Materials Science & Engineering A 823 (2021) 141749

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Materials Science & Engineering A

journal homepage: www.elsevier.com/locate/msea

Mechanically strong, stiff, and yet ductile AlSi7Mg/graphene composites by

laser metal deposition additive manufacturing
Pengxu Li a, Rui Cai b, Guang Yang a, *, Tianqi Wang a, Sensen Han c, Shuocheng Zhang c,
Wei Wang a, Qingshi Meng a, c, **
a
Key Laboratory of Fundamental Science for Aeronautical Digital Manufacturing Process, Shenyang Aerospace University, 37 Daoyi South Avenue, Shenyang, Liaoning,
110136, China
b
School of Mechanical, Aerospace and Automotive Engineering, Coventry University, Coventry, CV1 2JH, United Kingdom
c
College of Aerospace Engineering, Shenyang Aerospace University, 37 Daoyi South Avenue, Shenyang, Liaoning, 110136, China

A R T I C L E I N F O A B S T R A C T

Keywords: Laser metal deposition (LMD) with a coaxial powder feeding technology has been applied to fabricate pure
Additive manufacturing (AM) aluminum alloy (AlSi7Mg) and low oxidation graphene aluminum matrix (LOG-Al) composites with low
Aluminum matrix composites (AMCs) oxidation graphene (LOG) contents of 0.05 wt % and 0.1 wt % after the powder was prepared by wet ball milling.
Graphene oxide
The LOG-Al composites showed improvements in all properties including hardness, tensile strength, ductility,
Laser metal deposition (LMD)
modulus of elasticity and yield strength with the increase of LOG addition contents. The microstructures and
fracture surfaces of the composites were observed and the results of TEM, HRTEM, optical microscope, EBSD,
XRD spectra, Raman spectra, Vickers hardness, tensile properties were analyzed. The effects of wet ball milling,
the addition of low oxidation graphene and its contents and LMD process on microstructure formation and
resulting mechanical properties were discussed.

1. Introduction development, complex structure fabrication and cost reduction [15,16].

The techniques in aluminum alloy powder and its composites additive
Aluminum matrix composites (AMCs) have been widely used in manufacturing mainly include selective laser sintering (SLS) [17], se­
aerospace, automotive, electronics and other fields due to their advan­ lective laser melting (SLM) [18,19], a type of powder bed fusion, and
tages of high specific strength, high thermal conductivity, desirable laser metal deposition (LMD) [20,21]etc. LMD technology is fast
formability and low density etc. [1–3]. Conventionally, the AMCs are developed and has been successfully applied to titanium alloy [22–24],
fabricated via solid state methods (powder metallurgy) and liquid state ultra-high strength steel [25], Ti–Al alloy [26] and Al–Li alloy [27] due
methods (stir casting, squeeze casting and compo-casting method etc.) to its advantages, it does not require a mould, reduces material waste,
[4–6]. The selection of the fabrication route depends on many factors shortens production cycles, provides rapid prototyping and supports
including the mechanical/thermal/electrical demands of various in­ great design flexibility. The early concept of LMD appeared in a 1988
dustrial applications, types, properties and weight/volume fractions of patent describing a method of using lasers to melt deposition metal
reinforcement, and the degree of microstructural integrity desired [7]. powders to repair damaged parts [28]. Laser direct forming technology
Despite many advantages for conventional fabricating routes for AMCs, for high performance metal parts was first proposed in the United States
fabricating complex structures using these routes however proves to be in 1995 [29]. In 2005, the LMD with a coaxial powder feeding tech­
difficult and expensive in terms of labour cost [8,9]. Apart from con­ nology was applied in the aerospace industrial application by Wang
ventional fabrication routes for AMCs, additive manufacturing (AM) et al. [30] from Beihang University. In recent years, in 2017, Gu et al.
also called 3D printing has become a continuous trend in recent industry [31] studied the fabrication of nano-titanium carbide reinforced
applications [10–14] which reveals superiority in rapid product nickel-based composites by laser deposition. In 2017, Lu et al. [32]

* Corresponding author.
** Corresponding author. Key Laboratory of Fundamental Science for Aeronautical Digital Manufacturing Process, Shenyang Aerospace University, 37 Daoyi South
Avenue, Shenyang, Liaoning, 110136, China.
E-mail addresses: yangguang@sau.edu.cn (G. Yang), mengqingshi@hotmail.com, mengqingshi@sau.edu.cn (Q. Meng).

https://doi.org/10.1016/j.msea.2021.141749
Received 10 May 2021; Received in revised form 6 July 2021; Accepted 13 July 2021
Available online 21 July 2021
0921-5093/© 2021 Elsevier B.V. All rights reserved.
P. Li et al. Materials Science & Engineering A 823 (2021) 141749

