Journal of Materials Processing Technology 231 (2016) 89–99

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Journal of Materials Processing Technology

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

Effect of carbide dissolution on the corrosion performance of tungsten

carbide reinforced Inconel 625 wire laser coating
T.E. Abioye a,c , P.K. Farayibi a,c , D.G. McCartney b , A.T. Clare a,∗
a
Division of Manufacturing, Faculty of Engineering, University of Nottingham, Nottingham NG7 2RD, UK
b
Division of Materials, Mechanics and Structures, Faculty of Engineering, University of Nottingham, Nottingham NG7 2RD, UK
c
The Federal University of Technology, PMB 704, Akure, Ondo State, Nigeria

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

Article history: In this work, clad layers of Spherotene (a mixed tungsten carbide)/Inconel 625 wire composite suit-
Received 8 May 2015 able for hardfacing in corrosive environments were deposited. Varying laser processing conditions were
Received in revised form employed specifically to investigate carbide dissolution. The relative amount of Spherotene dissolution
15 December 2015
in each clad layer was analysed using a combination of methods including mass gain of clad layers, quan-
Accepted 23 December 2015
Available online 29 December 2015
titative microscopic and microchemical analysis of microstructures using scanning electron microscopy
(with energy dispersive X-ray analysis) and image processing software. The electrochemical corrosion
performance of two typical composite clad layers formed at low and high Spherotene dissolution lev-
Keyword:
Laser cladding els and Inconel 625 wire laser clad were investigated in de-aerated 3.5 wt.% NaCl solution. The results
Tungsten carbide indicate that microstructural in-homogeneity, caused by the formation of secondary phases, increases
Inconel 625 wire as the Spherotene dissolution increases. The Spherotene dissolution increases as the energy per unit
Corrosion length of clad increases. The composite clad layers demonstrate decreasing resistance to corrosion as the
Dissolution Spherotene dissolution increases. Through careful control of process parameters, the corrosion perfor-
Microstructure mance of composite clad layers can be improved by reducing the amount of tungsten carbide dissolution.
© 2016 Published by Elsevier B.V.

1. Introduction thermally sprayed WC/Ni-base alloy MMC coatings have been

Tungsten carbide/Ni-base alloy metal matrix composite (MMC)
coatings are currently being utilised in extending the life span
of engineering components in harsh environments (Katsich and
Badisch, 2011). According to Reyes and Neville (2003), these coat-
ings have, for example, found applications in crude oil exploration
where cost effective protection of high value down-hole drilling
tools against wear and corrosion damage is required. The most
commonly used among the Ni-based alloy for this application is
Inconel 625 which exhibits high toughness and excellent corrosion
resistance to oxidation and corrosive attack, as established by Al-
Fadhli et al. (2006). Compared to other carbides such as SiC and TiC,
tungsten carbide (WC) combines favourable properties such as high
hardness, low thermal expansion coefficient and good wettability
with molten Ni alloys (Abioye et al., 2013).
Currently, the most commonly used processing techniques for
making MMC coatings for off-shore applications are thermal spray-
ing and laser cladding. The characteristics and performance of
∗ Corresponding author. Fax: +44 0 115 951 3800.
E-mail address: adam.clare@nottingham.ac.uk (A.T. Clare).
investigated by several authors. Liu et al. (2007) revealed that
thermally sprayed coatings are limited in very demanding envi-
ronments. For example, Vespa et al. (2012), has identified the
decarburization of WC during spraying to form the brittle and less
wear resistant (W2 C) phase as a drawback of thermal spraying tech-
nique. Also, Guilemany et al. (1995) reported that thermal sprayed
coatings (including HVOF) are characterised by pores, intercon-
nected splat structures and a relatively weak (mechanical) bonding
at the coating–substrate interface. Morphology and characteriza-
tion of laser clad composite NiCrBSi–WC coatings has been a subject
of investigation by Tobar et al. (2006). It was established that the
aforementioned defects can be eliminated using laser cladding.
However, tungsten carbide dissolution remains a major challenge
limiting the optimal performance of the WC/Ni base alloy coatings
in wear and corrosive environments.
In the past, extensive work has been done on the abrasive wear
performance of tungsten carbide/Ni base alloy MMC coatings. For
example, Huang et al. (2004) revealed that the abrasive wear rate
of WC/Ni base alloy laser clad layers increases as the amount of
retained WC particle in the coating decreases. Also, Leech et al.
(2012) reported that a high content of uniformly distributed tung-
sten carbides in a WC–Ni based metal matrix composite has been

