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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 carbides (TiC, WC) [5,6], and different carbon allotropes [7]. How-
ever, graphene recently has attracted tremendous attentions as the
Nowadays, with the technology development in various high- promising MMCs filler, attribute to its superior mechanical prop-
tech areas, the demand for high-performance materials becomes erty. Numerous works of graphene reinforced MMCs have been
more and more pressing. In several fields, such as aerospace and reported, which demonstrates that graphene indeed improves the
national defense, metal matrix composite (MMC) has become the mechanical, thermal as well as electrical properties of the com-
object of favor, and sometimes it is even irreplaceable. The me- posites [8e17].
chanical property of most MMCs is dictated by their reinforcement Among enormous metallic materials, Aluminum and aluminum
fillers. The state-of-the-art reinforcements for MMCs include alloys are very important in many emerging industrial fields (e.g.,
nitride ceramic (TiN, BN) [1,2], oxide ceramic (Al2O3, SiO2) [3,4], 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
* Corresponding author. (SLS) and selective laser melting (SLM), are under extensive
** Corresponding author.
exploration [18,19]. In this respect, it is highly desirable to study the
E-mail addresses: huzengrong@suda.edu.cn (Z. Hu), Qiong.Nian@asu.edu
(Q. Nian).
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. MD300 Nd:YAG millisecond pulse laser system (wave length
Herein, 3D printing graphene reinforced aluminum matrix 1064 nm, pulse duration 0.1e20 ms, max frequency 50 Hz, max
nanocomposites were fabricated by the SLM technology. Mechan- average power 300 W, spot diameter 0.2 mm, focal length of
ical ball milling as an effective method to disperse graphene in focusing lenses 75 mm) was used to performer the laser melting
matrix metal powder [10,13,20e25], was used to prepare the process at the frequency of 25 Hz, pulse duration 2.5 ms, scanning
mixture of graphene and aluminum powders. Bulk composite speed 3 mm/s, and laser power of 90 W. The powder bed preparing
material was successfully printed by a modified SLM process for the system was located on a numerical controlled (NC) x-y stage. And a
first time. copper pipe which kept suitable position with the laser beam was
blowing argon (Ar) gas (15 L/min) to protect the samples from
2. Experiments oxidation and nitride during laser fabricating process. Fig. 3 shows
the 3D printing Gr-Al samples.
2.1. Materials
2.3. Microstructure characterization
The Al powders (99.5%, average diameter ~30 mm, Tianjin
Chemical Reagent Co. Ltd, China), and multi-layer graphene sheets A Rigaku UltimaⅣ Miltipurpose X-Ray diffraction system was
(<5 layers, Nanjing Kefu Nanotech Inc., China), were used for ball used to detect the material composite with Cu-Ka source. A Hitachi
milling first, and then 3D printing by SLM processing. The Al S-4700 Field emission SEM and Hitachi SU5000 were used to study
powders and graphene sheets were mixed together by planetary the surface morphology and cross-sectional microstructures. The
ball mill (speed 200 r/min, 2 h, stainless steel ball, 84 mm, stainless Raman spectra were obtained by a HORIBA LabRAM HR800 Raman
jar). The ratio of ball to powder was 5:1, and ball milled without spectrometer (HORIBA Jobin Yvon, NJ, USA). A 632.8 nm He-Ne
protection gas. Pure aluminum powder and three kinds of mixed laser was focused by an Olympus 50 objective (MPLN50x,
powders were prepared: Al, -0.5 wt % Gr-Al, 1 wt % Gr-Al, and 2.5 wt Olympus America) as an excitation source, at the center of the
% Gr-Al, as shown in Fig. 1aed. It can be observed from Fig. 1 that sample placed in an open air environment at room temperature.
when graphene contain ratio was low, graphene sheets were The instrument has a spectral uncertainty of 0.27 cm 1 and peak
mostly absorbed on the aluminum particles surface, and when the fitting uncertainty of 0.02e0.07 cm 1. A TenuPol-5 twin-jet elec-
graphene ratio was become higher, separated graphene sheets tropolishing system was used to prepare TEM samples via twin-jet
were easily find on the SEM image, as shown in Fig. 1d. electropolishing methods. Microstructure images were obtained by
the FEI Tecnai G-20 system, which operated at 200 keV.