studied the laser metal deposition of suspended structures with spatial mechanical properties of LOG-Al composites fabricated by coaxial
variable orientation. In 2015, Huang et al. [33] fabricated the wing rib powder feeding LMD process to compare with other 3D printing
strip of TC4 alloy using laser deposition additive manufacturing approaches.
technology. In this work, composite powder mixed of LOG (LOG, has a more
The studies of adding conventional reinforcement phases such as SiC, complete structure than high oxidation graphene, with less hydroxyl and
SiO2, and Al2O3 in the forms of fibers, whiskers, and particles have also epoxy groups on the surface) with different content up to 0.1 wt % and
been investigated, it indicates that the properties of AMCs such as me­ aluminum alloy (AlSi7Mg) was prepared by wet ball milling, which is an
chanical strength, toughness, hardness and wear resistance [34–37] are effective way to distribute LOG in the aluminum alloy matrix. LOG-Al
improved however at the expense of ductility [8,38]. This is due to the composites were then fabricated by coaxial powder feeding LMD pro­
agglomeration of reinforcement phases at the grain boundaries, leading cess. Optimized working parameters based on previous studies were
to grain boundary embrittlement. Carbon nanotubes (CNTs) in SLM for utilized here. The optical microscope, scanning electron microscopy
AMCs have also been applied as reinforcement [39–41]. The results, (SEM), transmission electron microscopy (TEM), high resolution trans­
however, show that poor dispersion, agglomeration and entanglement mission electron microscope (HRTEM), electron backscattered scat­
due to Van Der Waals forces between CNTs [42,43]. The structural tering detection (EBSD), X-ray diffraction (XRD) and Raman
integrity of carbon nanotubes in materials is also poor which affects the spectroscopy were employed to characterize the microstructures and
mechanical properties of AMCs [44]. components of the nanocomposites and the dispersion of graphene in
Compared with CNTs, graphene, a honeycomb two-dimensional LOG-Al composites. Mechanical properties for samples without heat
nanomaterial composed of carbon atoms, with superior mechanical treatment such as tensile tests, Vickers hardness tests were also carried
properties as well as high specific surface area [45–49], can be a out. The relationship between microstructures of LOG-Al composites
promising reinforcement material for aluminum matrix. Different kinds and their mechanical properties were investigated. The experimental
of graphene and its derivatives have different characteristics. Pristine results suggested that coaxial powder feeding LMD produces LOG-Al
graphene can be fabricated by the micromechanical method, but cannot composites with both highly improved strength and ductility.
produce processable 2D nanosheets in either water or solution due to
lack of sufficient oxygen-based functional groups [50]. Therefore, 2. Experimental method
chemical oxidization has been widely employed to fabricate graphene
oxide (GO) [51–53]. GO is electrically insulating, so chemical or thermal 2.1. Materials
reduction is needed to reduce parts of the oxygen-based group and de­
fects [54]. However, the reduced GO (RGO) is still limited by low Aluminum alloy (AlSi7Mg) powders with an average size of 60–120
structural integrity implying unsatisfactory mechanical property and μm, as shown in Fig. 6(a1), were supplied by Beijing COMPO Advanced
electrical conductivity (<10 S/cm) with a risk of sacrificing its solution Technology CO., LTD. The chemical composition of aluminum alloy
processability [55]. LOGs feature high structural integrity, relatively (AlSi7Mg) is shown in Table 1, the contents of Si, Mg and Ti were
low content of oxygen-based groups. They show a much higher struc­ 6.70–7.50 wt %, 0.45–0.60 wt % and 0.10–0.20 wt % respectively.
tural integrity (ID/IG) ratio than that of conventional GO (ID/IG = 1) and Natural graphite powders (40–50 μm) were provided by Qingdao Huatai
RGO (ID/IG ≥ 0.6) [57,58], thus no reduction is needed. Technology CO., LTD.
The addition of graphene or GO improves the mechanical properties
of AMCs in conventional fabrication routes such as vacuum hot pressing 2.2. Sample preparation
[59], spark plasma sintering (SPS) [60], hot extrusion [61,62] etc. given
that the reinforcement was uniformly distributed. However, the study in The low oxidation graphene was produced according to a previously
the graphene/GO AMCs fabricated by 3D printing is limited. From the reported procedure [66]. 0.4 g KMnO4, 6 g H2SO4, 26 g H3PO4 and 0.1 g
only several research in this topic, researchers [39,63–65] generally natural graphite powders were firstly well mixed, then left in an ultra­
agree that the graphene/GO AMCs fabricated by laser 3D printing have sonic oscillator and sonicated at low temperature (20–30 ◦ C) for 1 h.
relatively improvement in mechanical properties. Among these re­ Next, 150 ± 50 ml distilled water was added into the mixture and
searches, Zhao et al. [63] added Al-coated graphene into the AlSi10Mg filtered three times. After being dried at 80 ◦ C, the low oxidation gra­
alloy and fabricated the AMCs by SLM. It was discovered that the tensile phene powder was finally prepared.
strength, elongation and hardness of the material are improved by 11 %, Fig. 1 shows preparation schematic of low oxidation graphene
13 % and 41 % respectively; Hu et al. [65] studied the property of aluminum (AlSi7Mg) matrix (LOG-Al) composites. LOG-Al powders with
graphene AMCs prepared by laser additive manufacturing (SLM), and good sphericity were used to guarantee better fluidity for the benefit of
indicated that the Vickers hardness of the best composite sample ach­ LMD processing. The aluminum alloy powder and LOG were ball milled
ieves a 75 % increase compared with that of pure aluminum matrix. with an F–P8L ball mill (Hunan Focucy Technology CO., LTD, China) for
However, studies also revealed that although the strength and hardness 16–20 h in a vacuum with the rotational speed of 280 RPM. The stainless
of AMCs increase with the addition of graphene/graphene oxide, the jar with the volume of 2 L and the stainless-steel balls with a diameter of
elongation improves only up to 6.2 % [39,63–65]. In addition, the 5 mm were used in this study. The mass ratio of powders to balls was 1:5.
graphene contents in the above researches are all higher than the weight During the process, the anhydrous ethanol was applied as a solvent. An
of 0.20 %. interval of 10 min was set after each 30 min of milling to keep the
The research in graphene and its derivatives (GNPs and GO or RGO) powders at low temperature. Finally, the LOG-Al composite powder
Al-based composites, fabricated by laser metal deposition (LMD), one of with well-distributed LOG was prepared. Three kinds of powders were
the 3D printing methods, however, is rarely reported in recent publi­ prepared for experiments as shown in Fig. 6: aluminum alloy powder,
cations. The coaxial powder feeding LMD process utilizes controllable 0.05 wt %LOG-Al powder, 0.1 wt %LOG-Al powder. LOG was evenly
heat input to melt metal powder quickly, and the metal pool cools fastly, dispersed and coated on aluminum alloy powder as observed from Fig. 6
create minimal dilution and heat effect zones and thereby minimizing (b1-c3).
stress and distortion on final parts with high form quality and fine grain.
The rapid cooling rate and thermal cycles usually lead to the formation Table 1
of unique microstructures in alloys fabricated by a coaxial powder AlSi7Mg aluminum alloy powder composition (wt. %).
feeding technology, which are different from microstructures obtained Element Si Mg Ti Al
using conventional fabrication techniques. Due to these advantages, it is
Content (wt. %) 6.50–7.50 0.45–0.60 0.10–0.20 Bal.
highly desirable to study the microstructure and corresponding

