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Surface & Coatings Technology 202 (2008) 2885 – 2890

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Microstructure and corrosion properties of plasma-sprayed NiCr–Cr3C2

coatings comparison with different post treatment
Guozhi Xie a,⁎, Yijun Lu a , Ziyi He b , Bing Hu b , Keyu Wang c ,
Xiangyin Mo c , Yuping Wu a , Pinghua Lin a
a
College of Materials Science and Engineering, Hohai University, Nanjing 210098, PR China
b
Analysis and Testing Center, Life Sciences, Nanjing Agricultural University, Nanjing 210095, PR China
c
Analysis and Testing Center, Nanjing Normal University, Nanjing 210097, PR China
Received 13 June 2007; accepted in revised form 22 October 2007
Available online 30 October 2007

Abstract

The effects of laser and plasma arc remelting on the microstructure and properties of plasma-sprayed NiCr–Cr3C2 coatings on steel substrates
have been investigated. The microstructure of the coatings has been analyzed by X-ray diffraction (XRD) and scanning electron microscope (SEM). It
is found that the Cr3C2, δ-(Cr,Ni), Cr7C3 and Cr23C6 phases were obtained for both coatings, before and after remelting treatment. The laser remelting
was operated in a continuous way with 800 W power in different scan speed, while the plasma arc remelting was operated with a plasma cladding
machine under different scan currents. However, the denser microstructure of both remelted coatings can be obtained, especially for the plasma arc
remelted coating. The Vickers microhardness measurement showed certain enhancement values for both remelted coatings. The corrosion behavior
was evaluated through salt spray corrosion (SSC) method. Energy-dispersive spectroscopy (EDS) showed that the chloride was produced during SSC
process. The higher corrosion resistance for plasma arc remelted coating may be due to the more compact microstructure, less porosity rate and tensile
residual stress. Compared with laser remelting method, plasma arc remelting is a cheap, convenient and effective remelting method.
© 2007 Elsevier B.V. All rights reserved.

PACS: 52.77.Fv; 52.50.Dg; 42.62.Cf; 81.65.Kn

Keywords: Plasma spray; NiCr–Cr3C2; Laser remelting; Plasma arc remelting; Salt spray

