coatings

Article
Microstructure and Properties of Cladding Layers
Prepared by Argon-Shielded Arc Cladding of
CuZn40-WC Powders on Pure Aluminum Substrate
Xinge Zhang 1 , Qing Sang 2 , Zhenan Ren 2, * and Guofa Li 1
1 School of Mechanical and Aerospace Engineering, Jilin University, Changchun 130025, China;
zhangxinge@jlu.edu.cn (X.Z.); lgfjlu@163.com (G.L.)
2 College of Materials Science and Engineering, Jilin University, Changchun 130025, China;
sangqing1991@126.com
* Correspondence: renzhenan@yeah.net; Tel.: +86-431-8509-5899




Received: 8 September 2018; Accepted: 26 October 2018; Published: 27 October 2018


Abstract: Aluminum and aluminum alloys have the advantage of a high strength-to-weight ratio,
but their low hardness and poor wear resistance often cause wear damage. In the present study,
the cladding layer was prepared using argon-shielded arc cladding of CuZn40-WC powders which
were pre-coated on a pure aluminum substrate. The effects of WC proportion on the morphology,
microstructure, and properties of cladding layers were investigated in detail. The results indicated
that the optimal WC proportion in CuZn40-WC powders was 60 wt.%. With the increase of WC
proportion, although the morphology of the cladding layer became slightly worse, the surface quality
of the cladding layer was acceptable for industrial application until the WC proportion was 80 wt.%.
Meanwhile, the top width and maximum depth of the cladding layer decreased. The maximum
microhardness and optimal wear resistance of the cladding layer were 4.5 and 2.5 times that of the
aluminum substrate, respectively. The increased microhardness and wear resistance were mainly
attributed to the formation of Al4 W in the cladding layer. The wear scar of the high wear resistance
specimen was smoother and some bulk Al4 W compounds were clearly observed on the wear surface.

Keywords: argon-shielded arc cladding; aluminum substrate; CuZn40-WC powders; microstructure;

wear resistance

1. Introduction
Due to the demands for lightweight, energy-saving, and environmentally friendly materials,
aluminum and aluminum alloys are increasingly applied in mechanical engineering, automobile,
rail traffic, aerospace, shipping, and other industrial fields [1–3]. However, the shortcomings of a
poor wear resistance, low strength, and low melting point have limited their extensive application.
For example, high hardness, wear resistance, and high temperature resistance are required for cylinder
and friction pair parts, and an aluminum alloy is difficult to apply. Therefore, improvement of the
wear resistance and high temperature resistance of aluminum alloy surfaces has become an important
issue [4–6].
At present, laser and arc heat sources are mainly used for the surface strengthening and treatment
of aluminum and aluminum alloys. Ravi et al. [7] studied laser surface alloyed aluminum with Ni-Cr
powder. The results showed that metallurgical bonding was formed between the cladding layer and
the substrate without crack defects, and the microhardness of the cladding layer increased with the
increasing Cr concentration. Ye et al. [8] prepared an Fe-Al intermetallic coating on an aluminum
alloy substrate by laser cladding, and the composite cladding layer consisted of α-Al, FeAl, FeAl3 ,
Fe2 Al5 , and Fe3 Al phases. Compared with the aluminum substrate, the microhardness of the cladding

Coatings 2018, 8, 382; doi:10.3390/coatings8110382 www.mdpi.com/journal/coatings

Coatings 2018, 8, 382 2 of 13

layer was greatly improved, and the maximum hardness reached up to 890 HV. Jendrzejewski et al. [9]
performed laser cladding of SiC and WC powders on an aluminum alloy by synchronous powder
feeding, and the cladding layers had no defects and were more wear and corrosion resistant than the
aluminum alloy substrate. Ouyang et al. [10] conducted laser cladding of yttria partially stabilized ZrO2
(YPSZ) ceramic coatings on three different aluminum alloys (AlSi9Cu3, AlZn10Si8Mg, and AlSi10Mg
alloys), and ZrO2 ceramic coatings with a low dilution ratio and high hardness were obtained, but
there were pore and crack defects. Man et al. [11] put forward a process to prepare a composite
layer on a 6061 aluminum alloy by laser cladding technology. The pre-coated Ti-C-W-WC mixed
powders were laser cladded using a coaxial nozzle to synchronously feed Ni-Al-Al2 O3 mixed powders,
and the Ni-Al-based composite layer was obtained by in-situ synthesis of TiC and WC particles.
Nath et al. [12] achieved laser surface alloying of commercially pure aluminum with WC-Co-NiCr
powders. The alloyed layer without defects and a uniform microstructure was successfully prepared
under the optimum process parameters, and the microhardness of the alloyed layer was greatly
increased compared with the aluminum substrate. Although the application of laser cladding on
aluminum and aluminum alloys is very popular, it is also limited because of the easy occurrence of pore
and crack defects, as well as the high cost of laser equipment and operating. Arc cladding technology
has the advantages of being low-cost and easy to operate, and having a high production efficiency,
and thus has gradually become one of the choices for aluminum alloy surface cladding [13–15].
Lotfi et al. [16] used the tungsten inert gas (TIG) welding process to fabricate an Al-Si/SiCp composite
layer on an aluminum substrate with Al, Si, and SiC mixed powders. They found that the SiC particles
distributed evenly on the aluminum matrix and the hardness and wear resistance of the cladding
layer was improved with the additional silicon, due to the formation of eutectic silicon particles.
Tang et al. [17] prepared TiC particles in the cladding layer of a 1060 Aluminum alloy by an in-situ
synthesis method using an argon-shield arc heat source. Good metallurgical bonding was formed
between the cladding layer and the substrate, with a large current parameter and without pore or
crack defects. The cladding layer was composed of α-Al, TiC, and a small amount of Al3 Ti and Al4 C3 .
However, to date, research on argon-shield arc cladding of aluminum alloys is limited.
In previous literature, aluminum surface strengthening was mostly limited to aluminum alloys.
Compared with aluminum alloys, pure aluminum is lighter weight, and displays better heat transfer,
conductivity, and corrosion resistance, but its hardness and strength are lower, so it has a greater
requirement for surface strengthening. Therefore, pure aluminum was chosen as the substrate material
in the present study. The cladding materials used for the surface modification of aluminum and
aluminum alloys were mainly Ni-based, Cu-based, and Fe-based alloy powders with a certain amount
of ceramic phase powders, such as Al2 O3 , SiC, TiC, and WC [18–21]. On the basis of good wettability
between the Cu-Zn alloy and WC, and good wettability and compatibility between the Cu-Zn alloy
and Al, CuZn40-WC mixed powders were employed to prepare cladding layers on the pure aluminum
substrate using the argon-shield arc technique. The effects of the composition of CuZn40-WC mixed
powders on the morphology, microstructure, and properties of cladding layers were investigated
in detail.