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P. Li et al. Materials Science & Engineering A 823 (2021) 141749

Fig. 1. Preparation schematic of LOG-Al composites.

2.3. LMD processing mm × 6 mm on top of aluminum alloy (AlSi7Mg) substrates. The opti­
mized working parameters used in this study are listed in Table 2.
The laser metal deposition manufacturing machine with coaxial
powder feeding and the maximum output power of the IPG fiber laser of
6000 W was implemented in this study. Fig. 2a shows the basic sche­ 2.4. Microstructural observation
matic diagram of laser coaxial powder feeding additive manufacturing.
The high-energy laser was used as the heat source to melt the powder After the LMD fabrication, the samples were separated from the
from the powder feeder and deposit it to the base material. Through the substrates by wire electro-discharge machining for microstructural ob­
relative movement of the worktable and laser cladding head, the net servations. The observation surfaces were parallel to the XOY plane as
shaping of metal parts is realized. The processing of LMD was from point shown in Fig. 2a and at a depth of 2 ± 0.2 mm from the top surface. The
to line, from line to surface and finally from surface to body. Therefore,
the metal parts can be obtained by controlling the laser moving track. A Table 2
close-up of the laser cladding head is shown in Fig. 2b. The LMD process Optimized LMD working parameters in this study.
was under argon (Ar gas) protection, the oxygen was less than 50 ppm. LMD conditions Parameters
The laser operation power was set to the range of 1800–2200 W and Laser power 1800–2200 W
which allowed aluminum alloy powders (aluminum alloy and its low Spot diameter 4 mm
oxidation graphene composites) melted completely. The powders of Scanning speed 3–7 mm/s
aluminum alloy, 0.05 wt % LOG-Al and 0.1 wt % LOG-Al were dried at Powder-feeding speed 2 g/min
Scanning spacing 2 mm
80 ◦ C before being processed for the samples with a size of 75 mm × 25

Fig. 2. Laser metal deposition process (a) schematic diagram and (b) photograph of the laser cladding head.

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observation surfaces were first polished and then etched with a solution and 2D-band, respectively. In general, the D-band intensity increases
of 9 vol% HF+91 vol% H2O before the metallographic structures were with the degree of oxidation and impurity, whilst high G-band intensity
observed with an optical microscope (OLYMPUS-DP71), the micro­ implies regular graphene structure corresponding to conducting prop­
structure was analyzed using a scanning electron microscope (Zeiss) erties and high strength. The D-to G-band ratio of 0.23 is far smaller than
equipped with EBSD, the characterization of grain size was analyzed by that of graphene oxide in previous studies [69,70], implying a low
MATLAB. X-Ray diffraction (D8 ADVANCE) system was used to detect oxidation degree and defects.
the phase composition of the samples. For the TEM (Hitachi, Japan) and The FT-IR spectra (Fig. 5b) demonstrates sufficient functional groups
HRTEM (JEM-2100F) detection, the samples were prepared with a such as hydroxyl groups (3400 cm− 1), carboxyl groups (1650 cm− 1) and
diamond cutter and focused ion beam (FIB) for observing LOG disper­ epoxide and ether groups (1250 cm− 1), which are important for the
sion and interfacial bonding in the aluminum alloy matrix. The Raman suspension of LOG sheets in various organic solvents.
spectrometer (HR800, France) was employed for Raman spectra.
3.2. Morphology of aluminum alloy (AlSi7Mg) powder and its low
2.5. Mechanical property testing oxidation graphene (LOG) coated composite powders