http://dx.doi.org/10.1016/j.jmatprotec.2015.12.023
0924-0136/© 2016 Published by Elsevier B.V.
90 T.E. Abioye et al. / Journal of Materials Processing Technology 231 (2016) 89–99
shown to give a very high resistance to wear in pure abrasion. This
was explained by the fact that the matrix binder mean free path (i.e.
average distance in-between the reinforcing particles in the MMC
coatings) becomes larger as the amount of retained WC particle in
the MMC coating reduces. When the mean free path is large, there is
more penetration of the abrasives which results in increased degra-
dation of the soft matrix binder. Also, there is increased pull-out
of the un-dissolved reinforcing particles during abrasion through
ploughing. However, if the mean free path is shorter, the penetra-
tion of the abrasives will be hindered thus reducing the abrasive
effect on the softer matrix. It has been established by Guo et al.
(2012) that the wear and hardness of WC–Ni coatings increased
because of the increased dissolution of carbon into the matrix.
The corrosion behaviour of the tungsten carbide/Ni base alloy
composite coatings has not been well researched. Also, the corro-
sion performance of tungsten carbide/Inconel 625 composite laser
clad layers for offshore applications has not been well investigated.
Previous work showed that the composite coatings compared
to the Inconel 625 coatings showed lower resistance to corro-
sion. For example, seawater corrosion performance of Inconel 625
alloy and WC/Inconel 625 alloy composite laser coatings has been
studied by Cooper et al. (1996). Also, Liu et al. (2007) investi-
gated the electrochemical corrosion performance of diode laser
treated HVOF-sprayed Inconel 625 and WC–Inconel 625 coatings.
In both research works, a wide performance gap in corrosion resis-
tance was observed as the MMC coatings demonstrated lower
corrosion resistance. The reason is due to WC dissolution which
usually results in some degree of microstructural modification
and compositional in-homogeneity. Most often, the precipitation
of secondary carbides (or compounds) including Fe3 W3 C, Cr23 C6 ,
Ni2 W4 C, Mo3 W3 C, etc. are found in the MMC coatings (Liyanage
et al., 2012). Due to the fact that such carbides and the metal-
lic matrix are of different electrochemical-potentials, complex
galvanic couplings are formed. The galvanic couplings are often
formed (1) between the secondary carbides (i.e. secondary com-
pounds) and (2) between each of the carbides and the Ni alloy
matrix regions surrounding them. Consequently, MMC coatings are
more severely attacked than the Ni base alloy coatings because
of the tungsten carbide dissolution. However, it has not been
established the extent to which reducing the WC dissolution will
improve the corrosion performance of tungsten carbide reinforced
Ni base alloy MMC coatings.
In this study, Spherotene reinforced Inconel 625 composite coat-
ings were deposited at varying processing parameters with the
specific aim of controlling the Spherotene dissolution. Thereafter,
the effect of reducing Spherotene dissolution on the corrosion
performance of the MMC coating was investigated. In this work,
Inconel 625 was fed in wire form as it gives an improved process
economy over powdered feedstocks. Also, Spherotene is a special
spherical cast tungsten carbide and it was used as the reinforce-
ment because of its extremely high hardness and high density
(16300 kg m−3 ). Concurrent wire and powder feeding system was
used in this work because it allows for the variation of the compo-
sition of the deposits in process. This cannot be achieved with the
pre-mixed powder feeding system.
2. Experimental procedure
2.1. Materials
The chemical composition, as defined by the manufacturers, of
the substrate (304 stainless steel) and Inconel 625 wire (Ø 1.2 mm)
are given in Table 1. The mass density of the wire, as specified
by the manufacturer, is 8.44 × 10−3 g mm−3 . The substrate and
the feed wire were respectively supplied by Smith Metal Centre,
Nottingham and VBC group, Loughborough, UK. The dimension of
the substrate is 100 mm × 80 mm × 6 mm.
The Spherotene (WC/W2 C) was made by Technogenia, France
and supplied by laser cladding Technology (LCT), Sheffield, UK. The
powder is nearly spherical as shown in Fig. 1a and the mass density,
as stated in the material safety data sheet, is 16.3 × 10−3 g mm−3 .
It is produced using a patented process called cold crucible induc-
tion fusion system. As determined using Malvern Masterizer-S, the
powder size ranged between 40 and 160 ␮m with a mean size of
124 ␮m. Results from the XRD analysis revealed that the powder
comprises WC and W2 C phases. Back scattered electron (BSE) image
of the powder cross sections, as shown in Fig. 1b and c, revealed its
main microstructural feature termed by the manufacturer, as ‘tan-
gled needles’. The composition of the powder, as obtained by energy
dispersive X-ray (EDX) analysis, analysis showed 92.9 wt.% W and
7.1 wt.% C.
2.2. Laser processing
Fig. 2 shows the concurrent wire and powder laser deposi-
tion system used in this work. A 2 kW ytterbium doped fibre laser
(IPG Photonics) operating at 1070 nm wavelength was used for the
cladding process. Cladding was performed using a beam diameter
of ∼3.1 mm at a distance 20 mm beyond the focal plane. This gave
a working distance of 212 mm.
The wire was “front fed” (ahead of the laser) at an angle of
42◦ ± 1 to the horizontal so as to aim the wire tip at the centre
of the meltpool. A WF200DC wire feeder (Redman Controls and
Electronic Ltd.) was used. Spherotene powder was simultaneously
back-fed into the meltpool by argon gas flowing at 10 l min−1 . A
Praxair (model 1264) powder feeder was used. The powder noz-
zle was set to an angle of 67◦ to the horizontal in an attempt
to improve the Spherotene deposition rate. Single clad layers of
Spherotene/Inconel 625 wire composite were deposited at varying
processing parameters giving different energy levels. The param-
eters were selected from the processing conditions found suitable
for concurrent laser cladding of Spherotene/Inconel 625 wire, as
detailed in the previous work by Abioye et al. (2013). The selected
processing conditions are presented in Table 2. In order to effec-
tively study the amount of the secondary carbide formation due to
Spherotene dissolution in the clad layers at different energy levels
(i.e. energy per unit length of clad, (60P/V)), material deposition rate
(i.e. WFR and PFR) was kept constant throughout this experiment.
Overlapped-clad layers consisting of at least five single parallel
clad layers were deposited at the varying cladding conditions. 60%
overlapping ratio was used. The clad layers were deposited in a uni-
lateral direction and a minimum of 30 s cooling time was allowed
between successive single clad depositions. The entire laser pro-
cessing was performed inside a transparent enclosure which was
filled with high purity argon gas. The gas was supplied at 25 l min−1 .
2.3. Macrostructural analysis
The term ‘dissolution ratio’ in this study indicates the relative
amount of Spherotene dissolution in the composite clad layers.
The procedure for determining the dissolution ratio is detailed as
follows.
2.3.1. Mass of Spherotene captured in the meltpool (MPC )
It was assumed that the volume change during solidification
process is negligible. A single clad layer (80 mm long) of Inconel
625 wire was first deposited and its mass is given as Mwire . Also, a
single clad layer (80 mm long) of Spherotene/Inconel 625 wire com-
posite was deposited and its mass is given as Mcomp . The substrate
dimension for the two depositions is the same. The processing con-
dition is the same except for the concurrent injection of Spherotene
 T.E. Abioye et al. / Journal of Materials Processing Technology 231 (2016) 89–99 91

