Surface & Coatings Technology 333 (2018) 104–114

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Surface & Coatings Technology

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

Underwater laser cladding in full wet surroundings for fabrication of nickel MARK
aluminum bronze coatings
Xiangru Fenga, Xiufang Cuia,⁎, Guo Jina,⁎, Wei Zhengb,⁎, Zhaobing Caia, Xin Wena, Bingwen Lua,
Jianming Liua
a
Institute of Surface/Interface Science and Technology, Key Laboratory of Superlight Material and Surface Technology of Ministry of Education, College of Material
Science and Chemical Engineering, Harbin Engineering University, Harbin 150001, China
b
College of Material Science and Chemical Engineering, Harbin Engineering University, Harbin 150001, China

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

Keywords: Underwater laser repairing technology as a new type of on-line maintenance technology will promote the de-
Underwater velopment of oceanographic engineering. However, there are many difficulties during the process of underwater
Laser cladding laser repairing. In this paper, underwater laser cladding process in full wet surroundings (or WULC, for short) for
Coatings fabrication of nickel aluminum bronze (or NAB, for short) has been reported, and laser cladding process in the air
Bronze
for fabricating NAB coatings was used for comparative study. The homemade protective covering was used to
Maintenance
solve the problems of underwater laser repairing. For comprehending the effect of full wet surroundings and
protective covering on microstructure and electrochemical performance of the NAB coatings, a series of char-
acterization tests including SEM, EDS, XRD and TEM and a series of electrochemical measurements were carried
out. The alloy coatings fabricated by WULC possess good formability through optimizing the processing para-
meters. The elements distribution of the coatings shows different patterns compared to conventional cast copper
alloy and NAB coating fabricated by laser cladding in the air. In addition, the ordered solid solution and twinning
structure have been observed in the WULC-NAB coatings. These unique microstructures and elements dis-
tribution patterns caused the better electrochemical performance of NAB coating fabricated by WULC. These
findings suggest that the idea of using a protective layer in underwater laser cladding in full wet surroundings is
feasible. The WULC process reported in this paper can provide some theoretical guidance for repairing damaged
parts in full wet surroundings.

1. Introduction
Underwater repair and maintenance techniques have been paid
extensive close attention recently for the reason of its convenience to
repair the damaged parts in underwater environments [1]. Among
those techniques, the underwater arc welding is the most extensively
studied and widely used in the repair and maintenance of marine
constructions [2]. However, underwater arc welding will become more
and more difficult with the increase of water depth [3]. To be more
specific, arc strike during wet-welding and establishment of pressure
chamber for dry-welding are difficult because of ultrahigh hydraulic
pressure. In recent years, underwater laser welding has become re-
search focus, and the most representative research achievement is local-
dry underwater laser cladding [4]. As well as the underwater arc
welding, constructing the local-dry pressure chamber during under-
water laser welding will become more and more difficult with in-
creasing the water depth. Using wet-underwater laser repair
techniques, by contrast, will not run into those problems. Recently,
Ning Guo et al. have studied the effect of water depth on weld quality
and welding process in underwater fiber laser welding. They pointed
out that water has a strong hindering effect on ULBW [5]. Assuredly,
underwater laser repair in full wet surroundings is a very complex
process, including the interactions of laser-water, laser-metal and
metal-water.
The interactions among laser, target metal and water must affect the
surface nature of the workpiece. When the laser irradiates on the metal
surface, the water close to the metal surface absorbs enormous amount
of heat, and cavitation generates immediately. Once generated, the
cavitation bubble grows to a maximum size and then implodes, because
of the pressure gradient between the outside and inside of the bubble.
In general, the cavitation bubble oscillates several times, emitting
acoustic transients upon each collapse, until the bubble totally dissolves
into the liquid. When the bubble collapses in the vicinity of a solid
boundary, high-speed liquid jet forms and flows towards the surface of

⁎
Corresponding authors.
E-mail addresses: cuixf721@163.com (X. Cui), jinjg721@163.com (G. Jin), zhengwei75@126.com (W. Zheng).