2. Materials and Methods

In the present study, the pure aluminum plate was used as the substrate, with dimensions of
60 mm × 25 mm × 8 mm. As shown in Figure 1, the microstructure of the pure aluminum substrate
displays a distinct grain and grain boundary, and the X-ray diffractometer (XRD) analysis indicates that
the pure aluminum substrate is only comprised of an α-Al phase. The cladding material is CuZn40 and
WC powders, and the scanning electron microscopy (SEM) images are shown in Figure 2. The average
size of CuZn40 powder is 20 µm, and the average size of WC powder is 2 µm.
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(a) (b)
Figure 1. Pure aluminum substrate: (a) Microstructure; (b) X-ray diffractometer (XRD) pattern.

(a) (b)
Figure 2. Scanning electron microscopy (SEM) images
images of
of the
the powders:
powders: (a)
(a) CuZn40;
CuZn40; (b)
(b) WC.
WC.

Firstly,
Firstly, the
the pure
pure aluminum
aluminum platesplates were
were sanded
sanded with
with SiC sandpaper to
SiC sandpaper to remove
remove the the oxide
oxide film,
film,
and
and were
were then
then wiped
wiped withwith acetone
acetone to to remove
remove oiloil and
and debris.
debris. The CuZn40
CuZn40 powder
powder and and WC
WC powder
powder
with different proportions were mixed evenly, and the proportion of WC
with different proportions were mixed evenly, and the proportion of WC powder in the CuZn40-WCpowder in the CuZn40-WC
mixed
mixed powders ranged ranged from
from 00 toto 80%. The CuZn40-WC powders were pre-coated in pure aluminum
substrate
substrate with a 0.6
a 0.6 mmmm thickness.
thickness. The powder
powder pre-coating
pre-coating method
method was as as follows:
follows: a mould
mould with
with
dimensions 60 mm × 15 mm ×
dimensions of 60 mm × 15 mm × 0.6 mm was placed on the substrate surface, and the powders then
of 0.6 mm was placed on the substrate surface, and the powders then
were
were placed
placed and
and filled
filled within
within the
the mould;
mould; secondly,
secondly, aa proper
proper amount
amount of of sodium
sodium silicate
silicate solution
solution was
was
poured
poured into the powders to bond them together and adhere them to the substrate surface; finally, the
into the powders to bond them together and adhere them to the substrate surface; finally, the
samples were dried
driednaturally
naturallyfor for2424h h and put into ◦
samples were and put into thethe
ovenoven at 100
at 100 °C forC2for 2 h, then
h, and and cooled
then cooled
to roomto
room temperature
temperature for later
for later use. use.
The The argon-shielded
argon-shielded arc arc provided
provided byby a directcurrent
a direct currentusing
using the
the WP-300
Tungsten
Tungsten Inert
InertGas Gas (TIG) welding
(TIG) weldingmachine was employed
machine was employed to cladtotheclad
pre-coated CuZn40-WC
the pre-coated powders
CuZn40-WC
and prepare
powders andthe cladding
prepare thelayer on the
cladding pureon
layer aluminum
the pure substrate.
aluminumDuring the arc
substrate. cladding
During process,
the arc the
cladding
tungsten pole
process, the and specimen
tungsten pole andwere connected
specimen to the negative
were connected to theand positive
negative andterminals of the welding
positive terminals of the
power
welding source,
power respectively. The schematic
source, respectively. diagram
The of thediagram
schematic argon-shielded arc cladding process
of the argon-shielded is shown
arc cladding
in Figureis3.shown
process The main parameters
in Figure 3. Theofmainthe argon-shielded
parameters of arc the cladding processarc
argon-shielded arecladding
listed in Table
process1. are
listed in Table 1.
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Argon gas
Cladding direction
Arc
Cladding composite layer Pre-coated powders