Table 1
Chemical compositions of Inconel 625 wire and 304 stainless steel in wt.%.

Element Ni Cr Mn Si Al Ti Fe C Mo Nb P S

Inconel 625 Bal 22.46 – – 0.26 0.26 0.14 0.02 8.84 3.46 – –
304 stainless steel 7.86 18.58 1.78 0.42 – – Bal 0.08 – – 0.10 0.03

Fig. 1. SEM/BSE images showing the (a) spherical shape and (b and c) cross-section of the of the spherical cast Spherotene (WC/W2 C) powder as supplied by Technogenia,
France.

Fig. 2. Experimental set-up for concurrent laser cladding of Spherotene/Inconel 625 wire composite.

Table 2
Processing parameters.

A B C D E = 60P/V
Laser power (P) Traverse speed Wire feed rate Powder feed Energy per unit
(kW) (V) (mm min−1 ) (WFR) rate (PFR) length of clad
(mm min−1 ) (g min−1 ) (E) (J mm−1 )

1.8 100 600 25 1080

1.6 100 600 25 960
1.4 100 600 25 840
1.2 100 600 25 720
1.2 200 600 25 360
1.2 300 600 25 240

at PFR of 25 g min−1 . The mass of Spherotene captured (MPC ) in the 625 wire (Vwire ) deposited was found by multiplying the mass
composite clad was determined using Eq. (1). This was repeated for of the wire deposited (Mwire ) by the density of Inconel 625
all the processing conditions used in this study. This is important (8.44 × 10−3 g mm−3 ). The volume fraction of Spherotene captured
because powder capture is not 100% efficient. (VFPC ) in the meltpool was determined using Eq. (2).