2.2. Samples preparing
2.4. Mechanical property testing
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 The micro-hardness of samples was measured by HXD-1000TM/
area of 5 mm 5 mm, then put another layer of the mixture and LCD (Shanghai optical instrument factory, Shanghai, China) micro-
laser melting it again. Repeat it to realize the laser 3D printing hardness instrument with 100 g load and 10 s holding time. The
process, as shown in Fig. 2. The powder bed preparing system was nanomechanical properties of laser 3D-printing Gr-Al samples
homemade. It was simple and need long time to fabricating a were measured by Agilent Nano indenter G200. The metallographic
sample; however it has the greatest advantage of low cost. An SD- polishing machine was used to polish the samples surfaces by
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.
Z. Hu et al. / Journal of Alloys and Compounds 746 (2018) 269e276 271
removing a very thin layer in order to get fine and flat surface for printing process. On HRTEM image of Gr-Al samples, as shown in
the micro-hardness measuring. All the tests were carried out at Fig. 5b, the lattice profile of aluminum carbide also can be found.
room temperature and in a laboratory environment. 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
3. Results and discussion much larger specific surface area, that is, it will be easier to react
with aluminum, especially in graphene sheets edge and defect area.
The surface morphologies of pure Al and Gr-Al with different Raman spectroscopy was useful in the structure and defects
graphene weight ratio were similar to each other, as shown in investigation of carbon materials. Fig. 6 is Raman spectrum of Gr-Al
Fig. 4aed. As observed from these SEM images, the entire sample by laser 3D printing. It can be seen the clear peaks at ~1334, ~1582
surface has a rather flat morphology, without continued pore area. and ~2673 cm 1, are attribute to D, G and 2D peaks of multilayer
This indicates the laser 3D printing process was effective to fabri- graphene, respectively. Similar Raman spectrum also can be found
cate high quality composite material. However, as the graphene on other graphene reinforced aluminum matrix composites fabri-
weight ratio increasing, the Gr-Al samples surface show slightly cated by other technology [13]. Compared with the original gra-
different morphology, i.e., rugged location and particle-like area. phene Raman spectrum, which provided by the graphene
This may ascribe to that the mixed graphene flakes would be in- manufacturer, D, G and 2D peaks were located at ~1325, ~1568 and
clined to connect the matrix material together as well as agglom- ~2658 cm 1, it should be noticed that after laser process, the po-
erated together by itself, along with its weight ratio increasing. sition of those characteristic peaks were shifted to right, as well the
XRD patterns, as shown in Fig. 5a revealed that the structure of ratio changing of the intensity of D peak (ID) to the intensity of G
the Gr-Al samples mainly consisted of graphene and Al. The C (002) peak (IG). ID/IG data from the manufacturers was about 0.053,
peak at 2q degree of 26.3 can be obviously observed, well index to while on Fig. 6, ID/IG was about 0.48. Our previous laser sintering
crystalline structure of carbon allotropes. The composites only graphene reinforce MMCs works showed similar results [11,28]. It
contain graphene and Al originally, thereby it is intuitively derived was reported that laser irradiation on graphene sheets could cause
that graphene was still kept in the composites after laser 3D G peak shifted, but it has less effect than that of defects [29,30].
printing process. According to reported research results, laser help to decrease the
Other peaks can be also found easily at 2q degree of about 38.5 , defects of graphene sheets [29]. However, in this laser 3D printing
44.7, 65 , 78.2 , and 82.4 . They are well indexed to Al (111), (200), process, due to thermal accumulation, the high temperature will
(220) (311) and (222) (PDF #04-0787: 2004), and similar signals cause graphene sheet defects increase. And the induced thermal
also has been reported by other reports [26,27]. After inspected the stress also will cause Raman peaks shifting. The ID/IG value
XRD patterns carefully, as shown in the magnified pattern inserted increased significantly after laser fabricating process, also indicates
in Fig. 5a, several tiny diffraction peaks on Fig. 5a can be found at 2q the structure defects of graphene increased [31,32]. The defects
degree of about 36 , 40.1 and 43.5 , and they can be indexed to increase of graphene sheets may be due to both thermal damage
Al4C3 (015), (107) and (0012) peaks. These diffraction peaks indicate and the reaction between graphene and aluminum.