http://dx.doi.org/10.1016/j.surfcoat.2017.10.056
Received 17 July 2017; Received in revised form 16 October 2017; Accepted 19 October 2017
0257-8972/ © 2017 Elsevier B.V. All rights reserved.
X. Feng et al.
workpiece [6]. High-speed liquid jet will invade into the melting pool
during underwater laser processing. Then, the melting pool will solidify
quickly, and the water injected into melting pool will vaporize in-
stantaneously. This series of reactions can fill the surface of metal
workpiece with pores. Moreover, during the laser machining process, a
metal plasma plume is generated on the target metal surface, because of
the irradiation of high-energy laser [7]. The hot and dense plasma is
important for laser processing especially for laser cladding to carry out
successfully. In underwater environment (the water depth is over
8 mm), a kind of water vapor mixed with metal vapor plasma will be
formed when the high-energy laser irritate onto the surface of the target
metal. This plasma can attenuate the laser beam, and with the increase
of the water vapor content in this plasma the attenuation of the laser
beam will be seriously [8]. As a result, the absorbed laser energy by the
workpiece is reduced severely. In another hand, the cavitation may
affect the stability of the plasma, and then the stability of the beam
channel will be influenced. The stability of beam channel have an im-
portant influence on the weld bead quality and the welding process
stability [5]. In addition, the high-energy laser irritation can cause the
water decompose into oxygen and hydrogen. The oxygen and hydrogen
will influence the performance of the target metal [9]. In conclusion,
the water has a strong hindering effect on the process of underwater
laser processing. If we want to practice the underwater laser processing
successfully, those problems mentioned above should be dissolved ap-
propriate.
In this paper, the underwater laser cladding in full wet surroundings
has been reported, which is a comparatively new conception. In this
study, nickel aluminum bronze (NAB) was selected as the experimental
material of substrate and coatings. It should be noted that the protective
covering was used to ensure that the underwater laser cladding process
can be carried out successfully. NAB is a popular choice for industrial
applications [10] such as seawater lift pumps for the oil industry, hy-
draulic bushings for earth moving equipment, and hardware for the
marine industry, due to its good combination of mechanical and phy-
sical properties [11]. However, there is a close relationship between
properties of NAB and processing craft. For comprehending the effect of
full wet surroundings and protective covering on NAB coatings, a series
of characterization tests including SEM, EDS, XRD, TEM and electro-
chemical tests were carried out.
2. Experimental
In this study, preplaced layer of NAB powder and protective cov-
ering were used. The substrate material is as-cast NAB, and the com-
positions of as-cast NAB are listed in Table.1. The NAB powder was
mixed using elemental powders, and the composition of NAB powder
was designed as the same as as-cast NAB. The protective covering is
semi-volatile, and its compositions are shown in Table. 2. The function
of CaF2 is to remove the hydrogen produced by water decomposition.
Adding CaCO3 is to create the atmosphere for the formation of metal
plasma. Cu, Al, Fe, Ni, Mn and Cr are the supplementary elements,
meanwhile, they can also prevent oxygen from damaging the coating.
The function of TiO2 and Si are slagging. C6H7NO2 in the protective
covering acts as gas-forming constituents and binder. In this study, the
NAB powder and protective covering were preplaced in the air before
the process of WULC. The thickness of NAB powder is 1.5–1.8 mm, and
the thickness of protective covering is 0.5–0.8 mm.
NAB coatings were fabricated underwater by laser cladding system,
and the process of the underwater laser cladding in full wet
Table 1
Compositions of NAB.
Element Cu Al Fe Ni Mn C Cr The balance
Wt% 78.7 9.6 4.3 4.8 1.25 0.8 0.45 0.1
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Surface & Coatings Technology 333 (2018) 104–114
surroundings is shown in Fig.1 schematically. In addition, the video
which shows the process of WULC has been included in supplementary
data, and Fig.1 b was captured from the video. The laser system are
equipped with ytterbium laser device (IPG Photonics Corporation),
programmable manipulator (KUKA) and cladding head YC52 (Precitec).
In order to find the instructive maintenance methods for underwater
damaged parts, a series of parameters of the WULC process have been
studied in this paper. Those parameters are as follows: water depth,
power density, the application of protective covering and processing
