(220) (311) and (222) (PDF #04-0787: 2004), and similar signals
also has been reported by other reports [26,27]. After inspected the
XRD patterns carefully, as shown in the magnified pattern inserted
in Fig. 5a, several tiny diffraction peaks on Fig. 5a can be found at 2q
degree of about 36 , 40.1 and 43.5 , and they can be indexed to
Al4C3 (015), (107) and (0012) peaks. These diffraction peaks indicate
a reaction between graphene and Al was occurred in the laser 3D
271
printing process. On HRTEM image of Gr-Al samples, as shown in
Fig. 5b, the lattice profile of aluminum carbide also can be found.
The reaction is reasonable according to the binary phase diagram of
graphite-aluminum, when the temperature was over 500  C,
graphite will react with aluminum to form Al4C3. Graphene has a
much larger specific surface area, that is, it will be easier to react
with aluminum, especially in graphene sheets edge and defect area.
Raman spectroscopy was useful in the structure and defects
investigation of carbon materials. Fig. 6 is Raman spectrum of Gr-Al
by laser 3D printing. It can be seen the clear peaks at ~1334, ~1582
and ~2673 cm 1, are attribute to D, G and 2D peaks of multilayer
graphene, respectively. Similar Raman spectrum also can be found
on other graphene reinforced aluminum matrix composites fabri-
cated by other technology [13]. Compared with the original gra-
phene Raman spectrum, which provided by the graphene
manufacturer, D, G and 2D peaks were located at ~1325, ~1568 and
~2658 cm 1, it should be noticed that after laser process, the po-
sition of those characteristic peaks were shifted to right, as well the
ratio changing of the intensity of D peak (ID) to the intensity of G
peak (IG). ID/IG data from the manufacturers was about 0.053,
while on Fig. 6, ID/IG was about 0.48. Our previous laser sintering
graphene reinforce MMCs works showed similar results [11,28]. It
was reported that laser irradiation on graphene sheets could cause
G peak shifted, but it has less effect than that of defects [29,30].
According to reported research results, laser help to decrease the
defects of graphene sheets [29]. However, in this laser 3D printing
process, due to thermal accumulation, the high temperature will
cause graphene sheet defects increase. And the induced thermal
stress also will cause Raman peaks shifting. The ID/IG value
increased significantly after laser fabricating process, also indicates
the structure defects of graphene increased [31,32]. The defects
increase of graphene sheets may be due to both thermal damage
and the reaction between graphene and aluminum.
272 Z. Hu et al. / Journal of Alloys and Compounds 746 (2018) 269e276

Fig. 4. SEM images of surface morphology of laser 3D printing (a) pure aluminum, (b) 0.5 wt % Gr-Al, (c) 1 wt % Gr-Al, (d) 2.5 wt % Gr- Al composites.

Fig. 5. Laser 3D printing Gr-Al composites (a) the XRD patterns, and (b) HRTEM images.

As proved by XRD and Raman measurement, graphene sheets
existed in laser 3D printing Gr-Al nanocomposites. This implies the
relative long heating time and repeated heating in the laser fabri-
cation process, were not the obstacles for Gr-Al nanocomposite
preparation. Graphene sheets remain the intrinsic structure, but as
mentioned above the defects increased and aluminum carbides
were formed. To make it more clearly, XPS results were collected
from the surface of Gr-Al samples.
Fig. 7 aec shows X-ray Photoelectron Spectroscopy (XPS) results
of Gr-Al composites. XPS has been widely used for measuring the
elemental composition, chemical state, and electronic state of the
elements. As shown in Fig. 7a, the whole spectra of the composites
indicate that the measured samples surface mainly contains Al, O, C
elements. The peaks at ~284.5 eV and near ~74 eV are
corresponding to Aluminum and carbon contents in composite,
respectively. The binding energy of 282.2 eV and 72.7 eV peaks
were reported belonging to Al4C3 [33]. The peak located at ~531 eV
is indexed O 1s, and might result from slight oxidation of metallic
powders before printing. Fig. 7b shows the high resolution XPS
spectrum of carbon element. The three peaks at 282.2 eV, 284.5 eV
and 288.9 eV, are attribute to Al4C3, carbon, and eCOO- groups [34],
respectively. The high-resolution Al 2p XPS spectrum also has been
shown in Fig. 7c. There are five peaks locating at 72.7, 73.4, 74.3, 75
and 75.5 eV. The peak at 72.7 eV was corresponding to aluminum
and aluminum oxide. And this was also consistent with the oxygen
peak at 531 eV. It means the composites have the Al2O3 component.
The oxidization phase might ascribe to oxidized metallic powder or
the sample exposure to air for a relatively long time before the XPS
 Z. Hu et al. / Journal of Alloys and Compounds 746 (2018) 269e276 273