Materials Vickers hardness testing machine (TMHVS-1000, China) Fig. 6 (a1-a3) show the SEM morphology of pure aluminum alloy
was used to measure the microhardness at the load of 50 g for 10s. The particles with a good degree of sphericity. Fig. 6 (a1) shows the overview
tensile tests of the composites at room temperature were carried out by of aluminum alloy powder observed at low magnification, the surface of
MTS-810 mechanical property testing machine (MTS-810, USA) with a the aluminum alloy powder is relatively smooth but with lumpy fea­
strain rate of 2 mm/min. The tensile loading direction applied to the tures. Fig. 6 (b1-b3) show the SEM images of LOG-Al composite powder
specimen was perpendicular to deposition direction (as shown in with a low oxidation graphene content of 0.05 wt %. It was observed in
Fig. 2a). Fig. 3a shows the geometry and dimensions of the tensile Fig. 6 (b1) that the surface of the aluminum alloy powder coated with
specimens, and Fig. 3b shows the test sample. low oxidation graphene sheets was relatively rough compared with the
pure aluminum alloy powder. Fig. 6 (b2) as a partially enlarged view of
2.6. Characterization of graphene sheets Fig. 6 (b1) shows that the low oxidation graphene adhered tightly to the
surface of the aluminum alloy powder. From Fig. 6 (b3), low oxidation
TEM images were obtained with a TEM (Hitachi, Japan) at 200 kV graphene sheets can be observed. Fig. 6 (c1-c3) show the SEM images
acceleration voltage. Raman spectra tests were investigated by UV LOG-Al composite powder with a low oxidation graphene content of 0.1
micro-Raman spectrometer (HR800, France) at room temperature, wt %. It was observed that as the content of low oxidation graphene
excited by 633 nm He–Ne laser and recorded in the frequency range of increased, the surface of the aluminum alloy powder coated with low
10–1000 cm− 1 with a spectral resolution of 0.5 cm− 1. The functional oxidation graphene in Fig. 6 (c1) became even rougher compared with
groups of LOG nanosized flakes were analyzed using a FT-IR spec­ Fig. 6 (b1). The surface of the aluminum alloy powder binds well with
trometer (PerkinElmer 65, USA). The thickness of LOG was obtained by low oxidation graphene sheets as shown in Fig. 6 (c2). In Fig. 6 (c3),
atomic force microscopy (AFM, Bruke icon) under a tapping mode, as craters on the surface are observed in the low oxidation graphene
shown in Fig. 4c. attached to the surface of the aluminum alloy powder.
The LOG has a number of irregular curls and folds, implying that ball
milling did not make any influence on the appearance characteristics
3. Results and discussion
such as sheet features and winkles on the surfaces of low oxidation
graphene. The tight bond between low oxidation graphene and
3.1. Characterization of low oxidation graphene (LOG)
aluminum alloy powder is due to intermolecular van der Waals forces.
To prove this, the LOG-Al composite powders were oscillated at a fre­
Fig. 4a (b) show the TEM (at 200 kV accelerated voltage) micrograph
quency of 40 Hz for 30min, no separation of low oxidation graphene
of one large low oxidation graphene sheet fabricated by the low
from the aluminum powder was found. The LOG-Al composite powders
oxidation method introduced in section 2.2. The large graphene sheet
were then kept at room temperature in a vacuum for three weeks or
was investigated due to the demand of the selected area to exam the
more. The low oxidation graphene still well wrapped around the surface
crystalline electron diffraction, which was conducted on a randomly
of the aluminum alloy powder without layering and stripping.
selected region (red rectangle) of Fig. 4a. The electron diffraction
pattern (Fig. 4b) exhibits a typically shaped six-fold symmetry, which
keeps identical to the hexagonal crystalline structure of our low oxida­ 3.3. Microstructural evolution
tion graphene sheet [67]. At least 10 LOG sheets were selected for the
measurement. The thickness was measured by AFM as shown in Fig. 4c, Fig. 7 (a)(b)(c) show the metallographic microstructure of LOG-Al
the resulting average thickness is 3.81 ± 0.10 nm. The five representa­ composites with different weight fractions of low oxidation graphene
tive measurements are shown in Fig. 4d. The data is also consistent with under an optical microscope. No defects such as porosity and poor
the published studies [68]. bonding were found. There was no significant difference in the types of
Fig. 5a contains Raman spectra of low oxidation graphene sheets, microstructure phases, mainly composed of α-Al dendrite and Al + Si
and the absorptions at 1338, 1567, and 2683 cm− 1 correspond to D, G eutectic (indicated in Fig. 7a). Fig. 7a shows the microstructure without

Fig. 3. Configuration of the samples used for the tensile tests (unit: mm) (a), the test sample (b).

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Fig. 4. TEM images of (a) graphene sheets made by a low oxidation method and (b) its electron diffraction pattern and (c) AFM image of low oxidation graphene and
(d) the typical thickness of five low oxidation graphene sheets.

Fig. 5. Raman (a) and FTIR spectra (b) of low oxidation graphene sheets.