a reaction between graphene and Al was occurred in the laser 3D
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 corresponding to Aluminum and carbon contents in composite,
existed in laser 3D printing Gr-Al nanocomposites. This implies the respectively. The binding energy of 282.2 eV and 72.7 eV peaks
relative long heating time and repeated heating in the laser fabri- were reported belonging to Al4C3 [33]. The peak located at ~531 eV
cation process, were not the obstacles for Gr-Al nanocomposite is indexed O 1s, and might result from slight oxidation of metallic
preparation. Graphene sheets remain the intrinsic structure, but as powders before printing. Fig. 7b shows the high resolution XPS
mentioned above the defects increased and aluminum carbides spectrum of carbon element. The three peaks at 282.2 eV, 284.5 eV
were formed. To make it more clearly, XPS results were collected and 288.9 eV, are attribute to Al4C3, carbon, and eCOO- groups [34],
from the surface of Gr-Al samples. respectively. The high-resolution Al 2p XPS spectrum also has been
Fig. 7 aec shows X-ray Photoelectron Spectroscopy (XPS) results shown in Fig. 7c. There are five peaks locating at 72.7, 73.4, 74.3, 75
of Gr-Al composites. XPS has been widely used for measuring the and 75.5 eV. The peak at 72.7 eV was corresponding to aluminum
elemental composition, chemical state, and electronic state of the and aluminum oxide. And this was also consistent with the oxygen
elements. As shown in Fig. 7a, the whole spectra of the composites peak at 531 eV. It means the composites have the Al2O3 component.
indicate that the measured samples surface mainly contains Al, O, C The oxidization phase might ascribe to oxidized metallic powder or
elements. The peaks at ~284.5 eV and near ~74 eV are 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
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 easier. Fig. 9b shows graphene, aluminum and Al4C3 area on the
other hand, in our laser 3D printing experiments; this will help to HRTEM image. The lattice fringes of graphene in 0.34 nm (C (002)),
delay the reaction between aluminum and graphene. Al (200) in 0.20 nm and Al4C3 (107) and (110) can be observed. It
Furthermore, in order to delve insight into the interaction be- was consistent with XRD and XPS results. In fact, as mentioned
tween graphene and aluminum in the laser 3D printing process, the above, graphene and aluminum were inevitably reacted with each
TEM and HRTEM images were collected and analyzed. Fig. 9a was other in this laser 3D printing process, for the temperature was
the TEM image of Gr-Al composites. After twin-jet electropolishing, definitely over 500 C. The formation of Al4C3 was a two fold sword
the hole edge area only leave a very thin layer composite material, for Gr-Al composites. It was reported that excessive Al4C3 will
and it was transparent to electron beam, graphene sheets, totally fail the composites mechanical properties [20], on the other
aluminum matrix and aluminum carbides can be observed on the hand, a certain amount Al4C3 can also have positive affect, for the
image. The black rod like material was proved to be Al4C3. The wettability of graphene and aluminum. Since Al4C3 appears to
insert images were magnified white rectangle area on the Fig. 9a improve the wettability, so it improve the mechanical strength-
and the selected area electron diffraction (SAED) pattern of the ening of the final composites [17,39]. The most critical issue is to
magnified image. The resulted Al4C3 was in nanosize. It's about control the composites processing parameters to achieve the op-
150 nm in length and 35 nm in diameter, and this was similar to timum situation.
CNTs reinforced Al matrix composites reported before [38]. As we For further investigate the mechanical properties, a series of
know, CNTs have a more stable structure than that of multilayer samples were prepared. There were laser 3D printing pure Al,
graphene, which means graphene should react with aluminum 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
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