measurements. Therefore, the initial surface of the samples was

inevitably oxidized [35].
Fig. 8a is the SEM image of cross-section morphology of laser 3D
printing fabricated Gr-Al composites. Graphene sheets can be seen
in the composite which was marked on the SEM image. Fig. 8b and
c are EDS mapping of Fig. 8a, which exhibits the elements of carbon
and aluminum distribution in the cross section. Fig. 8b marks the
carbon element in red color, in consistent with marked area on
Fig. 8a. As observed, continuous shapes of graphene flake can be
found, which is indicated by the concentration of the carbon
element. And on Fig. 8c, except for the graphene flake area, there
were dark regions. It further confirms graphene does exist in the
composites after laser 3D printing process. The other thing should
be noticed was the graphene sheets shape. The Laminated gra-
phene sheets can be observed and as well as spherical shape gra-
phene. Due to the huge specific surface area, it has been reported
that graphene sheets have an inherent tendency to form agglom-
erates due to strong Van der Waals attraction and p-p interaction
[36]. So it is prone to form spherical shape, this phenomenon also
can be found in other reports [37]. The agglomeration will affect the
Fig. 6. Raman spectra of laser 3D printing Gr-Al composites.

Fig. 7. The XPS spectra of the laser 3D printing Gr-Al composites on the surface, (a) the whole survey XPS spectra, (b) carbon spectrum (c) Al spectrum.
274 Z. Hu et al. / Journal of Alloys and Compounds 746 (2018) 269e276

Fig. 8. SEM images of laser 3D printing Gr-Al composites, (a) section morphology, (b) and (c) are carbon, aluminum EDS maps of (a).

mechanical properties of graphene reinforced composites, on the
other hand, in our laser 3D printing experiments; this will help to
delay the reaction between aluminum and graphene.
Furthermore, in order to delve insight into the interaction be-
tween graphene and aluminum in the laser 3D printing process, the
TEM and HRTEM images were collected and analyzed. Fig. 9a was
the TEM image of Gr-Al composites. After twin-jet electropolishing,
the hole edge area only leave a very thin layer composite material,
and it was transparent to electron beam, graphene sheets,
aluminum matrix and aluminum carbides can be observed on the
image. The black rod like material was proved to be Al4C3. The
insert images were magnified white rectangle area on the Fig. 9a
and the selected area electron diffraction (SAED) pattern of the
magnified image. The resulted Al4C3 was in nanosize. It's about
150 nm in length and 35 nm in diameter, and this was similar to
CNTs reinforced Al matrix composites reported before [38]. As we
know, CNTs have a more stable structure than that of multilayer
graphene, which means graphene should react with aluminum
easier. Fig. 9b shows graphene, aluminum and Al4C3 area on the
HRTEM image. The lattice fringes of graphene in 0.34 nm (C (002)),
Al (200) in 0.20 nm and Al4C3 (107) and (110) can be observed. It
was consistent with XRD and XPS results. In fact, as mentioned
above, graphene and aluminum were inevitably reacted with each
other in this laser 3D printing process, for the temperature was
definitely over 500  C. The formation of Al4C3 was a two fold sword
for Gr-Al composites. It was reported that excessive Al4C3 will
totally fail the composites mechanical properties [20], on the other
hand, a certain amount Al4C3 can also have positive affect, for the
wettability of graphene and aluminum. Since Al4C3 appears to
improve the wettability, so it improve the mechanical strength-
ening of the final composites [17,39]. The most critical issue is to
control the composites processing parameters to achieve the op-
timum situation.
For further investigate the mechanical properties, a series of
samples were prepared. There were laser 3D printing pure Al,
0.5 wt %, 1 wt % and 2.5 wt % Gr-Al samples, which were made