MPC = Mcomp − Mwire (1) VPC

2.3.2. Volume fraction of Spherotene captured (VFPC ) and
retained (VFPR )
The volume fraction of Spherotene captured is defined as the
percentage fraction of the volume of the Spherotene captured to
the total volume of the composite clad layer. First, the volume
of Spherotene captured (VPC ) was determined by multiplying the
mass of the Spherotene captured (MPC ) by the Spherotene den-
sity (16.3 × 10−3 g mm−3 ). Likewise, the volume of the Inconel
VFPC = × 100 (2)
VPC + Vwire
The volume fraction of Spherotene retained in the composite
clad (VFPR ) was determined using image analysis of the micro-
graphs taken by SEM as detailed in the prior work by Abioye et al.
(2013). The image processing analysis was carried out on three
samples cut from the middle of each deposited clad. The average of
the three values is taken as the volume fraction of the Spherotene
retained in the composite clad.
92 T.E. Abioye et al. / Journal of Materials Processing Technology 231 (2016) 89–99
2.3.3. Dissolution ratio (Dratio )
The difference between the volume fractions of the Spherotene
captured (VFPC ) and Spherotene retained (VFPR ) is considered to be
the volume fraction of the Spherotene dissolved in the composite
clad.
VFPC − VFPR
Dratio = × 100
VPC
The ratio of this difference to the volume fraction of the
Spherotene captured is termed as dissolution ratio, as illustrated
in Eq. (3).
2.4. Microstructural characterisation
In order to determine the effect Spherotene dissolution on the
chemical composition of the clad layers, chemical microanalysis
was done. First, clad layers were cross-sectioned around the mid-
length. Then, the cut samples were ground and polished to 1 ␮m
diamond paste finish. The elemental composition of the secondary
phases, Ni matrix and different regions within the cross-sectioned
surface of the clad samples were determined using scanning elec-
tron microscope (SEM; FEI XL30) in combination with energy
dispersive X-ray (EDX).
2.5. Corrosion testing
The corrosion behaviour of two typical clad layers having low
and high dissolution ratios were investigated using potentiody-
namic polarisation testing. The tests were carried out according to
the guidelines stated in ASTM standards G5-94 and G61-86 respec-
tively. Approximately 10 × 10 mm2 surface area was prepared from
the overlapped laser clad layers of Spherotene/Inconel 625 wire
composite. The prepared clad was exposed to the saline media
(3.5 wt.% NaCl) at room temperature using a three electrode cell.
The electrolyte was de-aerated by nitrogen gas purging for a mini-
mum of 30 min prior to sample immersion in order to ensure that
the experiment was carried out in an oxygen free environment.
This continued for the duration of the experiment. Each sample
(i.e. working electrode) was allowed to settle for 60 min before
polarising the potential against Ag/AgCl electrode (the reference
electrode). A platinum plate was used as the counter electrode.
With the use of potentiostat (ACM instruments, Cumbria, UK),
potentiodynamic polarisation scans were performed for each of
the samples with a sweep rate of 20 mV min−1 from the 1 h open
circuit potential. Three samples from each of the clad layers were
prepared and tested. The potential was scanned over the range of
−200 mV to 1500 mV. The corresponding current flow between the
working and counter electrodes was recorded for each scan. The
exposed area of the sample, after each scan, was then determined
using image analysis software. For reference purpose, the corrosion
test was repeated for a typical Inconel 625 wire laser clad formed
at 1.8 kW laser power, 100 mm min−1 traverse speed and wire feed
rate of 600 mm min−1 .
3. Results and discussion
3.1. Spherotene (tungsten carbide) dissolution
The cross-sections of the clad layers showing strong fusion at
the clad-substrate interface and absence of cracks are presented in
Fig 3. In all the clad samples, Spherotene dissolution was observed
but at different degrees as the energy per unit length of clad varied,
for example, as shown in Fig. 4. This is consistent with a change
to the maximum temperature experienced by the clad, a change to
the degree of mixing and cooling rates. Most of the analysis in this
work considered two typical clad layers whose cross-sections are
shown in Fig. 4. They were deposited at high (1080 J mm−1 ) and low
(240 J mm−1 ) energy per unit length of track. The reason for their
selection is that clear differences in the extent of Spherotene dis-
solution and other microstructural features were noticed between
the two clad layers.
As seen in Figs. 3 and 4, the white contrast phase with near cir-
(3) cular shape marked as ‘A’ is the retained Spherotene. The number
density of the retained Spherotene in the clad layers is seen to vary
as the energy level changes, as shown in Fig. 3. This is probably due
to the (1) different amount of Spherotene captured in the clad melt-
pool and (2) extent of carbide dissolution as the cladding conditions
vary. The mass (i.e. amount) of Spherotene captured in the clad
layer as a function of the energy per unit length of clad was inves-
tigated using mass analysis (weighing) method as detailed earlier
in the experimental (see Section 2.3.1).
As shown in Fig. 5, the mass of Spherotene captured increases
as the energy per unit length of clad increases (60P/V). Previously,
Hofmeister et al. (2001) has established that the meltpool size
increases as the laser power (P) increases. This usually results in
increased powder catchment (deposition) efficiency. Also, decreas-
ing the traverse speed (V) increases the meltpool size and the
powder delivery volume per unit length of clad. Therefore, the
increase in the mass of Spherotene captured at higher energy per
unit length of clad is attributed to the roles played by the laser
power and traverse speed on powder deposition efficiency. The
combined effect of the laser power and traverse speed on the melt-
pool size is evidenced by the increase in the clad width as the energy
per unit length of clad increases. This is graphically presented in
Fig. 5.
A summary of the analysis of the Spherotene dissolution in the
composite clad layers is presented in Table 3. The results presented
in column B and C in Table 3 are averages of three measurements.
The term dissolution ratio gives the relative amount of Spherotene
dissolution in each of the clad layers. The dissolution ratio is the
volume fraction of Spherotene dissolved to the volume fraction of
Spherotene captured. The volume fraction of Spherotene dissolved
is the difference between the volume fractions of Spherotene cap-
tured and retained in the composite clad layers. The result of the
analysis revealed that the dissolution ratio increases as the energy
level increases indicating more Spherotene dissolution at higher
energy level. A value of 57% at 1080 J mm−1 and 5% at energy level
of 240 J mm−1 were found for the two selected clad layers.
It has been previously mentioned that the dissolution of
tungsten carbide (Spherotene) in Ni-alloy matrix results in the
formation of secondary phases (i.e. secondary compounds). These
usually appear distributed in the matrix as light contrast angu-
lar phases. Therefore, from a physical observation, the degree of
Spherotene dissolution can be measured by the amount of light
contrast angular phases around the boundary of the retained
Spherotene, as clearly revealed in the clad cross-sections in Fig 4. A
higher number density of these phases were observed in the clad
cross-section formed at 1080 J mm−1 compared to the clad layer
formed at 240 J mm−1 . This confirms the result of the previous anal-
ysis revealing that there is more Spherotene dissolution at higher
energy level. The reason for this is that a higher energy meltpool due
to the increased laser beam energy is produced at 1080 J mm−1 . This
is believed to have caused the Spherotene to suffer more intense
heating causing increased melting of the Spherotene. In addition,
the meltpool remains molten for longer period allowing more time
for Spherotene dissolution to take place.
3.2. Microstructural characterisation
Phase identification and composition of the Spherotene/Inconel
625 wire composite laser clad has been investigated in prior work
 T.E. Abioye et al. / Journal of Materials Processing Technology 231 (2016) 89–99 93