Substrate

3. Schematic diagram of the argon-shielded arc cladding process.

FigureFigure
3. Schematic diagram of the argon-shielded arc cladding process.
Table 1. Main parameters of the argon-shielded arc cladding process.
Table 1. Main parameters of the argon-shielded arc cladding process.
Electrode Diameter Cladding Current Cladding Velocity Flowing Velocity of
(mm) (A) (mm/s) Argon (L/min)
Electrode Diameter Cladding Current Cladding Velocity Flowing Velocity of Argon
2.4
(mm) (A) 160 (mm/s)2.8 10
(L/min)
2.4 160 2.8 10
After cladding, the samples were transversely sectioned, and then mounted, polished, and etched
After cladding, theobservation.
for microstructure samples were The etch solution consisted
transversely of 1 mland
sectioned, HCl,then
1 ml mounted,
HF, and 8 mlpolished,
H2 O. and
The optical microscope (Axio Scope.A1, ZEISS, Jena, Germany) and scanning
etched for microstructure observation. The etch solution consisted of 1 ml HCl, 1 ml HF, and 8 ml electron microscope
(SEM) (JXA-840, JEOL, Tokyo, Japan) with an energy dispersive spectrometer (EDS) were employed to
H2O. The optical microscope (Axio Scope.A1, ZEISS, Jena, Germany) and scanning electron
observe the microstructure characteristics and to analyze the chemical compositions. The EDS analysis
microscope (SEM) (JXA-840,
was performed JEOL,
using a 20 Tokyo, Japan)
kV accelerating with
voltage, an energy
35 µA emissiondispersive
current, andspectrometer
10.5 mm working (EDS) were
employed to observe
distance, and the the microstructure
images were obtained in characteristics and to
the secondary electron analyze
imaging theThe
mode. chemical compositions.
phase structure
was measured using an X-ray diffractometer (XRD) (D/MAX-2500PC, Rigaku,
The EDS analysis was performed using a 20 kV accelerating voltage, 35 μA emission current, and Tokyo, Japan) machine
10.5 mmand the maindistance,
working operating and
parameters included
the images a 40 kV
were voltage, in
obtained 250the
mAsecondary
current, Cu Kα radiation,
electron 0.02◦ mode.
imaging
◦
angle step-length, and 4 /min scanning rate. The microhardness was measured on the cross-section
The phase structure was measured using an X-ray diffractometer (XRD) (D/MAX-2500PC, Rigaku,
of the cladded specimen by the hardness testing machine (Everone MH-3, Everone Enterprises, Ltd.,
Tokyo, Japan)
Nanjing,machine
China) andand the
the main
load and operating
load time wereparameters
100 g and included a 40 kVThe
10 s, respectively. voltage, 250with
specimens mA current,
Cu Kα radiation,
dimensions0.02° angle
of 5 mm × 5step-length,
mm × 8 mm (wear and 4°/min scanning
test surface was 5 mmrate.
× 5The
mm,microhardness
and holding height waswasmeasured
8 mm) were prepared
on the cross-section of theto conduct
claddedthespecimen
wear experiment
by theat room temperature.
hardness testingThe two-body(Everone
machine abrasive MH-3,
experiment was performed using an abrasive wear test machine
Everone Enterprises, Ltd., Nanjing, China) and the load and load time were 100 (ML-100, Jinan Jingcheng Testing
g and 10 s,
Technology Company, Jinan, China) and the schematic diagram of the wear experiment is indicated in
respectively. The specimens with dimensions of 5 mm × 5 mm × 8 mm (wear test surface was 5 mm
Figure 4. Six-hundred-grit SiC sandpaper was employed as a friction counterpart and the constant
× 5 mm,normal
and holding
load was 3height
N. Eachwaswear 8 mm)
test were prepared
was performed with the to
sameconduct
stroke ofthe
20 m.wear experiment
The wear resistance at room
temperature. The two-body
was evaluated accordingabrasive experiment
to the weight waswear
loss of the performed
specimen.using an the
Finally, abrasive wear test
wear surface was machine
(ML-100,observed by the SEM-JXA840.
Jinan Jingcheng Testing Technology Company, Jinan, China) and the schematic diagram of
the wear experiment is indicated in Figure 4. Six-hundred-grit SiC sandpaper was employed as a
friction counterpart and the constant normal load was 3 N. Each wear test was performed with the
same stroke of 20 m. The wear resistance was evaluated according to the weight loss of the wear
specimen. Finally, the wear surface was observed by the SEM-JXA840.

Load

Clamp
V

Wear specimen
SiC sandpaper

n
(ML-100, Jinan Jingcheng Testing Technology Company, Jinan, China) and the schematic diagram of
the wear experiment is indicated in Figure 4. Six-hundred-grit SiC sandpaper was employed as a
friction counterpart and the constant normal load was 3 N. Each wear test was performed with the
same stroke of 20 m. The wear resistance was evaluated according to the weight loss of the wear
Coatings 2018, 8, 382 5 of 13
specimen. Finally, the wear surface was observed by the SEM-JXA840.

Load

Clamp
V

Wear specimen
SiC sandpaper

Base

Figure
Figure 4. Schematicdiagram
4. Schematic diagram of
ofthe
thewear
wearexperiment.
experiment.
3. Results and Discussion