craft. First of all, the effect of water depth on formability of NAB
coatings with protective covering and without protective covering in
full wet surroundings were studied. After this experiment, we can make
a progress on the water depth of underwater laser processing. In this
study, the water depth of underwater laser processing will get up to
10 mm.Then, single track NAB coatings were manufactured with dif-
ferent power density under the water depth of 10 mm for studying the
effect of power density on formability of NAB coatings. So far, the
optimal parameters for fabricating NAB single-track coatings under-
water in this paper were obtained. Then, multi-track NAB coatings with
different processing crafts were fabricated. The first processing method
is shown in Fig.2 a, and another method is shown in Fig.2 b schema-
tically. The method shown in Fig.2 a is a kind of continuous process,
and is called method A. NAB powder layer and protective covering were
preplaced on the whole surface of substrate NAB plate, and then, WULC
process was carried out underwater until multi-track NAB coating was
finished. Another method shown in Fig.2 b is not continuous, and is
called method B. The whole NAB coating was finished track by track. In
other words, when a single track of NAB coating was finished, laser
beam would be removed until the second preplaced layer was prepared.
This method is an imitation of the synchronous feeding system.
Through rational design, the synchronization of laying materials and
laser irradiation can be achieved, and the repair efficiency will be im-
proved for underwater laser processing in the future. In order to con-
trast, the NAB coatings were also fabricated in the air with the same
parameters as NAB coating fabricated by underwater laser cladding
except for the full wet environment.
After fabricating NAB coatings, the microstructure characterization
including SEM, EDS, XRD and TEM were carried out to understand the
process of WULC. Scanning electron microscopy (SEM, FEI Quanta 200,
Netherlands) with an acceleration voltage of 20 kV was utilized to ob-
serve the microstructure of WULC-NAB. An energy-dispersive X-ray
spectroscopy (EDS) was used to understand the elements distribution
mechanism of the WULC process. The phase-analysis of the different
portions in WULC-NAB coatings were performed on PANalytical X'Pert
Pro MPD X-ray diffraction with Cu Kα radiation, and the parameters
used in this test are as follows: the tube voltage of 40 kV, the tube
current of 40 mA and the scanning speed of 2°/min. JEM-2010 trans-
mission electron microscopy (TEM) was utilized to observe the micro-
structure further. Electrochemical testing of the substrate, NAB coating
fabricated in the air and NAB coating fabricated underwater were stu-
died on individual samples (with surface area of 1 cm2) for assessing the
corrosion properties. The surface of the samples are all polished,
without any scratches. Aerated 3.5 wt% sodium chloride solution with
pH of 6.8 was applied to this whole electrochemical experiment at room
temperature. For electrochemical measurements, a three electrode
configuration was employed using platinum plate as the counter, sa-
turated calomel as the reference and prepared specimens as the working
electrodes, respectively. All electrochemical measurements were per-
formed using a CHI600E electrochemical workstation
(CHINSTRUMENTS Inc. China). Each of the corrosion tests was re-
peated three times for checking the reproducibility of the electro-
chemical experiments, and the most representative data that was closest
to average values was selected for plotting.
X. Feng et al.
Table 2
Compositions of protective covering.
Constituent CaF2 CaCO3 TiO2 Cu
Wt% 40.1 19.6 18.9 8.7
3. Results and discussion
3.1. The effect of key parameters on formability (coating quality) of the
coatings fabricated by WULC
In this paper, the authors devoted their time to finding a prospective
method to repair damaged parts underwater. However, other research
has reported that increasing water depth will cause the failure of un-
derwater laser processing [5]. In this study, experiments similar to Ref.
5 have been finished, and the results are shown in Fig.3. In the whole
experiment, the fixed laser power (2800 W), fixed laser spot diameter
(3.5 mm) and fixed scan velocity (6 mm/s) will be adopted. Fig.3 a
shows the result of underwater laser cladding process without protec-
tive covering. In this experiment, the similar results as Ref. 5 have been
obtained. With increasing water depth (over 6 mm), the forming of NAB
coatings came to nothing. The coating integrity became poor under a
water depth of 6 mm. When the water depth was more than 8 mm, the
coating almost disappeared. That is to say, underwater laser cladding