Fig. 3. SEM/BSE images showing the cross-sections of Spherotene/Inconel 625 wire composite deposited at varying laser parameters. Where the energy per unit length of
clad (J mm−1 ) = 60P/V. P = laser power (W) & V = traverse speed (mm min−1 ).

Fig. 4. SEM/BSE images of the cross-sectioned clad layer formed at (a) 1080 and (b) 240 J mm−1 showing the dissolution around the Spherotene boundary.

(Abioye et al., 2013). The clad was found to compose of Ni-matrix
(FCC), WC/W2 C (i.e. Spherotene), W2 C, Fe3 W3 C (M6 C) and Cr23 C6
(M23 C6 ), as shown in Fig. 6.
In this work, EDX analysis using area scan of 50 × 50 ␮m was
conducted randomly on the clad region away from the retained
Spherotene. This was done so as to determine the effect of the
Spherotene dissolution on the composition of the Ni-matrix as the
energy per unit length of clad changes. The results are presented in
Fig. 7. The clad region away from the retained Spherotene is increas-
ingly enriched in W and depleted of Cr as the energy per unit length
of clad increases.
Since the composition of the feed wire (Inconel 625) contains
no trace of W, the occurrence of W in the composition of the clad
region away from the retained Spherotene after cladding can then
be attributed to the dissolution of the Spherotene captured in the
meltpool. As shown in Fig. 7, increased W composition in the clad
94 T.E. Abioye et al. / Journal of Materials Processing Technology 231 (2016) 89–99

Fig. 5. Variation of the amount of Spherotene captured in the clad meltpool and clad width as a function of the energy per unit length of clad. PFR = 25 g min−1 ,
WFR = 600 mm min−1 .

Table 3
Analysis of the Spherotene dissolution in the composite clad layer as the energy per unit length of clad varies. (PFR = 25 g min−1 , WFR = 600 mm min−1 ).

A B C D = (B − C)/B
Energy per unit length Volume fraction of Volume fraction of Dissolution ratio (%)
of clad (J mm−1 ) Spherotene captured Spherotene retained
(%) (%)

1080 42.3 ± 2.6 18.2 ± 2.4 57.4

960 39.2 ± 1.6 20.8 ± 1.7 47.1
840 37.1 ± 2.2 23.3 ± 1.8 38.2
720 34.6 ± 0.8 27.8 ± 1.5 19.1
360 27.7 ± 2.6 25.2 ± 2.1 9.7
240 24.2 ± 4.5 23.1 ± 1.9 4.8

The volume fraction of Spherotene retained was measured using image processing software.

Fig. 6. BSE/SEM images showing the identified phases present in the cross-sections of the Spherotene/Inconel 625 composite clad layer formed at 1060 J mm−1 . (b) is a higher
magnification image of the box region shown in (a).