3.1. Morphology of Cladding Layer

The morphology of the typical cladding specimen is shown in Figure 5. The cladding layers are all
gray except for that prepared with 100% CuZn40 powder, which is yellow (the color of Al-Cu-Zn alloy).
When the CuZn40 proportion in the mix powders was large, the cladding layer was very smooth,
but as the WC proportion was increased, spherical particles, voids, and poor fusion defects appeared
on the cladding layer surface. Because of the low melting point of CuZn40 powder (967 ◦ C) and the
high mutual solubility between Cu, Zn, and Al, the CuZn40 powder was prone to melt and dissolve
with aluminum or produce a small amount of compounds, and so the flow of the melting pool was
relatively stable during the cladding process with the high CuZn40 proportion powders. Owing to
the high melting point of WC powder (2870 ◦ C), a large part of WC powders was not melted by the
arc and moved to the melting pool, which resulted in an unstable flow of the melting pool and in
defects during the cladding process with the high WC proportion powders. Although the morphology
of the cladding layer deteriorated slightly with increasing WC proportion, the surface quality of the
cladding layer would be acceptable for industrial application until the WC proportion was 80 wt.%.
The surface of the cladding layer should then be performed with fine grinding for subsequent industrial
application. Figure 6a shows the typical morphology of the cladding layer cross-section. The top width
(W) and maximum height (H) of the cladding layer were used to evaluate the effect of the composition
proportion of CuZn40-WC powders on the cladding layer morphology. On the whole, the top width
(W) and maximum height (H) of the cladding layer decreased with increasing WC proportion in the
CuZn40-WC powders, as shown in Figure 6b. While the WC proportion was no more than 40 wt.%,
the decreases of W and H were obvious with the increase of WC proportion, and subsequently became
relatively constant. In this study, the parameters of the argon-shielded arc were constant, namely,
the total heat input was constant. Therefore, while the WC proportion in CuZn40-WC powders was
smaller, the argon-shielded arc heat was mostly used for the melting of CuZn40 powder and aluminum
substrate, which resulted in larger W and H. While the WC proportion in CuZn40-WC powders was
larger, more heat was expended to melt the CuZn40 powder and in particular the WC powder, and the
aluminum substrate exhibited less melting. Consequently, the W and H became smaller.
proportion in CuZn40-WC powders was smaller, the argon-shielded arc heat was mostly used for
the melting of CuZn40 powder and aluminum substrate, which resulted in larger W and H. While
the WC proportion in CuZn40-WC powders was larger, more heat was expended to melt the CuZn40
powder and in particular the WC powder, and the aluminum substrate exhibited less melting.
Coatings 2018, 8,
Consequently, the382W and H became smaller. 6 of 13

(a) (b) (c) (d) (e)

Figure
Figure 5. Morphology
5. Morphology of cladding
of cladding layer:
layer: (a) wt.%
(a) 100 100 wt.% CuZn40;
CuZn40; (b)wt.%
(b) 30 30 wt.% CuZn40
CuZn40 + 70+wt.%
70 wt.%
WC; (c)
WC; CuZn40
50 wt.% (c) 50 wt.% CuZn40
+ 50 wt.% +WC;
50 wt.% WC;
(d) 30 (d) CuZn40
wt.% 30 wt.% CuZn40 + 70WC;
+ 70 wt.% wt.%(e)
WC;
20 (e)
wt.%20 wt.%
CuZn40CuZn40
+ 80 +wt.%
Coatings 2018, 8, x FOR PEER REVIEW 6 of 13
WC. 80 wt.% WC.

W 7
H
7

Maximum height of cladding layer (H)/mm

W

Top width of cladding layer (W)/mm

6 6
Cladding layer
H 5 5

4 4

3 3

2 2

1 1

0 0
0 10 20 30 40 50 60 70 80 90

WC Proportion in CuZn40-WC powders/wt.%

(a) (b)
Figure6.6. Morphology
Figure Morphology of
of the
the cladding
cladding layer
layer cross-section:
cross-section: (a)
(a) Typical
Typical morphology;
morphology; (b)
(b) effect
effect of
of WC
WC
proportionin
proportion inCuZn40-WC
CuZn40-WCpowders
powderson oncladding
claddinglayer
layercross-section.
cross-section.

3.2.
3.2. Microstructure
Microstructure of
of Cladding
CladdingLayer
Layer
The
The microstructures
microstructures of of the
the cladding
cladding layers
layers prepared
prepared by by the
the argon-shielded
argon-shielded arc arc cladding
cladding of of the
the
CuZn40-WC
CuZn40-WC powders with different proportion components are indicated in Figure 7. While the
powders with different proportion components are indicated in Figure 7. While the
cladding
cladding powder
powder was was 100
100 wt.%
wt.% CuZn40
CuZn40 powder,
powder, the the microstructure
microstructure of of the
the cladding
cladding layer
layer was
was
homogeneous,
homogeneous, which was similar
which was similarto tothat
thatofofthe
thealuminum
aluminumsubstrate,
substrate,asas shown
shown in in Figure
Figure 7a, 7a,
andandthe
the
cladding layer was comprised of α-Al solid solution (containing Cu and Zn elements) and aa small
cladding layer was comprised of α-Al solid solution (containing Cu and Zn elements) and small
amount
amount ofof Al-Cu
Al-Cucompound.
compound. While While the
thelow
lowproportion
proportion((≤30 ≤30 wt.%)
wt.%) ofof WC
WC powder
powder was was mixed
mixed with
with
CuZn40 powder and used to clad, the cladding layers were also mainly
CuZn40 powder and used to clad, the cladding layers were also mainly comprised of α-Al comprised of α-Al solid
solid
solution. However, there
solution. However, there were
were small
small amounts
amounts of of agglomerated
agglomerated CuZn40CuZn40 and and WCWC powders
powders in in the
the
cladding layers, as shown in Figure 7b. Figure 8 shows the SEM microstructure
cladding layers, as shown in Figure 7b. Figure 8 shows the SEM microstructure and EDS analysis and EDS analysis
results
results of
of line
line scanning
scanning inin the
the typical
typical local
local zone
zone of ofFigure
Figure7b.7b. The
The results
results indicated
indicated that
that there
there were
were
large
large amounts
amounts of of W
W and
and Zn
Zn elements
elements andand small
small amounts
amounts of of Cu
Cu and
and Al
Al elements,
elements, which
which should
should be be
melted CuZn40 powder and non-melted WC powder infiltrated with a
melted CuZn40 powder and non-melted WC powder infiltrated with a small amount of aluminum small amount of aluminum
melt
melt at
at point
point A. A. At
At point
point B,
B, there
there was
was aa large
large amount
amount of ofAl
Aland
and aa small
small amount
amount of ofW W element,
element, which
which
was
was an Al-W compound with a maximum size of around 8 μm. Point C should be located at the grain
an Al-W compound with a maximum size of around 8 µm. Point C should be located at the grain
boundary
boundary of of the α-Al solid
the α-Al solid solution,
solution, which
which contained
contained aa large
large amount
amount of of Al
Al and
and CuCu elements
elements andand
represents
representsthethelow
lowmelting
meltingpoint
pointeutectic
eutecticcompound
compoundof ofAl-Cu.
Al-Cu.