LOG content, where only thick dark Al + Si eutectic and bright α-Al alloy. Fig. 7b shows the microstructure with 0.05 wt % LOG content,
dendrite can be observed. The aluminum alloy was heated by a high- where uniform and fine microstructure of α-Al dendrites and the Al + Si
energy laser and melted quickly. During the solidification process, the eutectic can be observed. According to the heterotrophic nucleation
high melting point Si phase dominated the heterogeneity in the molten theory, both α-Al and Al + Si eutectic adhesion nucleated on uniformly
pool. As the temperature decreased, α-Al nucleated and grew around the dispersed LOG prematurely, and the addition of LOG inhibited the
nucleated Si particles. The continuous solidification of α-Al led to an growth of α-Al dendrite and Al + Si eutectic, resulting in the micro­
increase in the Si concentration in the residual liquid phase, and the structure from coarse to fine, the excellent thermal conductivity of LOG
liquid phase components gradually developed towards eutectic, forming also contributed to the grain refinement. Fig. 7c shows the microstruc­
Al + Si eutectic, Al + Si eutectic promoted the strength of aluminum ture with 0.1 wt % LOG content, which has relatively more

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Fig. 6. SEM images show the morphology of pure aluminum alloy powder (a1-a3), 0.05 wt %LOG-Al composite powder (b1-b3) and 0.1 wt %LOG-Al composite
powder (c1-c3).

Fig. 7. Optical microscope of LMD process pure aluminum alloy (a), 0.05 wt %LOG-Al composites (b) and 0.1 wt %LOG-Al composites (c). The EBSD of LMD process
pure aluminum alloy (d) and 0.1 wt %LOG-Al composites (e).

homogeneous and finer grains, compared with the first two groups, with characteristics on the 101 crystal plane. After the addition of LOG, the
the increase of LOG content, the inhibition effect on grain growth grain was refined and the dendritic crystal and columnar crystal were
became more obvious. transformed to equiaxed crystal, which weakened the texture charac­
Fig. 7 (d)(e) show the EBSD of LMD process pure aluminum alloy and teristics of the material in the 101 direction and improved the unifor­
0.1 wt %LOG-Al composites. It can be seen from Fig. 7d and (e) that with mity of the microstructure.
the addition of LOG, the grain orientation has changed, which was still MATLAB image processing software was used to measure and
randomly distributed and the performance of the composite had a low calculate the grain sizes of the composite materials, the average grain
anisotropy. According to Fig. 7 (d), pure aluminum alloy had texture sizes are shown in Table 3. As can be seen from Fig. 7 and Table 3, the

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Table 3 oxidation graphene was about 0.2, which indicated that pure LOG has
Average grain size of LMD process LOG-Al composites. high structural integrity. While on Fig. 8, the ID/IG of 0.05 wt % and 0.1
Content (wt. %) 0 0.05 0.1 wt % LOG-Al composites were 1.0 and 0.9 respectively. This phenom­
enon can be explained by the following two reasons: (a) during the
Mean grain size (μm) 12.2 ± 0.4 8.6 ± 0.2 6.7 ± 0.2
forming process, the laser radiation led to the reduction of the structural
integrity of LOG in composites; (b) at relative higher LOG contents (0.05
grain sizes and grain distribution ranges of LOG-Al composites were wt % and 0.1 wt %), overlap or aggregate structures were formed. These
significantly smaller than that of pure aluminum alloy matrix. The relative complex structures may cause a disordered change of structural
average grain size was refined from 12.2 ± 0.4 μm to 6.7 ± 0.2 μm. Grain integrity. Similar results were found in the published literature on laser
refinement was a result due to many small grains with LOG as the cores sintering graphene reinforce metal matrix composites [73], it was re­
in aluminum alloy are formed in the solidification of aluminum alloy. In ported that the G peak shifted was caused by laser radiation, but the
the subsequent growth process, the grains growth space of α-Al dendrite impact of peak migration is less than that of defect density [65,74]. In
and Al + Si eutectic was also effectively inhibited by LOG, leading to fine this study, high temperature and heat accumulation led to an increase in
microstructures [34,39,64,71]. The higher the GO content in the ID/IG. The increase of ID and ID/IG value indicates that the structure of
nano-reinforced phase, the stronger the inhibitory effect on grain LOG is damaged [75]. Therefore, in this study, laser thermal radiation
growth, the more equiaxed grains are formed [31]. In addition, Rashad and chemical reactions increased the defect density of LOG, although,
et al. [62] reported that dislocations are generated in the processing of from a previous report [76], a laser can reduce and repair the defects on
composite ascribable to the dissimilar thermal expansion coefficients of graphene sheets. However, the damage degree of its structure is not
graphene and aluminum alloy (αgraphene = 0.9 × 10− 6/K at 873–1073 K enough to affect the performance of the whole LOG-Al composites.
and αAl = 3.6 × 10− 6/K), grain motion is therefore resisted by Fig. 9 shows the TEM images of LOG-Al composites. 0.1 wt % com­
reinforcement. posite sample was selected as a representative to investigate the com­
The structure and defects investigation of carbon materials were posite structure. It shows that the interface between LOG and aluminum
analyzed by Raman testing. Fig. 8 demonstrates the Raman spectra of alloy matrix is generally neat and without impurities, pores and other
aluminum alloy, 0.05 wt % LOG-Al and 0.1 wt %LOG-Al composites defects. In Fig. 9 (a), LOGs (indicated by black arrows) were generally
fabricated by LMD. The chain-dotted curve shows the Raman spectrum well dispersed in Al matrix (indicated by black circles). The well-bond
of neat AlSi7Mg alloy without containing the typical characteristic peak interface between LOG and aluminum alloy matrix indicates that the
of graphene. The dashed and solid curves represent Raman spectrum of aluminum alloy matrix wetted the LOG sheets well. LOG sheets were
0.05 wt % LOG-Al and 0.1 wt %LOG-Al, respectively. As can be seen evenly dispersed in the aluminum alloy matrix and no rod-shaped
from the dashed curve and the solid curve, the D, G and 2D peaks were aluminum carbide was formed. One reason for the evenly disperse of
found. A similar Raman spectrum can be found in the published litera­ LOG sheets in the aluminum alloy lies in its low contents (up to 0.1 wt
ture [72]. Two main peaks, D and G, which arise from lattice disorder at %). Ball milling also contributes to improving the dispersion of LOG
the edges of the sp2 clusters and in-plane stretching of the graphene along with good cold bonding and interfacial adhesion between re­
lattice, are commonly employed to identify the nanocarbons such as inforcements and matrix. The interface bonding between the LOG and
graphene nano platelets, and the 2D peaks are commonly used to the aluminum alloy matrix, is mainly formed by van der Waals attrac­
characterize the stacking of carbon atoms in graphene, graphene with tions, which helps effectively transfer the load from ductile metal matrix
fewer layers has a higher 2D peak. The content of LOG in the dashed to hard reinforcements. In addition, anhydrous ethanol plays several
curve is lower than that in solid, fewer LOG layers are dispersed in the roles in this study: It increases the wettability between LOG and
matrix, the 2D peak strength in the dashed curve is higher than that in aluminum which improves the binding between the reinforcement and
solid and sharper. Compared with the original LOG Raman spectrum matrix; as a solvent, it effectively avoids the agglomeration of LOG; and
which made by a low oxidation method (as shown in Fig. 4a), D, G and it helps to control the temperature at a low level in the ball milling
2D peaks were identified at ~1338, ~1567 and 2683 cm− 1, after the process.
laser metal deposition manufacturing, ID/IG data from the original low Fig. 9 (c) (d) shows the HRTEM morphologies of LOG-Al composites.
The LOGs (yellow arrows) were observed in the grain or near grain
boundary (white arrows) and embedded in aluminum matrix (Fig. 9c).
The dislocations (white arrows) were found in Fig. 9 (d), considering
different thermal expansion coefficients of LOG and aluminum matrix,
the mismatch of thermal residual stress occurred near the interface be­
tween these two, which led to the dislocation accumulation during the
forming process. In addition, during the deformation, dislocations
continue to be generated, and LOG could pin the dislocations, resulting
in high strength.