1. Introduction Furnace heat treatment is easy, but requires long annealing

Thermally-sprayed ceramic coatings possess high porosity in
their matrix. This imperfection can noticeably reduce the
corrosion resistance, since it provides channels of penetration
by which the aggressive media reaches the materials of the
substrate. Furthermore, poor inter-lamellar contact arising from
the porosity of sprayed coatings causes a reduction in the
hardness and bond strength of the coating [1,2]. Due to the above
reasons, much of the work to improve the properties of these
coatings has therefore been focused on post-deposition mod-
ification of the coatings: either sealing of the surface by means of
heat treatment, i.e. furnace or laser heat treatment [3–5], or by
infiltration of substances, such as gels, in the surface pores and
cracks to prevent their propagation [6].
⁎ Corresponding author. Tel.: +86 25 83787233; fax: +86 25 83787972.
E-mail address: guozhixie@yahoo.com.cn (G. Xie).
0257-8972/$ - see front matter © 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.surfcoat.2007.10.024
times, and can generate new phases in the materials, which can
lead to reduce mechanical properties [7]. Laser treatment may
induce a high number of microcracks that are generated by the
thermal stress induced by the rapid heating and cooling rates
[5]. Furthermore, the laser treatment is more expensive.
A plasma arc is a kind of constricted arc with high energy
density and an extremely high temperature. The temperature at
the exit of the plasma nozzle is over 10,000 °C. Plasma arc has
been widely used in traditional metal processes, such as plasma
spray, plasma welding, plasma cutting, etc. Plasma arc processes,
as compared to laser processes, are easy to operate and to
generate a high-power plasma arc. The plasma arc equipment
costs less than the laser equipment does. Therefore, plasma arc is
often used as a heating source in the field of material research to
prepare new materials [8–10].
In the present investigation, two heating treatment methods,
laser and plasma arc, were used to heat plasma-sprayed NiCr–
2886 G. Xie et al. / Surface & Coatings Technology 202 (2008) 2885–2890
Cr3C2 coatings. The remelted coating's composition, micro-
structure, microhardness and salt spray corrosion (SSC)
properties were analyzed.
2. Experimental
To deposit the coating, a NiCr–Cr3C2 cermet feedstock was
used. This cermet is manufactured by PPPC and its composition
is (wt.%) 20% of Ni, 5% of Cr and 75% of Cr3C2, with a melting
point equal to 1400 °C.
A GB 45 steel (China) with the nominal composition of
0.43 wt.% C, 0.52 wt.% Mn, 0.22 wt.% Si, 0.01 wt.% P,
0.02 wt.% S and a balance of Fe was used as the substrate. The
substrate was shaped as rectangular specimens of dimension
60 × 30 × 6 mm. Prior to coating, the substrates were grit-blasted
on one side to clean and roughen the surfaces. The projection
was carried out with a TAFA-Paraxair 3710 equipment, with a
SG-100 gun, using Ar and He as fuel gases. A NiCoCrAlY
bond coat alloy was applied and then the ceramic coating was
sprayed on the surface of the bond coat. The layer of bond alloy
had an approximate thickness of 100 μm, while the layer of
ceramic had an approximate thickness of 350 μm. The spray
parameters were listed in Table 1.
Once the NiCr–Cr3C2 was deposited, the remelting was
carried out by using either a CO2 laser (PRC—2000, operating
in a continuous way) or a plasma cladding machine. The laser
remelting parameters were as the follows:
• spot diameter = 4 mm;
• power = 800 W;
• scanning speed = 1.2 m/min (LR1), 1.5 m/min (LR2) and
1.8 m/min (LR3);
• overlapping = 40%.
Argon gas was used in the process as the cooling and
shielding gas. The plasma remelting was carried out by using a
non-transferred arc plasma cladding machine (LHD-300 type,
Taian, China). The argon gas used in the process served as the
functions of both plasma gas and shielding gas. The specimens
were put under the plasma torch and the plasma jet uniformly
traversed above the as-sprayed coating. After the plasma arc
remelting, the specimen was directly cooled down at the room
temperature. The processing parameters for the plasma arc
remelting are given below:
• Plasma gas (Ar) flow rate: 1.0 m3/h;
• Plasma arc current: 50A (PR1), 60A (PR2) and 70A (PR3);
• Plasma gun velocity: 30 mm/min.
Table 1
Spray parameters for NiCr–Cr3C2
Feedstock Ar He Current Powder gas Powder feed Spray
(L/min) (L/min) (A) (L/min) speed distance
(RPM) (mm)
NiCr–Cr3C2 50 5 800 5 2 110
Table 2
Remelting methods and parameters for the sprayed coatings
Remelting method
Laser remelting LR1 LR2 LR3
1.2 m/min 1.5 m/min 1.8 m/min
Plasma arc remelting PR1 PR2 PR3
50A 60A 70A
Table 2 shows the remelting methods and the parameters
used for the sprayed coatings.
Microstructure of the coatings was observed using an optic
microscopy (OM, XJG—05) and a scanning electron micro-
scopy (SEM, HITACHI 3000 and JEOL JSM). Energy-
dispersive spectroscopy (EDS, HORRIBA 250) was used to
determine the composition distribution. Also X-ray diffraction
(XRD, Cu Kα radiation, i.e. 1.54 Å wavelength) was used to
detect the phases for both powder and coatings. Porosity (% area)
was determined from micrographs with the aid of an image
analyzer (CIMAS 2.0). Microhardness measurements were
performed on the mounted samples by using a conventional
Vickers microhardness tester (HXD-1000TC) with a 200-g
load. The measurements were made in the middle part of the
coating cross-section. The value presented is the average of 10
or 15 measurements after the highest and lowest values were
discarded.
The China GB/T 10125-1997 salt spray test was used to
evaluate the corrosion properties of the coatings. The salt spray
test is an accelerated corrosion test by which samples exposed to
the same condition can be compared with each other. Hence it
can be used to rank the relative corrosion resistance. In the
corrosion test, the samples were exposed to a salt fog generated
from a 5 wt.% NaCl solution with a PH between 6.5 and 7.2.
The temperature in the chamber was held at 35 °C. The uncoated
edges were protected with epoxy resin. No coating/substrate
combination placed in the salt fog chamber was removed until the
corrosion blister or stripe appeared at least once. The weight
loss was measured by weighing the specimen before and after
the salt spray corrosion using an electron balance with a
Fig. 1. X-ray spectrum for NiCr–Cr3C2 powder, as-sprayed coating and plasma
remelting coating (PR3) and laser remelting coating (LR3).
 G. Xie et al. / Surface & Coatings Technology 202 (2008) 2885–2890 2887