α-Al
WC

CuAl2 Agglomerated powders

Al4W
Eutectic phase
50μm 50μm
large amounts of W and Zn elements and small amounts of Cu and Al elements, which should be
melted CuZn40 powder and non-melted WC powder infiltrated with a small amount of aluminum
melt at point A. At point B, there was a large amount of Al and a small amount of W element, which
was an Al-W compound with a maximum size of around 8 μm. Point C should be located at the grain
boundary of the α-Al solid solution, which contained a large amount of Al and Cu elements7 of
Coatings 2018, 8, 382
and
13
represents the low melting point eutectic compound of Al-Cu.

α-Al
WC

CuAl2 Agglomerated powders

Al4W
Eutectic phase
50μm 50μm
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(a) (b)
Figure 7. Cont.

Al
Al44W
W

Al
Al44W
W

50μm
50μm 50μm
50μm
(c)
(c) (d)
(d)
Figure
Figure 7.
7. Microstructure
Microstructure of
Microstructure of the
of the typical
typical cladding
typical cladding layer:
cladding layer: (a)
layer: (a) 100
(a) 100 wt.%
100 wt.% CuZn40;
wt.% CuZn40; (b)
CuZn40; (b) 70
(b) 70 wt.%
70 wt.% CuZn40
wt.% CuZn40 +++
CuZn40
30 wt.% WC; (c) 40 wt.% CuZn40 + 60 wt.%
30 wt.% WC; (c) 40 wt.% CuZn40 ++ 60 wt.% WC; (d) 20 wt.% CuZn40 +
wt.% WC; (d) 20 wt.% CuZn40 ++ 8080 wt.%
80 wt.% WC.
wt.% WC.
WC.

EDS
EDS scanning
scanning line
line

Figure 8.
Figure
Figure 8. Energy dispersive
8. Energy
Energy dispersive spectrometer
dispersive spectrometer (EDS)
spectrometer (EDS) results
(EDS) results of
results of line
line scanning in the
scanning in the local
local zone
zone of
of Figure
Figure 7b.
7b.
7b.

While the WC
While WC proportion increased
increased to 60 60 wt.%, the
the cladding layer
layer mainly consisted
consisted of the
the α-Al
While the
the WC proportion
proportion increased to to 60 wt.%,
wt.%, the cladding
cladding layer mainly
mainly consisted of of the α-Al
α-Al
matrix
matrix and
and many
many bulk
bulk Al
Al 4 W
W compounds,
compounds, as
as shown
shown in
in Figures
Figures 7c
7c and
and 9.
9. Figure
Figure 10
10 displays
displays the
the SEM
SEM
matrix and many bulk Al4W compounds, as shown in Figures 7c and 9. Figure 10 displays the SEM
4
image and EDS
image results of of
the cladding layer prepared with 40 wt.% CuZn40CuZn40
and 60 wt.% 60WC powders.
image and
and EDS
EDS results
results of thethe cladding
cladding layer
layer prepared
prepared withwith 4040 wt.%
wt.% CuZn40 and and 60 wt.%
wt.% WCWC
The results
powders. showed that there were large amounts of Al and W elements at point “a” and point “d”,
powders. The
The results
results showed
showed that that there
there were
were large
large amounts
amounts of of Al
Al and
and WW elements
elements at
at point
point “a”
“a” and
and
point “d”, and so the lath and bulk structures were an Al W compound. Meanwhile,
point “d”, and so the lath and bulk structures were an Al4W compound. Meanwhile, a large amount
4 a large amount
of
of Al
Al and
and Cu
Cu elements
elements existed
existed at at point
point “b”
“b” and
and point
point “c”
“c” located
located on
on the
the grain
grain boundary
boundary of of the
the α-Al
α-Al
matrix,
matrix, and
and were
were Al-Cu
Al-Cu and
and Al-Cu-Zn
Al-Cu-Zn compounds.
compounds. During
During thethe argon-shielded
argon-shielded arc
arc cladding
cladding process
process
with
with high
high WC
WC proportion
proportion powders
powders (e.g.,
(e.g., ≥60
≥60 wt.%),
wt.%), only
only small
small parts
parts of
of WC
WC powders
powders were
were heated,
heated,
melted, and decomposed, which then constantly dissolved and diffused into the matrix, and reacted
 Coatings 2018, 8, 382 8 of 13

