Metallurgical processing- While discussing about the carbonaceous

reinforcement in metal matrices, the focus has been mainly on CNTs as

compared to graphene or its derivative till recent past. This might be
explained as the difficulty in exfoliation of graphite oxide into graphene,
which was achieved successfully few years back only. The dispersion of
graphene is also more challenging altogether due to much higher interfacial
area and surface tension. The main metallurgical processing techniques,
used till date, for fabrication of metal-graphene composite include hot
extrusion, hot rolling, mechanical alloying and solid state friction stirring.
Apart from these there are some discrete efforts of using different routes for
processing such composites. While discussing about the fabrication of metalgraphene composites, the major challenges have always been the extreme
conditions, required for consolidation of metals, i.e., high temperature and
pressure. Attention was always paid to secure the safe existence of the
reinforcement phase, graphene, through these processing extremities.
Following subsections provide a brief discussion on each processing
techniques,
highlighting
their
success,
advantages
and
challenges/shortcomings in fabricating metal-graphene composites.
Mechanical alloying- It is one of the widely used power metallurgical
technique, which is used to manufacture GNP/metal MMC. It is a simple
technique that allows improved dispersion of powder based constituents
through mechanical milling, before consolidation. Mechanical alloying starts
with the mechanical milling of metal powders and GNPs in a high energy ball
mill in the presence of a process control agent, like, methanol to prevent
agglomeration. The whole process is conducted and in an inert atmosphere,
like, Ar to protect graphene and metal powders from oxidation. After milling
is done, the composite powder is generally cold consolidated and then
sintered under inert atmosphere.
For milling ball mill to powder ratio, milling time and intensity of
milling are important factors. High milling time and low energy ball mills,
small milling time and high energy ball mills or high milling time and high
energy ball mills all will lead to amorphous carbon as it either increases the
number of impacts or the intensity of impacts increases. But in case of MMC
the presence of metal prevents to a great extent the formation of amorphous
carbon as it forms a coating outside graphene (1). Therefore milling time and
GNP concentration will influence the morphology, powder size,
microstructure and properties of GNP/metal MMC.

Hot Extrusion- Hot extrusion is a hot working process in which the material
is forced to go through a die. Being a hot working process it prevents work
hardening. This technique is the most widely used than any other
metallurgical process for fabrication but requires a lot of preparation in terms
of blending, milling, pressing and then finally extrusion. The biggest
drawback observed while working with CNTs or graphene is that at high
temperature the formation of carbides at the interface of metal and the
damaged introduced in the structure, which hampers the strength of the
composite.
Almost all previous research on carbon based metal matrix composite
used spherical metal powder with particle size ranging between 1-22 m (2)
(3) (4) (5) (6). However, it was observed that by replacing spherical powders
with nano flakes and their surface modification with poly vinyl alcohol(PVA)
improved the compatibility with graphene (3). The morphological similarity of
matrix and reinforcement powders is supposed to ensure homogeneous
mixing and better consolidation. Graphene/GNPs used were either purchased
(4) (5) chemically synthesized (6) or thermally exfoliated (2) from graphene
oxide, which were prepared using hummers method (2) (6). Blending of
metal powder and graphene was done either in dry state by adding them
together in presence of stearic acid (2wt%) to prevent agglomeration in
acoustic mixer (2) (6) or by slurry blending i.e. mechanical agitation of
sonicated graphene oxide and Al slurry in acetone (5) or ethanol (4). To
obtain the homogeneous mixture milling is done which also refines the grains
and breaks the oxide layer (2), then the mixture is compacted into billets
either through hot isostatic pressing (2) or compacted and then sintered in
muffle furnace up to 600C with (3) or without Ar gas (5). Finally the
compacted powder is extruded at temperatures above the recrystallisation in
extrusion ratio desired (2) (3) (4)(5) (6).