3.4. XRD spectrum

Typical XRD spectra of LMD pure AlSi7Mg alloy and LOG-Al com­
posites are depicted in Fig. 10. The types of diffraction peaks of the three
samples were not significantly different. The strong diffraction peaks
corresponded to Al and Si were generally identified.
The peaks of Al appeared at 38.5 ◦ C, 44.8 ◦ C, 65.1 ◦ C, 78.3 ◦ C and
82.5 ◦ C, respectively. They were known as Al (111), (200), (220), (311)
and (222) (PDF #04–0787). The remaining peaks can be found at 2θ
degree of about 28.4◦ , 47.3◦ , and 56.1◦ . They were known as Si (111),
(220) and (311) (PDF #27–1402). Other papers had similar results [65,
77,78]. However, the presence of C has not been found in the LOG-Al
Fig. 8. The Raman spectra of aluminum alloy, 0.05 wt %LOG-Al and 0.1 wt % composites, this may due to the very low content (0.05 wt % and 0.1
LOG-Al fabricated by LMD. wt %) of LOG addition. The presence of aluminum carbide Al4C3 was

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Fig. 9. TEM images of 0.1 wt % LOG-Al composites fabricated by LMD (a) (b), HRTEM images of 0.1 wt % LOG-Al (c) (d).

3.5. Mechanical properties

Fig. 11 shows the average Vickers hardness of LMD processes of pure

aluminum alloy, 0.05 wt % LOG-Al and 0.1 wt % LOG-Al composites
samples, which were processed by LMD under the same processing
conditions. The average hardness is 86.19HV, 125.36HV and 147.80HV
for pure aluminum alloy, 0.05 wt % and 0.1 wt % LOG-Al composite
respectively. It has a nearly linearly increase of 45.45 % and 71.48 % for
0.05 wt % and 0.1 wt % LOG-Al composites compared with pure
aluminum alloy along with the LOG content up to 0.1 wt % in this study.
The addition of nano LOG led to grain refinement, and the microstruc­
ture characteristics had a significant impact on the hardness
distribution.
In other research works [65], the average hardness increases to
66.6HV at graphene content of 2.5 wt %. However, it also concluded
that increasing graphene content may reduce the microhardness of

Fig. 10. XRD spectra of LMD process pure aluminum alloy, 0.05 wt %LOG-Al
and 0.1 wt %LOG-Al composites.

also not observed in either XRD or TEM results. This is because the
thermally stable graphene did not easily interact with the aluminum
alloy. This is also due to the low content of graphene (only 0.05 % and
0.1 %), less aluminum carbide produced by chemical reactions, and
trace amounts of dispersed aluminum carbide that cannot be detected.
However, the presence of aluminum carbide Al4C3 was reported in
other studies such as in adding graphene weight of 1 % in the aluminum
alloy in hot extrusion [62]. It is worth mentioning that, a certain amount
of aluminum carbide will improve the wettability of LOG and aluminum
alloy, this has a positive effect on the properties of the material [63].
Fig. 11. The Vickers hardness of LMD process pure aluminum alloy, 0.05 wt %
LOG-Al composites and 0.1 wt %LOG-Al composites.