and so the lath and bulk structures were an Al4 W compound. Meanwhile, a large amount of Al and
Cu elements existed at point “b” and point “c” located on the grain boundary of the α-Al matrix,
and were Al-Cu and Al-Cu-Zn compounds. During the argon-shielded arc cladding process with
high WC proportion powders (e.g., ≥60 wt.%), only small parts of WC powders were heated, melted,
Coatings 2018, 8, x FOR PEER REVIEW 8 of 13
and decomposed, which then constantly dissolved and diffused into the matrix, and reacted with
Al and other elements. Because of the substantial difference in the density, melting point, and poor
thereCoatings
were a2018,
large8, x number
FOR PEER of Al4W compounds with a maximum size of around 35 μm in the 8cladding
wettability between the REVIEW
liquid Al and C, the Al-C compound (Al4 C3 ) was not found in the cladding of 13
layer.layer. The Al and W can react to form a variety of Al-W compounds, such as Al W , Al W , Al W,
7 3 77 23 12
there
When were
theaWC largeproportion
number of Al 4W compounds
increased to 80with a maximum
wt.%, size oflayer
the cladding around 35 μm
was in thecomprised
mainly cladding of
Al 5 W, and Al4 W, and the minimum Gibbs free energy required to form different Al-W compounds is
α-AlAllayer.
solid solution and bulk Al4W compound, and the maximum size of Al4W was around 60 μm, as
4 W. Namely, Al4 W is the most easily generated Al-W compound when the W content satisfies the
shown When
in Figure the
7d.WC proportion
However, increased topoor
80 wt.%, the cladding layer wasWCmainly comprised of
formation conditions [22,23].because
When theofWC
the wettability
proportion was 60 between
wt.%, thehigh
compositionproportion
in most ofpowders
the
α-Al solid solution and bulk Al4W compound, and the maximum size of Al4W was around 60 μm, as
and the
meltaluminum
pool regions matrix, thethe
satisfied quantity of WC
formation powder
conditions of entering
the Al4 Wthe claddingand
compound, molten pool were
thus there decreased,
a
shown in Figure 7d. However, because of the poor wettability between high WC proportion powders
large number of Al W compounds with a maximum
resulting in a decrease4 of the quantity of Al4W compound. size of around 35 µm in the cladding layer.
and the aluminum matrix, the quantity of WC powder entering the cladding molten pool decreased,
resulting in a decrease of the quantity of Al4W compound.

Figure 9. XRD
Figure analysis
9. XRD results
analysis resultsofofthe
thecladding layer
cladding layer
cladding preparedwith
layer prepared
prepared with
with 6060
60 wt.%
wt.%
wt.% WCWC
WC powders.
powders.
powders.

(a) (b)
(a) (b) EDS results of
Figure 10. (a) SEM image; of the
the cladding
cladding layer
layer prepared (b)
prepared with
with 60 wt.%
60 wt.% WC
WCpowders.
powders.

Figure 10. (a)

When theSEM image; (b) EDS
WC proportion resultstoof80the
increased cladding
wt.%, layer prepared
the cladding with
layer was 60 wt.%
mainly WC powders.
comprised of α-Al
3.3. Microhardness
solid solution and bulk Al4 W compound, and the maximum size of Al4 W was around 60 µm, as shown
The microhardness experiments were carried out on a cross-section of the cladding layer, and
3.3. Microhardness
in Figure 7d. However, because of the poor wettability between high WC proportion powders and the
the schematic diagram of microhardness test is shown in Figure 11. The average microhardness
aluminum matrix, the quantity of WCwere
The microhardness powder entering
outthe cladding molten pool decreased, resulting
values of the cladding experiments
layers prepared using carried
the differentonWC a cross-section
proportions areofindicated
the cladding layer,
in Figure 12. and
in a decrease of the quantity of Al4 W compound.
the schematic
During thediagram of microhardness
microhardness test, when theretest wasis shown
a small in amount
Figure of
11.agglomerated
The averageCuZn40-WC
microhardness
values of the cladding
powders layers WC
and non-molten prepared
powder using
in the thecladding
different WC proportions
layers, the individualare indicated in values
microhardness Figure 12.
During
werethe microhardness
higher than 1100 HVtest,
0.3 duewhen
to thethere wasofaWC
existence small amount
particles of had
which agglomerated CuZn40-WC
a very high hardness.
Because the ultra-high microhardness values were individual and
powders and non-molten WC powder in the cladding layers, the individual microhardness were in the minority, they were
values
werenot included
higher thanin1100
the calculation
HV0.3 dueoftothe average
the existence microhardness values of
of WC particles the cladding
which layers.high
had a very As shown
hardness.
in Figure
Because 12, compared
the ultra-high with the aluminum
microhardness values substrate (27 HV0.3), the
were individual andaverage
were inmicrohardness
the minority, values
theyofwere
the cladding layers all increased. As the WC proportion increased from 0 to 60 wt.%, the microhardness
not included in the calculation of the average microhardness values of the cladding layers. As shown
 Coatings 2018, 8, 382 9 of 13

3.3. Microhardness
The microhardness experiments were carried out on a cross-section of the cladding layer, and
the schematic diagram of microhardness test is shown in Figure 11. The average microhardness
values of the cladding layers prepared using the different WC proportions are indicated in Figure 12.
During the microhardness test, when there was a small amount of agglomerated CuZn40-WC powders
and non-molten WC powder in the cladding layers, the individual microhardness values were higher
than 1100 HV0.3 due to the existence of WC particles which had a very high hardness. Because the
ultra-high microhardness values were individual and were in the minority, they were not included in
the calculation of the average microhardness values of the cladding layers. As shown in Figure 12,
compared with the aluminum substrate (27 HV0.3 ), the average microhardness values of the cladding
layers all increased. As the WC proportion increased from 0 to 60 wt.%, the microhardness of the
cladding layer increased and reached a maximum value of 122 HV0.3 , which was 4.5 times that of the
aluminum substrate. However, as the WC proportion continued to increase, the microhardness of
Coatings
the2018,
Coatings 8,
8, xx FOR
cladding
2018, PEER
layer
FOR REVIEW
decreased
PEER REVIEW slightly. According to the microstructure analysis of the cladding layer 99 of
of 13
13
described in Section 3.2, as the WC proportion was increased, the strengthening phases (especially
(especially
(especially
Al4 W) inAl 44W)
Althe W) in
in the cladding
the layers
cladding cladding layers gradually
layersincreased.
gradually gradually increased.
increased.
Therefore, Therefore,
Therefore, the
the improvement the improvement
improvement
of the of
of the
microhardness the
microhardness
was mainly was mainly
attributed to attributed
the to
increase the
of theincrease of the
strengthening strengthening
phases in the phases
cladding in the
layer.
microhardness was mainly attributed to the increase of the strengthening phases in the cladding layer. cladding layer.