Fig. 9. TEM and HRTEM images of Gr-Al composites: (a) TEM image shows rod aluminum carbide with corresponding SAED patterns, (b) graphene, Al, aluminum carbide area and
their interface.
 Z. Hu et al. / Journal of Alloys and Compounds 746 (2018) 269e276 275

under the same processing conditions. Fig. 10 shows the average

Vickers hardness values of these samples. The sample were selected
randomly and polished to get flatten surface before hardness
measuring.
On Fig. 10, it can be noticed that the hardness values of pure Al
and Gr-Al samples were a function of graphene weight percentage.
The hardness performances of laser 3D printing fabricated samples
were: pure aluminum (38HV) and 0.5 wt% Gr-Al (47.1HV), 1 wt% Gr-
Al (49.6HV) and 2.5 wt% Gr-Al (66.6HV). Compared with pure
aluminum, the highest hardness value of Gr-Al has an increase of
nearly 75.3%.
The average hardness values of the samples were increasing
along with the graphene content increasing. In this work, the
highest graphene content is 2.5 wt%, and it achieve the peak Vickers
hardness. It seems we can make the hardness of Gr-Al improved
even more by increasing graphene content. However, unfortu-
nately, further increasing graphene content would cause reducing
of the hardness, especially after a certain graphene content value.
This has been confirmed before, as the aggregation of graphene
caused this effect [24,40]. For multilayer graphene, the out-of-plane
strength is significantly lower than that of in-plane properties, so Fig. 11. Loadepenetration depth curves of nanomechanical tests of 3D-printing Al and
the agglomeration will weaken the composites. And from the error 2.5 wt%Gr-Al composites.

bars of these average hardness values on Fig. 10, it can be also

deduced that higher graphene samples are prone to result in gra-
phene agglomeration, as the hardness values scattered. And it was
proved by our previous works and other researcher's works that the
mechanical properties improvement of graphene reinforced MMCs
mainly attribute to the excellent mechanical properties of graphene
and the interface state of matrix metal and graphene sheets [40,41].
Nano-indentation was used to further determine the Nano
mechanical properties of the laser 3D printing composites. Since
Vickers hardness results indicated that 2.5 wt% graphene content
samples have the best performance, thus, here only laser 3D
printing pure Al and 2.5 wt% Gr-Al samples were selected for
nanoindentation tests. And the Nano hardness was 1.04 GPa and
1.77 GPa for pure Al and 2.5 wt% Gr-Al samples, respectively. The
tendency is consistent with that of Vickers hardness results. But the
Nano hardness value for same graphene content sample obviously
higher than that of Vickers hardness. The difference maybe caused
by the different measuring method. Fig. 11 show the Nano inden-
tation load-penetration depth curves. The tested samples and the
position of test points were randomly selected. For all the tested
points, the load was limited to 10 mN. It can be observed from
curves that under the same load pure Al samples had deeper
penetration depth into the samples surface, and 2.5 wt% Gr-Al
samples had much less penetration depth on the contrast. This
result was consistent with the Vickers hardness values. It indicated
that comparing with the pure Al samples, the 2.5 wt% Gr-Al sam-
ples achieve better performance on Nano hardness. It also can be
found from Fig. 11 that the Al test results were concentrated
together, however, it was significantly different for the test results
of 2.5 wt% Gr-Al samples. This means that the high graphene con-
tent will inevitably introduce agglomeration, and this will weak-
ened the enforcement effect of graphene sheets. But these curves
do illustrated the enhanced mechanical properties for the addition
of graphene sheets.
4. Conclusion
3D printing (additive manufacturing) is considered to be a
revolution of manufacturing [42,43], especially laser or other high
power beam based metal 3D printing technology. This technology
was not only capable to fabricate complex parts, but also useful to
manufacture cutting edge nanocomposite material, for example,
high quality bulk graphene reinforced MMCs. Herein, different
graphene content Gr-Al composites were prepared by laser 3D
printing process. XRD, Raman XPS and EDS results proved that
graphene sheets exist in the composites. And graphene structure
had no physical change. But the defects of graphene sheets
increased. Al4C3 new phase was formed in the composites. TEM and
HRTEM images further proved that graphene existed in the fabri-
cated composites. With graphene sheets reinforcement, the com-
posites Vickers hardness increases by nearly 75.3% compared with
laser 3D printing pure aluminum. The nanoindentation tests have
similar results. These results indicate that graphene is a promising
reinforcement material for aluminum matrix and laser based 3D
printing technology can be used to prepare bulk Gr-Al composites.

Acknowledgments

The authors thank Lanlan Qin, Dr. Ying Song and Weiwei Liu of
College of Mechanical and Electrical Engineering, Soochow Uni-
versity, Weijian Gao and Mei Wang of Soochow University Testing
Fig. 10. The Vickers hardness of laser 3D printing Al and Gr-Al composites. and Analysis Center for their help in samples preparing and testing.
276 Z. Hu et al. / Journal of Alloys and Compounds 746 (2018) 269e276

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