Materials Science & Engineering A 844 (2022) 143170

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Materials Science & Engineering A

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

On the adhesion performance of gradient-structured Ni–P metallic coatings

Yan Lin a, 1, Fenghui Duan b, 1, Jie Pan a, b, **, Cheng Zhang a, Qi Chen c, Junyong Lu d, Lin Liu a, *
a
State Key Laboratory of Material Processing and Die & Mould Technology and School of Materials Science and Engineering, Huazhong University of Science and
Technology, Wuhan, 430074, China
b
Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, Shenyang, 110016, China
c
Wuhan National High Magnetic Field Center, Huazhong University of Science and Technology, Wuhan, 430074, China
d
National Key Laboratory of Science and Technology on Vessel Integrated Power System, Naval University of Engineering, Wuhan, 430033, China

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

Keywords: Hard metallic coatings can provide exceptional protection for industrial settings; however, they usually have a
Gradient structure uniform microstructure and suffer from poor adhesion with substrates because of stress/strain incompatibility
Ni–P coatings induced by the sharp interface. Here, a gradient structure that transitions from coarse-grained Ni to nano­
Electrodeposition
crystalline/amorphous Ni–P alloy has been designed to improve the adhesion performance of the electro­
Interface shear strength
Bending strength
deposited Ni–P coatings. Based on two measures of adhesion performance, a high interface shear strength of
~282.6 MPa and high bending strength of ~868.4 MPa have been determined for the gradient-structured Ni–P
coatings on the CuCrZr alloy substrate, which are increased, respectively, by ~90% and ~60% from those of the
conventional monolithic-structured Ni–P coating. Post-mortem fractographic analysis reveals that introducing
the gradient structure accommodates plastic deformation of the coating and provides exceptional crack arrest
capability, contributing to the enhancement of adhesion performances under both shearing and bending. The
present work not only reveals how the adhesion performance can be significantly improved in gradient-
structured Ni–P coatings, but also provides a promising methodology for manufacturing novel GS metallic
coatings with a combination of excellent surface functions and strong interface adhesion.

1. Introduction
Metallic coatings are workable and vital as they can provide excep­
tional protection for equipment and industrial settings when serviced in
harsh environments. The advance in engineering technologies has
imposed increasing demands for superior adhesion of metallic coatings
to ensure their durability and to perform their excellent surface prop­
erties (e.g., high hardness and high corrosion resistance) [1,2]. For
example, the damage-resistant metallic coating should be well-adhered
to the Cu alloy rail to avoid the peeling-off failure under mechanical
impact during electromagnetic launching. However, traditional
damage-resistant metallic coatings (e.g., hard Cr coating [3] and
nanocrystalline/amorphous Ni–P coating [4,5]) have a uniform struc­
ture. The significant difference in structure/properties between coating
and substrate usually causes a stress/strain incompatibility at the
interface region during deformation, leading to poor adhesion (e.g., the
adhesion strength of the Ni–P coating deposited on the steel is merely in
the range of 85–144 MPa [6]). Ensuring a robust adhesion of the hard
metallic coatings on the soft substrate has always been a long-term
challenge.
Taking a leaf out of Nature’s playbook, a promising strategy to
enhance the properties of materials is creating gradient structure
[7–13]. For example, the fiber content in bamboo and other plants in­
creases from the inner region outwards the outer region, forming a
gradient structure that generates marvelous flexibility and strength [14,
15]. Recent attempts have utilized the concept of the gradient in coating
structure design to avoid abrupt mechanical or chemical changes at the
interface between two different materials, and achieve a favorable
adhesion [16–20]. For instance, gradient Ni–Co/SiC coatings exhibited
higher adhesion strength, as compared to those of the uniform nano­
structured coatings with a microstructure similar to its outer surface
[20]. Concerning metallic coatings, gradient structures have also been

* Corresponding author.
** Corresponding author. State Key Laboratory of Material Processing and Die & Mould Technology and School of Materials Science and Engineering, Huazhong
University of Science and Technology, Wuhan, 430074, China.
E-mail addresses: jpan@hust.edu.cn (J. Pan), lliu2000@mail.hust.edu.cn (L. Liu).
1
These authors contributed equally to this work.