Figure 11.
Figure
Figure Schematic
11.11. Schematicdiagram
Schematic diagram of
diagram of the
of the microhardness
themicrohardness
microhardness test.
test.
test.

140
140

120
120
value/HV0.3
0.3
microhardnessvalue/HV

100
100

80
80
Averagemicrohardness

60
60

40
40
Average

20
20

00
00 10 20
20 30 40 50
50 60 70 80
10 30 40 60 70 80
WC
WC proportion
proportion in
in CuZn40-WC
CuZn40-WC powders/wt.%
powders/wt.%

Figure 12.
12. Effect
Figure
Figure Effect of
of WC
12. Effect WC proportion
of WC proportionon
proportion onthe
on theaverage
the microhardness
average microhardness
average microhardness values
values of
of cladding
of cladding
values layers.
layers.
cladding layers.

3.4.
3.4. Wear
Wear Resistance
Resistance
Wear
Wear resistance
resistance was
was carried
carried out
out by
by the
the abrasive
abrasive wear
wear test,
test, as
as described
described in
in Section
Section 2.
2. Five
Five
specimens prepared by each of the CuZn40-WC mixed powders were performed
specimens prepared by each of the CuZn40-WC mixed powders were performed on the wear on the wear
resistance
resistance test,
test, and
and the
the average
average value
value of
of weight
weight loss
loss was
was obtained
obtained toto evaluate
evaluate the
the wear
wear resistance
resistance of
of
 Coatings 2018, 8, 382 10 of 13

3.4. Wear Resistance

Wear resistance was carried out by the abrasive wear test, as described in Section 2. Five specimens
prepared by each of the CuZn40-WC mixed powders were performed on the wear resistance test,
and the average value of weight loss was obtained to evaluate the wear resistance of the cladding
layer. The effect of the WC proportion on the weight loss of the wear resistance specimen is shown
in Figure 13. The results show that the greatest weight loss was the aluminum substrate, indicating
that all cladding layers had a better wear resistance than the pure aluminum substrate. The weight
loss of the cladding layer decreased substantially with increasing WC proportion and decreased to
the minimum at 60 wt.%. When the WC proportion continued to increase, the weight loss increased.
It is well-known that the smaller the weight loss of a specimen is, the better its wear resistance is.
Therefore, when the WC proportion was 60%, the wear resistance of the cladding layer was optimal,
which was 2.5 times that of the aluminum substrate. The results of the wear resistance test correspond
to the effect of the WC proportion on microstructure and microhardness; that is, the larger the size and
quantity of the compound strengthening phase (especially Al4 W) in the cladding layer, the better the
Coatings 2018,
wear 8, resistance.
x FOR PEER REVIEW 10 of 13

28

24

20
Weight loss/mg

16

12

0
-10
Substrate 0 10 20 30 40 50 60 70 80
WC proportion in CuZn40-WC powders/wt.%

FigureFigure
13. Weight lossloss
13. Weight of of
thetheAlAlsubstrate anddifferent
substrate and different cladding
cladding layers.layers.

The wear morphology indicates the wear resistance and wear mechanism of specimens.
TheThewear morphology indicates the wear resistance and wear mechanism of specimens. The
morphology of abrasive wear is mainly furrow and some concave pits were formed by the
morphology of abrasive
separation wearThe
of material. is mainly
smaller thefurrow and
quantity of some
furrowsconcave pits concave
and shallow were formed
pits, theby the the
better separation
of material.
wear The smaller
resistance [24]. the quantity
Figure 14 showsof thefurrows andmorphology
typical wear shallow concave pits, the
of the aluminum betterand
substrate the wear
some cladding layers. The wear specimen of the aluminum substrate had many
resistance [24]. Figure 14 shows the typical wear morphology of the aluminum substrate and some furrow wear scars,
claddingwhich were wider and deeper than those in the cladding layers. According to Figures 13 and 14, the
layers. The wear specimen of the aluminum substrate had many furrow wear scars, which
better the wear resistance of the specimen, the fewer furrow wear scars and concave pits, and the
were wider and deeper than those in the cladding layers. According to Figures 13 and 14, the better
smaller the depth and width, which were consistent with the microhardness and weight loss results.
the wearTheresistance
cladding of the prepared
layers specimen, withthe
highfewer furrow wear
WC proportion scarshad
powders and concave
a good wear pits, and and
resistance, the smaller
the depth and
their width,
wear surfaceswhich were
had some consistent
bulk particles, aswith
shownthe microhardness
in Figure 14c,d. Energyand weight
dispersive loss results. The
spectrometer
claddinganalysis was carriedwith
layers prepared out on particle
high WCI proportion
and particle II. The EDS had
powders results are given
a good in Table
wear 2, which
resistance, and their
indicates that the bulk of the particles are an Al4 W compound. The Al4 W particle has a high hardness,
wear surfaces had some bulk particles, as shown in Figure 14c,d. Energy dispersive spectrometer
and the improvement in wear resistance is attributed to the existence of a large number of Al4 W
analysis particles,
was carried out on particle I and particle II. The EDS results are given in Table 2, which
as shown in Figure 14c.
indicates that the bulk of the particles are an Al4W compound. The Al4W particle has a high hardness,
and the improvement in wear resistance is attributed to the existence of a large number of Al 4W
particles, as shown in Figure 14c.
cladding layers prepared with high WC proportion powders had a good wear resistance, and their
wear surfaces had some bulk particles, as shown in Figure 14c,d. Energy dispersive spectrometer
analysis was carried out on particle I and particle II. The EDS results are given in Table 2, which
indicates that the bulk of the particles are an Al4W compound. The Al4W particle has a high hardness,
Coatings
and the2018, 8, 382
improvement in wear resistance is attributed to the existence of a large number of 11
Alof4W
13

particles, as shown in Figure 14c.