process without protective covering has failed when the water depth is
over 8 mm. Fig.3 b shows the last stage of laser cladding process
without protective covering under 8 mm water depth schematically.
The water-vapor plasma formed, and this plasma can weaken laser in-
tensity strongly. Moreover, in deep water, the plasma cannot break
through the water surface, and the air cannot come into the plasma bag.
So that the laser beam channel will be interrupted. As result, the WULC
process will come to nothing. As shown in Fig.3 c, the formability of
NAB coatings are well till underwater depth of 10 mm. Fig.3 d shows
the last stage of laser cladding process with protective covering un-
derwater depth of 10 mm schematically. In this study, the semi-volatile
covering has prevented the coatings from being invaded by water. The
WULC-NAB coatings were protected by the semi-volatile covering in
three aspects. First of all, water-repellent material contained in pro-
tective covering keeps the water from invading powder layer. On the
Surface & Coatings Technology 333 (2018) 104–114
Al Mn Fe Ni Si Cr C6H7NO2
1 0.2 0.5 0.5 0.4 0.1 10
Fig. 1. Schematic diagram of process of the underwater
laser cladding in full wet surroundings (a) and real manu-
facturing process photo (b).
other hand, water could hardly invade into the melting pool owning to
the protective gas which forms from the following reaction:
CaCO3 → CaO + CO2.
C6H7NO2 → H2O + CO2 + NO2.
The gas mixture will forms a bubble and expands in water. As the
reason of generation of enough gas mixture, the bubble will become so
big that the water near the surface of workpiece will be moved away. As
a result, the metal plasma replaces the water-vapor plasma in this area.
So that, the beam channel can be established successfully, and the
process of laser machining will finish in a very short period of time. The
third aspect is that slag produced at the last stage of cladding prevents
the WULC-NAB coating from being invaded by water further, so that the
formability of the coating is well under 10 mm water depth.
Although the NAB coatings have been fabricated under 10 mm
water depth successfully, the formability (coating quality) of the
coating is still not satisfactory. The key parameters have to be opti-
mized. It is well known that the formability of coating fabricated by
laser cladding is closely associated with power density. Outrageous and
inadequate power densities are not appropriate for the process of un-
derwater laser cladding. To study the effect of power density on NAB
coatings fabricated by WULC, the laser power of 2.8KW and the scan-
ning velocity of 2–16 mm/s were chosen. In addition to this, the other
processing parameters were constant and as follows: laser beam dia-
meter of 3.5 mm, laser input angle of 7–12°, NAB powder size of 30-
50 μm and water depth of 10 mm. The picture of real product is shown
in Fig.4 a. Tracing the yellow arrow, power densities of the process are
getting large. The real products of NAB coatings fabricated by under-
water laser cladding with different process parameters possess different
formability. In this study, NAB coatings fabricated by underwater laser
cladding with proper process parameters possess good formability. It is
worth mentioning that the power density of the WULC process in full
wet surroundings is almost same as laser cladding process in the air.
The section of the optimal coating is shown in Fig.4 b, and the
Fig. 2. Schematic diagram of processing methods, (a) con-
tinuous processing and (b) intermittent processing.
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X. Feng et al.
optimized parameters are as follows: power of 2800 W and scanning
velocity of 10 mm/s. As shown in Fig.4 b, few pores appear in the
section of the coating. Fig.4 c-e show the microstructure of top, center
and bottom portions of the coatings respectively. As shown in the pic-
ture, a certain number of minor microstructures appear in all areas of
the coating, and the size of those microstructures in the top area and in
the center area are smaller than the microstructure in the bottom area
of the coating. This phenomenon is attributed to the fast cooling rate in
full wet surroundings. The heat on the surface of the coating loses faster
than in the body of the coating.
So far we have discussed the effect of water depth and power
Fig. 4. Macrostructure (a, b) and microstructure (c, d, e) of NAB coatings via underwater laser cladding.
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Surface & Coatings Technology 333 (2018) 104–114
Fig. 3. NAB coating fabricated by WULC, real production of NAB
coating fabricated by WULC (a) without and (c) with protective
covering, diagram of mechanistic of WULC process (b) without
and (d) with protective covering under 10 mm water depth.