region at higher energy level indicates increased Spherotene dis-
solution as the energy per unit length of clad increases. This also
confirms the results of the analysis presented earlier in Table 3.
The increased dissolution is partly due to the higher Spherotene
powder catchment efficiency observed at higher energy per unit
length of clad. This is due to the fact that the meltpool size increases
as the energy level increases therefore, increasing the amount
of Spherotene particles captured. Since the Spherotene powder
catchment efficiency increased at higher energy per unit length of
clad, more melting of the powder is expected resulting in higher
dissolution ratio.
The Cr depletion in the clad region away from the retained
Spherotene as the energy per unit length of clad increases can be
explained by the fact that more carbon is released into the meltpool
as the Spherotene dissolution increases. During rapid solidification
of the meltpool, the released carbon from Spherotene dissolution is
 T.E. Abioye et al. / Journal of Materials Processing Technology 231 (2016) 89–99
Fig. 7. Cr and W compositions in the clad region away from the retained Spherotene as a function of energy per unit length of clad. PFR = 25 g min−1 , WFR = 600 mm min−1 .
believed to have combined with the Cr (due to strong Cr–C affinity)
resulting in the precipitation of Cr23 C6 phase at the grain bound-
aries of the Ni matrix. Also, Fe3 W3 C (M6 C) contains some traces of
Cr. Consequently, there is an increased Cr depletion in the Ni matrix
as the energy per unit length of clad increases. This is due to more
precipitation of Cr23 C6 and Fe3 W3 C as the amount of Spherotene
dissolution increases. The hardness values of the coatings have been
reported previously by the same author (Abioye et al., 2013). The
matrix hardness value ranged between 540–690 HV0.3 while the
retained Spherotene is between 2100 and 2400 HV0.3 .
3.3. Corrosion performance
Since Cr content of Inconel 625 is critical to its corrosion
performance, clad samples were subjected to potentiodynamic
polarisation testing. The test was conducted on two composite
coatings deposited at 240 and 1080 J mm−1 . The reason is that
the microstructures of the two clad layers are somewhat differ-
ent because of the varying amount of Spherotene dissolution in
them, as detailed in Table 3. Also, there is significant difference
in their Cr content, as presented in Fig. 7. For reference purpose,
similar test was performed for a laser clad Inconel 625 wire. Fig. 8
shows the potentiodynamic polarisation curves obtained for the
Spherotene/Inconel 625 wire composite laser coatings and Inconel
625 wire laser coating in de-aerated 3.5% NaCl solution at room
temperature. As shown in the Table 4, the corrosion attack on
Inconel 625 wire clad layer is the lowest. The polarisation curve for
Inconel 625 wire laser clad shows a transition from active to passive
to transpassive regions. Compared to the two Spherotene/Inconel
625 wire composite coatings, Inconel 625 wire coating exhib-
ited lower passive current density, higher corrosion potential and
higher breakdown potential which indicates greater resistance to
corrosion damage. For the Inconel 625 clad layer, the gradient of the
current density against potential is very low indicating the absence
of pit formation on the clad layer. The microstructural examina-
tion of the top surface of the Inconel 625 clad layer after corrosion
had been previously investigated by the same author (Abioye et al.,
2015). A uniform corrosion was observed throughout the surface.
The polarisation curves for the two composite coatings show
no significant evidence for passivation. However, a transition from
the active to transpassive region is noticed. This implies that
passive layer formation is unstable in the composite coatings
95
during the polarisation test. The absence of significant passivation
is possibly due to Spherotene dissolution during laser processing
which resulted in increased microstructural in-homogeneity. At
1080 J mm−1 , a significant increase in current density with a lit-
tle change in potential is observed in the transpassive region. This
indicates a possibility of pitting form of corrosion occurring. In the
case of the composite coating formed at 240 J mm−1 , the gradient
of the current density against potential reduced in the transpassive
region. Also, the corrosion potential value of the composite coat-
ing deposited at the low energy level (−295 mV) is higher than the
value obtained when the energy level was 1080 J mm−1 (−309 mV).
This indicates that the former is nobler than the latter.
Fig. 9d shows the top surface of the coating formed at
240 J mm−1 before and after the potentiodynamic polarisation scan
test. The Ni matrix region is observed to be covered by grey like
compound (marked as ‘A’) which is believed to be the corrosion
product. Conversely, the randomly precipitated secondary com-
pounds (marked ‘B’) showed no significant change in colour and
shape. Also, the result of EDX analysis (see Table 5) conducted on
the region marked ‘A’ and ‘B’ revealed that the phase marked ‘A’
is rich in O (22 wt.%) indicating that it is a product of oxidation
(corrosion). The other phase marked ‘B’ is composed of negligible
amount of O (1 wt.%) after polarisation test in de-aerated 3.5% NaCl.
This confirms that the secondary compounds suffered no significant
corrosion damage.
Previously, it has been discussed that the Spherotene dissolu-
tion in molten Inconel 625 alloy led to the precipitation of the
various secondary compounds including Fe3 W3 C (M6 C) and Cr23 C6
(M23 C6 ). Consequently, there was Cr depletion in the Ni-matrix.
Chromium, the main alloying elements in Inconel 625 alloy, is
added to promote resistance to corrosion. Its role is to passivate the
external surface of the alloy by forming passive layer (Cr2 O3 ) over
it. The corrosion attack on the Ni matrix is believed to be caused
by two things. First, the Cr depletion which reduces the corrosion
resistance of the matrix phase. Secondly, due to the differences
in the electrochemical potentials, galvanic couples are believed to
have been formed between the secondary compounds and the Cr
depleted regions of the matrix adjacent to them. Although there is
no data stating the positions of these compounds (i.e. secondary
carbides) including the Spherotene in the electrochemical series,
the Ni matrix (depleted of Cr) is believed to be the sacrificial
anode in the galvanic cell mechanism because it was preferentially
96 T.E. Abioye et al. / Journal of Materials Processing Technology 231 (2016) 89–99

Fig. 8. Polarisation curves of concurrently fed Spherotene/Inconel 625 wire composite laser coatings deposited at low and high values of specific energy and Inconel 625
wire laser coating.