Coatings 2018, 8, x FOR PEER REVIEW 11 of 13

(a) (b)
Figure 14. Cont.

(c) (d)
FigureFigure
14. Wear morphology
14. Wear of theof
morphology aluminum substrate
the aluminum and cladding
substrate layerslayers
and cladding prepared with different
prepared powders:
with different
(a) Substrate;
powders: (b)(a)
60 Substrate;
wt.% CuZn40(b) +6040wt.%
wt.%CuZn40
WC; (c) 40 wt.%
+ 40 CuZn40
wt.% + 6040wt.%
WC; (c) wt.%WC; (d) 20 +wt.%
CuZn40 CuZn40
60 wt.% WC;+ 80
wt.% (d)
WC.20 wt.% CuZn40 + 80 wt.% WC.

Table 2. The EDS results of particle I and particle II.

Table 2. The EDS results of particle I and particle II.
Element(at.%)
Element (at.%) Particle II
Particle Particle
ParticleIIII
AlAl 76.43
76.43 78.59
78.59
WW 21.62
21.62 20.35
20.35
Cu 0.83 0.26
Cu
Zn 0.83
1.12 0.0.26
77
Zn 1.12 0. 77
4. Conclusions
4. Conclusions
In this study, the argon-shielded arc was employed to clad the CuZn40-WC powders on a pure
In this study, the argon-shielded arc was employed to clad the CuZn40-WC powders on a pure
aluminum substrate to prepare a composite cladding layer, and the effects of powder composition on
aluminum substrate to prepare a composite cladding layer, and the effects of powder composition
the microstructure and properties of the cladding layer were investigated. The main conclusions are
on the microstructure and properties of the cladding layer were investigated. The main conclusions
as follows.
are as follows.
With the constant cladding process parameters and an increase in the WC proportion in
With the constant cladding process parameters and an increase in the WC proportion in CuZn40-
CuZn40-WC powders, the morphology of the cladding layer could be accepted for industrial
WC powders, the morphology of the cladding layer could be accepted for industrial application when
application when the WC proportion was below 80 wt.%, and the top width and maximum depth
the WC proportion was below 80 wt.%, and the top width and maximum depth of the cladding layer
of the cladding layer decrease. This is because, when the WC proportion was high, more heat was
decrease. This is because, when the WC proportion was high, more heat was expended to melt the
expended to melt the WC powder, and the wettability between the melted powder and aluminum
WC powder, and the wettability between the melted powder and aluminum substrate was poor.
substrate was poor.
During the argon-shielded arc cladding process, most of the pre-coated powders were melted
During the argon-shielded arc cladding process, most of the pre-coated powders were melted
by arc heating and several were agglomerated and then mixed with the molten aluminum substrate.
by arc heating and several were agglomerated and then mixed with the molten aluminum substrate.
When the WC proportion was less than 60 wt.%, the cladding layer was mainly composed of α-Al
solid solution, a small amount of Al 4W compound, and agglomerated CuZ40-WC powders. When
the WC proportion was greater than or equal to 60 wt.%, the cladding layer was mostly comprised
of α-Al and a large number of Al 4W existed in shapes of lath and bulk. With an increased WC
proportion, the quantity and size of the Al4W compound increased, and the morphology of the Al4W
Coatings 2018, 8, 382 12 of 13

When the WC proportion was less than 60 wt.%, the cladding layer was mainly composed of α-Al
solid solution, a small amount of Al4 W compound, and agglomerated CuZ40-WC powders. When the
WC proportion was greater than or equal to 60 wt.%, the cladding layer was mostly comprised of α-Al
and a large number of Al4 W existed in shapes of lath and bulk. With an increased WC proportion, the
quantity and size of the Al4 W compound increased, and the morphology of the Al4 W transited from
granular to lath and bulk. When the WC proportion was increased to 80 wt.%, the maximum size of
the Al4 W compound could be up to 60 µm.
With the increase of WC proportion in the pre-coated powders, the microhardness and wear
resistance of the cladding layer all increased at first and then decreased slightly. When the WC proportion
was 60 wt.%, the microhardness and wear resistance reached their maximum. The maximum average
microhardness of the cladding layer was 122 HV0.3 , which was 4.5 times that of the pure aluminum
substrate. The optimal wear resistance of the cladding layer was 2.5 times that of the substrate.
The wear scar of high wear resistance specimen was smoother and some bulk Al4 W compounds were
clearly observed on the wear surface.
The cladding layer on the aluminum substrate with a high wear resistance was successfully
prepared using the argon-shielded arc cladding process with 40 wt.% CuZn40 plus 60 wt.% WC mixed
powders. The present research results provide a new technology for aluminum surface strengthening,
which would help to promote the wider application of aluminum in engine piston-cylinder parts, the
drill pipe of a pumping unit, armature-guide rail parts of electromagnetic railgun launch, and other
industrial fields, because of its high quality, low cost, and high efficiency.

Author Contributions: Writing, Investigation, and Funding Acquisition: X.Z.; Validation and Investigation: Q.S.;
Conceptualization, Methodology and Supervision: Z.R.; Formal Analysis: G.L.
Funding: This research was funded by the Jilin Scientific and Technological Development Program
(No. 20160520055JH).
Acknowledgments: The work was supported by the program for the JLU Science and Technology Innovative
Research Team (JLUSTIRT) and Key laboratory of Automobile Materials of Ministry of Education (Jilin University).
Conflicts of Interest: The authors declare no conflict of interest.

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