8
P. Li et al. Materials Science & Engineering A 823 (2021) 141749

composites, peculiarly when the graphene content reached a certain Table 4

value, due to the enhancing phase aggregation [1,65,79]. Mechanical properties of pure aluminum alloy and LOG-Al composites.
Fig. 12 indicates the tensile properties of LOG-Al composites with Content Tensile Yield Elastic Ductility
different contents of LOG fabricated by LMD with the same working strength strength modulus (mm/mm)
parameters. Table 4 shows the mechanical properties of pure aluminum (MPa) (MPa) (GPa)
and LOG-Al composites. It can be seen from Fig. 12 and Table 4 that the 0 wt % 150.06 71.81 77.33 0.0299
tensile strength, yield strength and ductility of the composites show an 0.05 wt % 205.15 94.33 88.05 0.0575
upward trend with the increase of LOG content up to 0.1 wt %. 0.1 wt % 227.57 110.36 105.99 0.0641
Increase % Tensile Yield Elastic Ductility
The tensile strength of the material was 205.15 MPa with a LOG compared with strength strength modulus
content of 0.05 wt %, the yield strength, elasticity modulus and ductility aluminium alloy
were 94.33 MPa, 88.05 GPa and 5.75 %. These were significantly higher 0.05 wt % 36.7 % 31.4 % 13.9 % 92.3 %
than that of AlSi7Mg alloy without the addition of LOG, the increases 0.1 wt % 51.7 % 53.7 % 37.1 % 114.4 %
were 36.7 %, 31.4 %, 13.9 % and 92.3 % respectively. When the LOG
content was 0.1 wt %, the tensile strength of the material was 227.57
LOG and to enhance cold bonding and interfacial adhesion between
MPa, the yield strength, elasticity modulus and ductility were 110.36
reinforcements and matrix. The good interface facilitates effective load
MPa, 105.99 GPa and 6.41 %. The increases were 51.7 %, 53.7 %, 37.1
transfer and prevents debonding, thereby improving the tensile
% and 114.4 % compared with pure aluminum alloy.
strength, yield strength and elongation of LOG-Al composites [34,39,
Fig. 13 shows the SEM fracture surface of LOG-Al composites with
80]. However, Hu et al. [65] indicated in relatively high content of
different contents of LOG to further investigate the effect of adding LOG
graphene/GO in some studies that the agglomeration weakens the
on mechanical properties of aluminum alloy matrix. Fig. 13(a1-a4) show
composites as one reason is that for multilayer graphene, the
the SEM fracture surface of the pure aluminum alloy, the entire fracture
out-of-plane stress is much lower than that of in-plane strain properties,
surface is bright and light-reflecting, with small and shallow dimples,
which leads to the reduction of mechanical properties. With this high
which is consistent with the low elongation of the material. Fig. 13 (b1-
strength, good interfacial bonding between LOG and aluminum matrix
b4) show the fracture surface of LOG-Al composites with a LOG content
and the spread plastic deformation to an increased number of grains per
of 0.05 wt %, the dimples are larger and deeper. Fig. 13 (c1-c4) show the
unit volume due to refined grains, the ductility of the material is also
fracture surface of LOG-Al composites with LOG content of 0.1 wt %, the
improved.
dimples elongated along the loading direction (Fig. 13 c2-c3), indicating
By comparing the morphology of the three fractures and stress-strain
that it has undergone greater plastic deformation, which is consistent
curve, it can be concluded that with the increase of LOG content, the
with the ductility results and is better than when the LOG content is 0.05
mechanical properties including strength, hardness and ductility of the
wt % and 0 wt %. The observation of Fig. 13 (b4) and Fig. 13 (c4) reveal
composites have all been improved to a certain extent.
the presence of LOG at the fracture, indicating that LOG played an
Table 5 compares the mechanical properties of graphene-aluminum
important role in tensile testing. i. e LOG not only refines the grain but
composites with recent studies. According to the table, the tensile
also acts as a bridge to take a certain load during the fracture process,
strength of the composites was improved linearly with the addition of
thereby improving the tensile properties of the material.
graphene except for Rashad’s powder metallurgy (after extrusion) study
The LOG-Al sample made by LMD has significantly higher strength
where the tensile strength of the composites decreased initially and then
than the unreinforced pure aluminum alloy. This phenomenon is due to
increased as the graphene content increased [62]. The tensile strength of
the addition of LOG that leads to grain refinement and dislocations. The
composite material was increased 61.7 % at most in the conventional
microstructure refinement in a LOG-Al composite contributes signifi­
preparation method [8,62], and up to 51.7 % in 3D printing (LMD, this
cantly to the mechanical improvement of LOG-Al AMCs fabricated by
research).
LMD. This is explained by Gu et al. [39] that a reduction in grain size can
The yield strength and hardness of the graphene-aluminum com­
improve the mechanical performance of composites according to the
posites fabricated by the conventional process increase with the increase
Hall-Petch relationship. Al matrix is also strengthened by ultra-fine
of graphene content, while the elongation is the opposite. When the laser
nanostructures via the Orowan looping mechanism and thereafter the
additive manufacturing was used to prepare graphene-aluminum com­
nanoscale structures help hinder the movement of grain dislocations.
posites, the yield strength, hardness and elongation of the composites
Effective bonding between LOG and aluminum alloy matrix also
were all improved, the maximum increase was 53.8 % (LMD, this
plays a significant role in the mechanical improvement of LOG-Al
research), 75.3 % (SLM, Hu) and 114.4 % (LMD, this research) respec­
composites. The addition’s content of LOG is low (0.1 wt %) in this
tively. This may due to rapid cooling in laser additive manufacturing
study, which allows the LOG sheets to disperse evenly in aluminum
process resulting in finer grains than conventional processes, which
alloy. In addition, wet ball milling is used to improve the dispersion of