density on the coating quality of single-track NAB coatings fabricated
by underwater laser cladding, and the optimized parameters have been
obtained. In order to get materials which could guide engineering
practice, the article try to find a prospective way to fabricate multi-
track NAB coatings underwater. In this study, two different methods
(method A and B) which have been introduced in the section of ex-
periment were attempted, and the results are shown in Fig.5. The NAB
coating fabricated in the air with two different methods possess good
formability as shown in red frame of Fig.5 c and f. The real product of
multi-track NAB coating fabricated by underwater laser cladding with
two different methods are shown in the white frame of Fig.5 c and f.
X. Feng et al.
Fig. 5. Cross-section topography of NAB coating fabricated by method B (a) and (b) and by method A (d) and (e), and real product of NAB coating fabricated by method B (c) and by
method A (f).
Thereinto, multi-track NAB coating shown in Figure c is fabricated by
method B, and called coating C. For contrast, multi-track NAB coating
fabricated by method A is shown in Figure f, and called coating F. Fig a,
b, c and d show the cross-section topography of NAB coatings in the
white frame. There are fewer pores in coating C than in coating F. That
is to say, method B is more suitable for fabricate NAB coatings under-
water. The reason for failure of method A is that the protective covering
lose effectiveness gradually with the continuous input of heat. In this
article, coating C is the main research object, and the coating fabricated
in the air using the same parameters is applied for comparative study.
3.2. The microstructure and elements distribution of NAB coatings
fabricated by laser cladding in the air and laser cladding in full wet
surroundings
3.2.1. Metallographic structure of NAB coatings
NAB alloys usually comprise various phases, including α-phase, β-
phase, and κ-phase. The κ-phases in NAB alloy usually have four styles:
κI, κII, κIII, κIV. Among the four κ-phases, κI, κII, κIV are Fe-rich solid
solution which usually distribute in α grains, and κIII is Ni-rich solid
solution which usually distribute between α-phases and β-phases [12],
and the typical microstructure of as-cast NAB is shown in Fig.6. NAB
coatings in this study were manufactured in the air and in full wet
surroundings. To know the microstructure of the NAB coatings clearly,
the metallographic analyses were carried out. As shown in Fig.7, pic-
ture a, b, c and d are the microstructure of the transition area, fusion
zone, central and top zones of the WULC-NAB coating respectively, and
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Surface & Coatings Technology 333 (2018) 104–114
picture e-h are the enlarged images of the designated areas marked in
picture a-d. Simultaneously, the images of similar areas in NAB coating
fabricated in the air are presented in Fig.8. Above all, the overlapping
ratio and some else features of the multi-track NAB coatings will be
discussed. There are two double-sided arrow (in red) in Fig.7 d and
Fig.8 d. They represent the width of the not-overlapping part, and the
values are all about 1800 μm (1.8 mm). In this study, the laser beam
diameter is of 3.5 mm. So the overlapping ratio of the coatings are all
about 49% (3.5 − 1.8 3.5 ). Fig.7 g and Fig.8 g show the fusion area (track
band) of both NAB coatings. Refer to Fig.7 c and Fig.8 c, the width of
the fusion area of WULC-NAB coating (~ 100 μm) is narrower than NAB
coating fabricated by laser cladding in the air (~ 200 μm). The reason of
this phenomenon is that the heat-loss is faster in the full wet sur-
roundings than in the air. The details will be discussed next.
Apparently, there are obvious differences among substrate, WULC-
NAB coating and NAB coating fabricated in the air. First and foremost,
the grain size of WULC-NAB coating is much finer than the grain size of
substrate and NAB coating fabricated in the air. This phenomenon is led
by many causes, but the fast cooling rate underwater is an important
one. Second, the microstructure morphologies and grain orientation
among of substrate, WULC-NAB coating and NAB coating fabricated in
the air are also different. There are a lot of slender columnar dendritic
crystals in WULC-NAB, shown in Fig.7 h. This area is in the middle of a
single-track WULC-NAB layer of the multi-track layers. The grain or-
ientation in this area is chaotic. The reason of the chaotic grain or-
ientation is that the water close to the surface of the coating flows
without any rules during WULC process. In the early stage of WULC
Fig. 6. Typical as-cast NAB metallographic structure (a) and
magnifying picture (b).
X. Feng et al. Surface & Coatings Technology 333 (2018) 104–114