Fig. 9. SEM/BSE images showing the top surface of Spherotene/Inconel 625 wire composite laser coating formed at 240 J mm−1 (a and b) before and (c and d) after the
potentiodynamic polarisation scan test in de-aerated 3.5 wt.% NaCl solution.

attacked whereas the secondary compounds showed no corrosion
damage.
Also, the faceted structure exhibited by the retained Spherotene
is an indication that it slightly suffered from corrosion damage.
This is probably due to the galvanic couple formation between
the partially dissolved Spherotene and the secondary compounds
at its interphase. In the past, corrosion of tungsten carbide par-
ticulate has been observed by Cooper et al. (1996) after six
month exposure of laser melted WC-Inconel 625 powder com-
posite laser coating to seawater. This type of corrosion was
considered as unusual. Generally, the corrosion damage on the
Ni matrix and retained Spherotene is similar to the findings of
 T.E. Abioye et al. / Journal of Materials Processing Technology 231 (2016) 89–99 97

Fig. 10. SEM/BSE images showing the top surface of Spherotene/Inconel 625 wire composite laser coating formed at 1060 J mm−1 (a and b) before and (c and d) after the
potentiodynamic polarisation scan test in de-aerated 3.5 wt.% NaCl solution.

Table 4
Summary of the results of the corrosion test for Spherotene/Inconel 625 wire composite laser coatings deposited at low and high energy levels and Inconel 625 wire laser
coating.

Laser coatings Energy level (J mm−1 ) Eoc on immersion (mV) Eoc after 1 h (mV) Ecorr (mV) Eb (mV) Ip (mA cm−2 )

Spherotene/Inconel 625 wire 1080 −278 ± 19 −297 ± 3 −309 ± 4 Not observed Not observed
Spherotene/Inconel 625 wire 240 −253 ± 10 −282 ± 5 −295 ± 5 Not observed Not observed
Inconel 625 wire 1080 −176 ± 4 −176 ± 2 −222 ± 8 3.0 × 10−4 585 ± 5

Eoc : open circuit potential; Ecorr : corrosion potential; Eb : breakdown potential; Ip : passive current density.

Table 5
Chemical composition of the phases marked as A and B in Fig. 9d.