Fig. 2. Cross-sectional SEM image of the (a) as-sprayed; (b) laser remelting (LR2); (c) laser remelting (LR3) and (d) plasma remelting (PR1) coating.

sensitivity of 10− 4 g. The weight loss was divided by the weight
of corrosion consumed and was defined as the cumulative weight
loss (g/m2).
3. Results and discussion
Fig. 1 shows the X-ray diffractograms for the NiCr–Cr3C2
powder, as-sprayed coating, LR3 and PR3. It can be seen that no
peaks corresponding to metallic oxides were detected in any
samples, probably due to the lower content of metallic oxides. The
detected phases were Cr3C2, Cr7C3,Cr23C6 and δ-[Cr,Ni] phases.
Compared with the as-sprayed coating, the intensity of some X-
ray diffraction peak for the remelting coating seems decreased,
while the phases can still be observed in all coatings. The result
shows that the heat treatment caused no change in the phases
present in the coating, similar as reported by Guy Antou [11].
Fig. 2 shows the backscattered images of the cross-section of
the as-sprayed coating, LR2, LR3 and PR1. It can be seen there
are many unmelted particles, large voids and gaps between the
splats in the as-sprayed coatings, as shown in Fig. 2(a). After
remelting, the inter-particle porosity has been reduced through
remelting in Fig. 2(b) and (c). The porosity of the as-sprayed

Fig. 4. Cumulative weight loss versus corrosion time in salt spray test for
Fig. 3. Microhardness vs. depth. coatings with or without remelting.
2888 G. Xie et al. / Surface & Coatings Technology 202 (2008) 2885–2890

coating was about 12.3%, while that of the laser and plasma
remelted coating are 9.3% and 7.1%, respectively. It showed
that the heat treatment transformed the previously porous as-
sprayed coatings into a composite material with a denser matrix.
However, the coatings (LR2, as see Fig. 2(c)) showed the
typical under-remelted (partially remelting) coating with large
unclosed inter-particle void. It is easily observed that the over-
remelted (entirely remelting) coatings, which was shown in
Fig. 2(d), exhibit a very good integrity state in coating with the
porosity of 5.2%. It is easily deduced that the properly remelting
parameter is an important factor for the heat as-sprayed coating.
However, from Fig. 2(b) and (d), it can be seen that the more
compact and less voids coatings were obtained for the plasma
remelted coatings.
In Fig. 3 the average values of the microhardness are
represented in relation to the distance from the interface (0
represent interfaces), for the laser and plasma remelted coatings.
It can be seen that the microhardness value of the remelted
coatings, either laser or plasma remelted coating, is higher than
that of as-sprayed coatings. This was attributed to a decrease in
the void content of the coating. However, the measured
hardness is known to be a function of the stress state of the
material being indented [12], the increase in hardness of the
remelted coatings may also be due to a reduction in the tensile
residual stress of the coatings. The mocrohardness value is
nearly the same for both remelted coatings. On the other hand,
the microhardness value of the plasma heating substrates is
obviously higher than that of laser remelting coatings. The