Fig. 7. OM images of the microstructure of (a) transition area, (b) fusion area, (c) middle area, (d) top area, and (e-h) enlarged images of the designated areas of WULC-NAB coating.

Fig. 8. OM images of the microstructure of (a) transition area, (b) fusion area, (c) middle area, (d) top area, and (e-h) enlarged images of the designated areas of NAB coating
manufactured by laser cladding in the air.

Fig. 9. Element distribution of (a) substrate, (b) bottom area, (c) and (d) center area and (e)top area on the section of the coatings by WULC.

process, the water close to the protective covering was drained away,
and the melting pool generated simultaneously. Then, the melting pool
solidified quickly before the water came back. Almost immediately the
water flowed to the new surface of the coating chaotically. So, there is a
non-uniform temperature field (unsteady-state temperature field) [13]
in the body of the new WULC-NAB coating. As a result, the grain
orientation in this area is chaotic. Moreover, the fusion zone (shown in
Fig.7 g) between the two single-track coatings consists most of equiaxial
grain, because of that this area is far from the water, and the thermal
conduction is roughly identical in different directions. In addition, heat
dissipating is so fast underwater that the microstructure morphologies
are all the same in every single-track layer of the whole coating.

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X. Feng et al.
Subsequent thermal input has little impact on the microstructure of
previous layers. Concerning the microstructure of NAB coating manu-
factured in the air by laser cladding, there are not something extra-
ordinary. The microstructures of NAB coating fabricated by laser
cladding in the air show typical NAB morphologies after repeating
quenching [14]. The NAB coating manufactured by laser cladding in the
air contains predominately Widmanstȁtten α and fine martensite (dark
area) in both the fusion and the body areas of every single-track layer.
During the process of laser cladding in the air, the NAB coating will
experience the cycle of heating and cooling to repeat. Repeating heating
and cooling will cause α-phase and martensite grow up adjacently.
3.2.2. Elements distribution of NAB coatings
Distribution of element is a concerned problem due to the complex
interaction during underwater laser cladding. The energy disperse
spectroscopy (EDS) analysis results of different areas of the WULC-NAB
coating are shown in Fig.9. Picture (a-e) show the elements content of
bottom, center, margin and top areas of the coatings respectively. There
are different contents of carbon in different areas of the coatings, and
the distribution of carbon element is shown in Fig.9 f schematically. On
the other side, the distributions of other elements such as Al, Fe, Ni, Mn,
Cr and Cu in the coatings are homogeneous. In this study, carbon atoms
mainly come from the semi-volatile covering. In consideration of
melting pool dynamic characteristics, there is maximum temperature in
the central location. For this reason, the content of carbon is minimum
in the central location, and most of the carbon atoms diffused towards
other sites [15] (the surface and edge of the coating). In this paper, the
NAB coating is overlapped, so we naturally think that the subsequent
thermal input may influence the previous coating. That is indeed. Al-
though the heat dissipates fast underwater, but in the core of the
coating is another case. There is sufficient time for the carbon atoms to
diffuse. So, the distribution of carbon elements in the whole center area
of the NAB coating is homogeneous. Due to the fast cooling rate, it is
difficult for the carbon element to escape from the surface of the NAB
coating, so that the carbon content in the surface of the coating is high.
In addition, the minor elements coming from the protective covering
like Ti and F show a tendency to increase from the bottom to top area of
WULC-NAB coating. In this paper, the function of TiO2 are slagging and