Hot Rolling- The dispersion of Graphene into metal matrix is a difficult task
using traditional methods as the former tend to agglomerate due to large
surface area. Therefore the researchers have come up with different novel
routes for successful fabrication of Graphene/metal MMC. Recently, a
combination of high energy ball milling and rolling is being used effectively
for the fabrication of Graphene/metal MMC. The metal powder of desired
purity and size (generally 99.5% purity and size between 20 to 150 m) is
taken. Graphene was either purchased (7) or mechanically exfoliated from
graphite using ball milling in the presence of medium like isopropyl alcohol

intermittently to maintain ambient processing temperature without any

process control agent (8). It is expected that by using ball mill the graphite
flakes gets exfoliated by shear forces on contact between powder and balls
during milling.
To exfoliate the graphene further from Multi Layer Graphene (MLG) to Few
Layer Graphene (FLG) and to disperse it uniformly in metal powder it is either
first ball milled in planetary ball mill at around 100 r.p.m for 3 hrs in the
presence of process control agent i.e. Stearic acid to prevent agglomeration
or sticking to ball mill and finally ball milled in a high energy attritor mill (8)
or it is first vibration treated in ethanol for 1 hr at a frequency of
approximately 10kHz using ultrasonic cleaner and dried in air to remove
ethanol and then milled in high energy attritor mill with stearic acid added as
process control agent (7). In high energy attritor milling is done at 400-500
r.p.m for 4-6 hr in an inert atmosphere of argon (7) (8).
The processed metal & Graphene powder was compacted in the Cu
tube(30-60 mm outer diameter, 28-58 mm inner diameter & 150 mm height)
which was degassed sealed at both ends & heated to (400-500C). Then
finally the compacted powder is subjected to either Equal speed rolling (ESR)
or High Speed Differential Rolling (HSDR) (7) for the no. of passes till we get
the desired thickness generally between (1mm-2mm). The Cu layer can be
mechanically removed by polishing. The temperature during rolling may be
high (8) or low (7). In case of Graphene/metal MMC we intend high
temperature during rolling to ensure good bonding of graphene with metal
(8) but in case of few metals processing at high temperature may lead to
formation of carbides at the interface which would hamper its properties.
Solid State Friction Stirring- Solid state Friction stir processing (FSP)is a
solid state technique which uses same approach as friction stir welding. A
rotating tool is inserted into a material and it mechanically stirs the material
which is softened by frictional heat generated by tool. In fabrication of
CNT/metal composite by FSP either a hole or a groove is machined on the
surface of a metal which acts as a reservoir for them.
CNT/metal MMCs were successfully fabricated through FSP. But, in case of
Graphene the main challenge was the dispersion as garphene has a large
surface area due to which they tend to agglomerate. Thus, it was believed
that dispersion through FSP alone would be challenge nd a novel method was
developed (9). It is combination of liquid state ultrasonic processing followed
by solid state FSP. The GNPs were fed into the melt of metal through feeding

system at temperature around 50C above the melting temperature of metal

and ultrasonic stirring was done. After mixing, the melt was casted into
plates of thickness < 6 mm. However, SEM images showed clusters of
graphene, denoting poor dispersion. To improve the dispersion Solid state
processing technique was used so FSP was applied and SEM was done which
showed better dispersion (9).
Recently Graphene/metal MMC was made directly through FSP, where
graphene was applied on the surface of metal in the form of GO/water colloid
(15mg/ml),. The water evaporates as the tool starts to rotate because of the
heat produced due to friction. The GO is effectively reduced to RGO by heat
generated during FSP and it is validated by conducting TGA of GO. as it was
seen that at around 200-300C the major loss occurs due to pyrolysis of
oxygen containing functional group i.e. hydroxyl, carbonyl etc. to yield CO 2,
CO and H2O (10).

Other processing Methods- There are various methods for manufacturing

metal matrix composites out of which powder metallurgy is the most
practiced method these days specially to fabricate nanoparticle/metal MMC.
Casting or liquid state processing was also one of the frequently used
method in the past for fabricating MMC. However, liquid state process is
being rarely used with nanomaterials as reinforcement. This is due to the
challenge in uniform dispersion of nanomaterials, as they always tend to
agglomerate due to their high specific surface area.
Recently a novel route for fabrication of MMC was developed which
involved the liquid state ultrasonic stirring. In this process, graphene was fed
into the molten metal at temperature approximately 50C above the melting
temperature and then stirred with a probe at high frequency. The melt was
then casted into sheets having small thickness of 6mm. SEM of the casted
sheet showed the non uniform distribution of graphene. To improve
dispersion it was followed by solid state frictional processing FSP, which has
been discussed thoroughly in previous section (9).

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