Phase O Cr Fe Ni Nb Mo W

A 22 ± 4 11 ± 2 1 ± 0.3 9±2 4±1 4±1 50 ± 5

B 1 ± 0.1 8±1 0.1 ± 0.1 19 ± 2 2 ± 0.1 6±1 65 ± 4

Jones and Waag (2011) during the study of the influence of carbide
dissolution on the erosion-corrosion properties of cast tungsten
carbide/Ni-based PTAW overlays.
As shown in Fig. 10, a formation of pits around the retained
Spherotene particles was observed in the composite coating formed
at high energy level (1080 J mm−1 ) after the corrosion test. This
indicates an occurrence of localised (pitting) form of corrosion
suggesting that the composite coating suffered more damage com-
pared to the coating formed at the lower energy level. The possible
explanation for this severe damage is the extensive depletion of Cr
from Ni-matrix due to increased carbide dissolution, which is more
significant in the matrix region closer to the retained Spherotene.
This finding is in agreement with the findings of Cho et al., (2006)
and Zavareh et al. (2015). Although, in their works, the corrosion
performance of thermal sprayed (HVOF) Ni-based MMC coatings
was investigated electrochemically in salty solutions. The result
revealed that the higher the Cr content and the lower the amount of
pores formed in the coatings, the better the corrosion performance.
The cross-sections of the corroded composite coatings are
shown in Fig. 11. The corrosion damage in the two composite
coatings is limited to the top surface and there were no corrosion
products within the coating and at the coating-substrate interface.
This shows that the substrate is well protected from corrosion by
the laser clad layers of Spherotene–Inconel 625 wire composite.
4. Conclusion
• The fraction of Spherotene dissolved during laser processing was
found to increase with increasing laser energy per unit length
of clad. This is due to increased meltpool energy and higher
Spherotene deposition efficiency.
98 T.E. Abioye et al. / Journal of Materials Processing Technology 231 (2016) 89–99
Fig. 11. BSE/SEM images showing the cross-sections of the concurrently fed Spherotene/Inconel 625 wire composite laser coatings after the potentiodynamic polarisation
scan test in de-aerated 3.5 wt.% NaCl solution.
• The Spherotene dissolution resulted in the Cr depletion and
enrichment of W in the clad region away from the retained
Spherotene in the composite coating. These increases as the
energy per unit length of clad increases.
• The Spherotene/Inconel 625 wire composite laser coatings
exhibit lower corrosion resistance than Inconel 625 wire laser
coating and their corrosion resistance decreases as the propor-
tion of Spherotene that has dissolved during laser processing
increases.
• The study reveals that the corrosion mechanism in
Spherotene/Inconel 625 composite laser coatings is com-
plex. This is as a result of large amount of microstructural
modification and compositional in-homogeneity caused by the
Spherotene dissolution in the composite coating.
• The corrosion damage in the composite coating possibly results
from galvanic couples existing between (1) the precipitated sec-
ondary phases and the Cr depleted Ni-matrix, and (2) the retained
Spherotene and the secondary compounds precipitated at its
boundary.
References
Abioye, T.E., Clare, A.T., McCartney, D.G., 2015. Laser cladding of Inconel 625 wire
for corrosion protection. J. Mater. Process. Technol. 217, 232–240.
Abioye, T.E., Folkes, J., Clare, A.T., McCartney, D., 2013. Concurrent Inconel 625 wire
and WC powder laser cladding: process stability and microstructural
characterisation. J. Surf. Eng. 29 (9), 647–653.
Al-Fadhli, H.Y., Stokes, J., Hashmi, M.S.J., Yilbas, B.S., 2006. The erosion–corrosion
behaviour of high velocity oxy-fuel (HVOF) thermally sprayed Inconel-625
coatings on different metallic surfaces. Surf. Coat. Technol. 200 (20–21),
5782–5788.
Cho, J.E., Hwang, S.Y., Kim, K.Y., 2006. Corrosion behaviour of thermal sprayed WC
cermet coatings having various metallic binders in strong acidic environment.
Surf. Coat. Technol. 200 (8), 2653–2662.
Cooper, K.P., Slebodnick, P., Thomas, E.D., 1996. Seawater corrosion behavior of
laser surface modified Inconel 625 alloy. Mater. Sci. Eng. A 206 (1), 138–149.
Guilemany, J.M., Nutting, J., Miguel, J.R., Dong, Z., 1995. Microstructure
characterization of WC-Ni coatings obtained by HVOF thermal spraying. Scr.
Metall. Mater. 33 (1), 55–61.
Hofmeister, W., Griffith, M., Ensz, M., Smugeresky, J., 2001. Solidification in direct
metal deposition by LENS processing. JOM 53 (9), 30–34.
Huang, S.W., Samandi, M., Brandt, M., 2004. Abrasive wear performance and
microstructure of laser clad WC/Ni layers. Wear 256 (11–12), 1095–1105.
Jones, M., Waag, U., 2011. The influence of carbide dissolution on the
erosion–corrosion properties of cast tungsten carbide/Ni-based PTAW
overlays. Wear 271 (9–10), 1314–1324.
Katsich, C., Badisch, E., 2011. Effect of carbide degradation in a Ni-based hardfacing
under abrasive and combined impact/abrasive conditions. Surf. Coat. Technol.
206, 1062–1068.
Leech, P.W., Li, X.S., Alam, N., 2012. Comparison of abrasive wear of a complex high
alloy hardfacing deposit and WC–Ni based metal matrix composite. Wear
294–295, 380–386.
Liu, Z., Cabrero, J., Niang, S., Al-Taha, Z., 2007. Improving corrosion and wear
performance of HVOF-sprayed Inconel 625 and WC–Inconel 625 coatings by
high power diode laser treatments. Surf. Coat. Technol. 201 (16–17),
7149–7158.
Liyanage, T., Fisher, G., Gerlich, A.P., 2012. Microstructures and abrasive wear
performance of PTAW deposited Ni–WC overlays using different Ni-alloy
chemistries. Wear 274–275 (0), 345–354.
Reyes, M., Neville, A., 2003. Degradation mechanisms of Co-based alloy and WC
metal–matrix composites for drilling tools offshore. Wear 255 (7–12),
1143–1156.
 T.E. Abioye et al. / Journal of Materials Processing Technology 231 (2016) 89–99 99

Tobar, M.J., Álvarez, C., Amado, J.M., Rodríguez, G., Yáñez, A., 2006. Morphology and
characterization of laser clad composite NiCrBSi–WC coatings on stainless
steel. Surf. Coat. Technol. 200 (22–23), 6313–6317.
Vespa, P., Pinard, P.T., Gauvin, R., Brochu, M., 2012. Analysis of WC/Ni-based
coatings deposited by controlled short-circuit MIG welding. J. Mater. Eng.
Perform. 21 (6), 865–876.
Zavareh, M.A., Sarhan, A.A.D.M., Zavareh, P.A., Basirun, W., 2015. Electrochemical
corrosion behaviour of carbon steel pipes coated with a protective ceramic
layer using plasma and HVOF thermal spray techniques for oil and gas. Ceram.
Int., http://dx.doi.org/10.1016/j.ceramint.2015.10.134.