improving the fluidity of the melting pool. As is well-known, titanium
element is lighter than most of the other elements in NAB, so that ti-
tanium is easy to float during the process of laser cladding. As a result,
TiO2 protect the melting pool effectively. Furthermore, CaF2 protected
the melting pool of NAB from invading by H2. Fluorine is a light ele-
ment too. The fluoride in the molten pool will float to surface until the
melting pool solidify. For further understanding the effect of process of
WULC on the distribution of elements, the NAB coating fabricated in
Fig. 10. Element distribution of (a) substrate, (b) bottom area, (c) and (d) center area and (e)top area on the section of the coatings by laser cladding in the air.
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Surface & Coatings Technology 333 (2018) 104–114
the air is studied. As shown in Fig.10, similar conclusions that the
content of carbon is low in the middle and high on all sides can be
drawn. Alloy elements can affect the microstructure and performance of
materials forcefully, so that the microstructure on a more subtle level of
the two NAB coatings should be studied.
3.2.3. Microstructure (TEM) and phases-constitution of NAB coatings
The XRD results of WULC-NAB coating shown in Fig. 11 (a) indicate
that the coating portions (B, C, D) have lower peak of all phases as
compared to substrate (A). The same phenomenon also exists in NAB
coating fabricated in the air as Fig.11 (b). This phenomenon is resulted
from the peak broadening. The peak broadening is attributed to fine
grain structure of coating portions. Comparing Fig. 11 (a) with Fig.11
(b) the obvious difference can be observed. The XRD patterns of WULC-
NAB coating portions (B, C and D) occur excursion in the direction of
large angle, but this phenomenon does not exist in NAB coating fabri-
cated in the air. This result indicate that there is a greater degree of
solid solution in WULC-NAB coating than in substrate-NAB and NAB
coating fabricated in the air. Referring to Fig.9, the closer to the surface
of WULC-NAB the more F and Ti elements exist. The existence of these
smaller elements may increase the probability of solid solution.
The representative TEM analysis results of (a) substrate, (b) coating
fabricated in the air and (c) coating fabricated underwater are shown in
Fig. 12, thereinto, image (c) and (d) suggest that laser cladding NAB
coatings possess the same phase constitution as cast-NAB. The differ-
ence is that more β’-phases exist in both coating portion because of fast
cooling rate during laser cladding process [16]. As shown in Fig.12 b, a
very small amount of twin structures have been observed. The reason of
this phenomenon can be explained that the fast cooling rate and repeat
quenching caused the residual stress in some location of NAB coating
fabricated in the air, and the residual stress caused the lattice sheared.
Fig.12 c shows the representative microstructures and selected-area
electron diffraction patterns of WULC-NAB coating. Surprisingly, there
are some ordered solid solution in WULC-NAB coating as shown in
Fig.12 c1. In general, to form ordered solid solution, the low cooling
rate is needed. However, providing the condition of low cooling rate is
hardly possible during WULC process. So that, the complex composition
is the most likely reason for the forming of ordered solid solution. The
ordered solid solution might be the evidence for the excursion of XRD
patterns of WULC-NAB coatings. In addition, there are number of twin
structures in WULC-NAB coating as shown in Fig.12 c1, c2 and c3. The
twin structures almost exist from corner to corner of the coating fab-
ricated by WULC, which is unusual in cast NAB alloys. It always exist in
deformed copper alloys [17]. The most likely reason is that there is high
value of residual stress in WULC-NAB coatings. The large residual stress
caused the lattice sheared. The large residual stress may be introduced
X. Feng et al. Surface & Coatings Technology 333 (2018) 104–114