Fig. 5. SEM image of the coatings following salt spray test for 200 h: as-sprayed coating before (a), and after salt spray test (b); laser remelting coating (LR3) before (c),
and after salt spray test for (d); plasma remelting coating (PR1) before (e), and after salt spray test (f).
 G. Xie et al. / Surface & Coatings Technology 202 (2008) 2885–2890
Fig. 6. SEM image of the coatings for salt spray test (a) as-sprayed; (b) laser
remelted coating; (c) plasma remelted coating.
result can be attributed to the heating treatment effect and the
toughness distortion during the remelting process, such as heat-
affected zone (HAZ) [13]. The higher temperature and heating
zone obtained for plasma remelting may bring out the higher
heating process effect, so the higher microhardness value of
substrate the was obtained for the plasma remelting coatings.
Fig. 4 shows the corrosion weight loss as a function of
corrosion time for salt spray test in 5 wt.% NaCl solution. The
highest corrosion weight loss was obtained in the as-sprayed
coating, whereas the plasma remelted coating exhibited the
lowest rate. The weight loss for the laser remelted coating was
between the as-sprayed and the plasma remelted coatings. The
reason for the highest corrosion resistance of the plasma
remelted coating may be due to the more compact structure as
showed in Fig. 2(d).
2889
Fig. 5(a) shows a typical microstructure of the as-sprayed
coating. Individual splat were apparent in this figure, with some
appearing much darker than the others. It can be seen that the
formation of cracks in the laser remelting coatings due to
anisotropic thermal expansion mismatch combined with low
toughness, shown in Fig. 5(c). It can also be seen that the cracks
formed after laser treatment were large than those in the as-
sprayed coating. However, as seen in Fig. 5(e), the characteristic
of the columnar grains was observed in the plasma arc remelting
coating. The formation of this columnar dendritic structure was
promising as the thermal mechanical properties of the glaze are
concerned [10]. In addition, fine carbides were formed and lead
to a certain increase in microhardness, which is consist with
Fig. 3.
Corrosion product were dielectric, and the white zones in
Fig. 5(b),(d),(f) were the zones where corrosion occurred.
Corrosion attack could be clearly seen on both the coatings. It
was clear that corrosion products were present around the
defects such as pores, crack and inclusions, and this showed that
the corrosion was initiated from these spots. In order to give
more details about corrosion characteristics of the coatings, the
highly magnified rate image (SEM backscattering mode) of the
coatings with 120 h corrosion test were given in Fig. 6. From the
Fig. 6(a), it can be seen that the more rust corrosion products
were obtained for as-sprayed coating, according well with the
high porosity rate and crack, which is showed in Fig. 2(a). Fig. 6
(b) showed that the less rust corrosion products were obtained
for the laser remelted coating. It was noted that the corrosion
products were present around the crack. The least corrosion
products were observed for the plasma remelted coating, shown
in Fig. 6(c). It is noted that the more compact structure with
less crack and porosity may be due to the higher corrosion
resistance.
The EDS of the corrosion product for the as-sprayed coating,
as shown in Fig. 5(b), showed 6.76 wt.% Fe, 6.07 wt.% Cl,
21.76 wt.% O, 25.6 wt.% C, 13.64 wt.% Ni, 13.64 wt.% Na,
14.04 wt.% Cr and less than 1 wt.% impurity. It is revealed that
the corrosion product should consist of chloride and oxide of
iron.
4. Conclusion
The properties of NiCr–Cr3C2 coatings on steel substrates
have been investigated by the remelting methods. The
microstructure of the coatings has been analyzed. The
microstructure was found consist of Cr3C2, δ-(Cr,Ni), Cr7C3
and Cr23C6 phases and there are nearly no change for the phases
after the laser and plasma remelting. The Vickers microhardness
measurement shows certain enhancement for both of the
remelted coatings. The more compact and structure of coating
could be obtained from the plasma arc remelting methods,
which is the reason for the plasma arc remelting coating to have
the highest corrosion resistance during the salt spray corrosion
(SSC). The corrosion product consists of the chloride and oxide
of iron. Compared with the laser remelting method, the plasma
arc remelting is a cheap, convenient and effective remelting
method.
2890 G. Xie et al. / Surface & Coatings Technology 202 (2008) 2885–2890
Acknowledgments
This work is supported by Cyanine Project of Jiangsu
Province (2006), Postdoctoral Support Program in Scientific
Research of Jiangsu Province, No. 0204003425 and Natural
Science Foundation of Jiangsu Province, No. BK2007180.
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