Fig. 12. Mechanical properties (tensile strength and yield strength and tensile strength) (a) and stress-strain curve (b) of LMD process pure aluminum alloy, 0.05 wt
%LOG-Al composites and 0.1 wt %LOG-Al composites.

9
P. Li et al. Materials Science & Engineering A 823 (2021) 141749

Fig. 13. SEM images of LMD process pure aluminum alloy fracture surface (a1) (a2) (a3) (a4), 0.05 wt %LOG-Al composites fracture surface (b1) (b2) (b3) (b4), 0.1
wt %LOG-Al composites fracture surface (c1) (c2) (c3) (c4).

Table 5
Experimental tensile strength and yield strength and elongation and hardness of graphene aluminum matrix composites.
Fabrication techniques Graphene (wt. %) and Tensile strength (TS) 0.2 % Yield strength (YS) Elongation Hardness (HV) Reference
matrix (MPa) (MPa) (%)

Powder metallurgy (PM) (Before 0/0.25/0.5/1 (Al) 105/119/116/108 57/58/64/59 18/27/13/10 69/71/74/77 Rashad et al. [62]
extrusion)
Powder metallurgy (PM) (After 0/0.25/0.5/1 (Al) 186/166/175/203 112/117/120/145 15/22/08/13 76/80/85/90 Rashad et al. [62]
extrusion)
Hot extrusion 0/0.3 (Al) 154/249 N/A 27/13 N/A Wang et al. [80]
Hot extrusion 0/0.18 (Mg–1%Al–1% 236/269 161/208 16.7/10.9 N/A Rashad et al. [8]
Sn)
Selective laser melting (SLM) 0/0.5/1/2.5 (Al) N/A N/A N/A 38/47.1/49.6/ Hu et al. [65]
66.6
Selective laser melting (SLM) 0/1 (AlSi10Mg) 357/396 N/A 5.5/6.2 N/A Zhao et al. [63]
Selective laser melting (SLM) 0/0.5 (AlSi10Mg) 337/346 234/246 3.0/3.2 N/A Yachao Wang et al.
[81]
Laser metal deposition (LMD) 0/0.05/0.1 (AlSi7Mg) 150.06/205.15/ 71.81/94.33/110.36 2.99/5.75/ 86.19/125.36/ This research
227.57 6.41 147.80

helps to improve mechanical properties. (1) The addition of LOG and rapid cooling in LMD process helped to
In this study, LMD was used to fabricate LOG-Al composites with improve the microstructure of aluminum alloy. Significant grain
LOG content of 0 wt %, 0.05 wt % and 0.1 wt %. In addition to the refinement was achieved at LOG content of 0.1 %, where average
improvement of the above mechanical properties, the elastic modulus of grain size was reduced from 12.2 ± 0.4 μm to 6.7 ± 0.2 μm. The
composites was also increased from 77.33 GPa to 105.99 GPa. This may addition of LOG also helped transfer loads and prevented grain
be due to the low content of low oxidation graphene and its uniform dislocations.
dispersion in the matrix. Higher graphene content may not have a pos­ (2) Due to the low content of LOG, C and Al4C3 peak was not detected
itive effect on the ductility and elastic modulus of graphene-aluminum in the XRD of the composites. The types of “Al peak” and “Si
composites, as it increases the probability of producing more brittle peak” also did not change in the addition of LOG up to 0.1 %.
aluminum carbide. (3) With LOG sheets reinforcement, the hardness, tensile strength,
elongation, modulus of elasticity and yield strength of the com­
4. Conclusion posites increased with the increasing of LOG addition content. At
the content of LOG of 0.1 wt %, the hardness, tensile strength,
In this work, low oxidation graphene aluminum matrix (LOG-Al) elongation, elastic modulus and yield strength of the composites
composite powder was prepared by wet ball milling. Pure aluminum were 147.8HV, 227.57Mpa, 6.41 %, 105.99 GPa, 110.36Mpa,
alloy (AlSi7Mg), 0.05 wt %LOG-Al and 0.1 wt %LOG-Al composites were respectively, which increased by 71.5 %, 51.7 %, 114.4 %, 37.1
then fabricated by LMD process. The microstructures and fracture sur­ %, and 53.8 % compared with the aluminum alloy matrix.
faces of the composites were observed and the results of TEM, HRTEM, (4) Wet ball milling helped wrap LOG on the surface of aluminum
EBSD, XRD spectra, Raman spectra, Vickers hardness, tensile properties alloy powder and form a good combination with aluminum alloy
were analyzed. The main conclusions can be drawn as follows: powder, resulting in uniform dispersion of LOG in aluminum
alloy powders.

10
P. Li et al. Materials Science & Engineering A 823 (2021) 141749

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