Fig. 11. X-ray diffraction pattern of (a) WULC-NAB coatings and (b) NAB coatings fabricated in the air.

Fig. 12. TEM images of (a) substrate, (b) coatings fabricated in the air and (c) coatings fabricated underwater.

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Fig. 13. (a) Open-circuit potentials, (b) polarization curve and (c) higher magnification of polarization curves of substrate, NAB coating fabricated in the air and fabricated underwater
and (d) schematic illustration of Tafel extrapolation fits to extract the parameters from polarization curves.
by two ways. On the one hand, the fast cooling rate introduced large
internal stress. On the other hand, the explosion of the bubble near the
workpiece caused a degree of surface deformation, and more stress was
introduced. In addition, more elements such as Ti, F and Ca have been
introduced into the body of NAB coating fabricated by WULC. Those
elements may make the stacking fault energy of NAB reduce. As is well-
known, the metals which have low stacking fault energy can produce
twin structure more easily. However, the interesting question is whe-
ther a good thing it is. So that the electrochemical study will be dis-
cussed in the next part.
3.3. The electrochemical study of NAB coatings fabricated in the air and
underwater
Fig.13 a shows the results of open-circuit potential of substrate, NAB
coating fabricated in the air and underwater. The mean open-circuit
potential values of substrate, NAB coating fabricated by laser cladding
in the air and NAB coating fabricated by WULC are of -260 mV,
− 249 mV, and -250 mV respectively. That is to say, the NAB coatings
fabricated both in the air and underwater have smaller corrosion ten-
dency than substrate in aerated 3.5% sodium chloride solution. For
further comprehension of the corrosion mechanism, measurements of
polarization curves have been carried out, and the results are shown in
Fig.14 b and c. Moreover, a schematic illustration of the Tafel extra-
polation fittings for extraction of various parameters from polarization
curves is represented in Fig.13 d. Concerning Fig.13 b, at low positive
over-potential area where mixed charge transfer and mass transport
controlling kinetics apparent Tafel behavior can be observed [18]. In
this paper, specific corrosion processes is not focus. The point of this
part is to study the effect of the key factors of different processing
methods on the corrosion behavior of three samples. As shown in
Table.3, Ecorr (corrosion potential) of substrate, NAB coating fabricated
by laser cladding in the air and NAB coating fabricated by WULC are of
-275 mV, − 273 mV and -269 mV respectively. Those results are dif-
ferent from the open-circuit results. The coating fabricated by WULC
has the lowest corrosion tendency in polarization curves while the
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Surface & Coatings Technology 333 (2018) 104–114
coating fabricated by laser cladding in the air has the lowest corrosion
tendency in open-circuit potential curves. So that more evidence is
needed. The icorr results show that the coating fabricated by WULC
possesses the lowest corrosion current density value. In conclusion, the
coating fabricated by WULC has the lowest corrosion tendency, while
the substrate has the greatest corrosion tendency. The NAB coatings
fabricated by laser cladding have finer grain than substrate as shown in
Figs.6, 7 and 8, especially for NAB coating fabricated by WULC. Fine
grain possesses smaller cathode area than big grain, and this give rise to
the decrease of cathodic current [19]. According to the corrosion ki-
netics, increasing the cathodic area will promote the reduction process,
so that the anodic current will be increased. On the other hand, the
penetration rate of the corrosive medium of grain boundary will de-
crease with the decrease of the grain size [20]. Fig.14 show the cor-
rosion morphologies of (a) substrate, (b) NAB coating fabricated in the
air and (c) NAB coating fabricated by WULC. The pictures of corrosion
morphology were taken from the samples which were used to measure
the polarization curves. As shown in Fig.14, the surfaces of substrate
and NAB coating fabricated by laser cladding in the air are corroded
seriously, while the surface of NAB coating fabricated by WULC has the
lightest corrosion level. On the one hand, NAB coating fabricated by
WULC has finer grain size than others, and the reason of that it has the
best corrosion resistant performance has been explained. On the other
hand, there are some Ti and F in the top area (near to surface) of WULC-
NAB coating. Titanium has good corrosion resistance, and it is easy to
form dense oxidation film on the surface. That is to say, titanium may
have enhanced the corrosion resistance of the coating surface. So that,
the method for fabricated NAB coating underwater mentioned in this
paper is beneficial for the anti-corrosion properties of the material
surface.
4. Conclusions
The WULC process for fabrication of NAB coatings were carried out
successfully, and the process of fabricating NAB coatings in the air were
carried out for comparative study. It is worth mentioning that the
X. Feng et al. Surface & Coatings Technology 333 (2018) 104–114

Fig. 14. Corrosion morphology of (a) substrate, (b) NAB coating fabricated in the air and (c) fabricated underwater.

Table 3 provide theoretical guidance for repairing damaged parts in full wet
Potentiodynamic polarization parameters of the substrate NAB coating fabricated in the surroundings.
air and NAB coating fabricated by WULC in aerated 3.5% sodium chloride solution.
Supplementary data to this article can be found online at http://dx.
Materials Substrate Coating in the air Coating underwater doi.org/10.1016/j.surfcoat.2017.10.056.

Ecorr (V) − 0.275 − 0.273 − 0.268 Acknowledgement

icorr (A/cm2) 1.69 × 10− 5 8.58 × 10− 6 6.74 × 10− 6

This work was financially supported by National Natural Science

Foundation of China (No. 51775127, 51575118), National Basic
power density of the WULC process in full wet surroundings is almost
Research Program of China (973 Program) (No. 61328303), China
the same as laser cladding process in the air. Another thing worth
Postdoctoral Science Foundation (2017T100225) and Fundamental
noting that the operating water depth is of 10 mm and the protective
Research Funds for the Central Universities (HEUCFP201608).
covering has been used for protect the coatings. On the contrary, the
process of fabrication of NAB coatings underwater without the pro-
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