https://doi.org/10.1016/j.msea.2022.143170
Received 18 February 2022; Received in revised form 10 April 2022; Accepted 16 April 2022
Available online 20 April 2022
0921-5093/© 2022 Elsevier B.V. All rights reserved.
Y. Lin et al.
tailored to improve adhesion and other properties [21–26]. For
example, the gradient-structured (GS) pure Ni coating with the grain
size changing from microscale near the substrate to nanoscale on the
outer surface can be bent over 180◦ without cracking or interface
delamination [23]. In contrast, the nanocrystalline Ni coating ruptures
and separates from the substrate. Likewise, the gradient composition
and structure contribute to a decreased internal stress in Ni–Co coatings
[24], enabling reliable adhesion and enhanced tribological properties.
The aforementioned studies suggest that metallic coatings having
gradient structures can possess superior adhesion performances, in
comparison with those having a monotonic microstructure or homoge­
neous chemical composition. However, the systematical investigation
on how grain structure affects the adhesion performance is still lacking.
Furthermore, only a solo-type gradient structure was investigated in
most previous studies due to the limitation in the synthesis technology,
and the specific effect of gradient profile on the adhesion performance of
metallic coatings has rarely been explored. These unsolved problems
hinder the optimization of adhesion in GS metallic coatings, and thus
prevent the realization of their full potential in applications.
Recently, we reported the successful fabrication of GS Ni with
various gradient profiles via electrodeposition [27–30] and revealed the
influence of grain size gradient profile on mechanical properties. In the
present work, we go a step further and synthesize GS Ni–P coatings by
adding the solute atom P in pure Ni to enhance the hardness of coatings
while maintaining good interface adhesion. Our GS Ni–P coatings
encompass dual gradients, i.e., the chemical composition gradient plus
the grain size gradient, transitioning from coarse-grained (CG) pure Ni
to nanocrystalline/amorphous Ni–P alloy (P content is approximately 9
at.%). On these grounds, we demonstrate that GS Ni–P coatings can
indeed be highly adhesive at the interface and be strong at the surface
layer simultaneously, and reveal the effects of gradient structure and
gradient profile on the adhesion performance.
2. Experimental methods
2.1. Materials preparation
GS Ni–P coatings with a thickness of ~0.5 mm were deposited on the
soft CuCrZr alloy plate through a direct-current (DC) electrodepositing
set-up, as DC electrodeposition has high processing controllability and
good flexibility, and almost has no limitations on the coating thickness.
The basic plating bath was a modified Watts-type electrolyte. The bath
composition and processing parameters have been given in Table 1.
According to the previous works [23,27,31–33], the grain size of coating
can be refined by adding the grain refiner (e.g., sodium saccharin) and
increasing the current density; the P content of coating increases with
the increasing concentrations of phosphorous acid and sodium hypo­
phosphite in the electrolyte. Thus, the grain size gradient can be ach­
ieved with gradual increases in sodium saccharin content (0.5–15.5 g/L)
Table 1
Composition of plating bath and processing parameters for electroplating GS
Ni–P coatings.
Bath composition Nickel sulfate hexahydrate 100 g/L
Nickel chloride hexahydrate 45 g/L
Boric acid 40 g/L
Sodium dodecyl sulfate 0.2 g/L
Sodium saccharin 0.5–15.5 g/L
Phosphorous acid 0–7.5 g/L
Sodium hypophosphite 0–3 g/L
Processing parameters Current density 30–50 mA/cm2
Temperature 343 ± 1 K
Initial pH ~3.5
Substrate (CuCrZr alloy) 40 × 60 × 5 mm3
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Materials Science & Engineering A 844 (2022) 143170
and current density (30–50 mA/cm2); while the chemical composition
gradient can be attained via the continuous additions of phosphorous
acid (0–7.5 g/L) and sodium hypophosphite (0–3 g/L). Sodium
saccharin can also be used to adjust internal stress and inhibit cracking.
To investigate the influence of gradient profile, two different sets of GS
Ni–P coatings (i.e., GS Ni–P I and II) were prepared.
Monolithic-structured (MS) Ni and MS Ni–P coatings were also prepared
by electrodeposition for comparison. For simplicity, GS Ni–P I, GS Ni–P
II, MS Ni, and MS Ni–P coatings deposited on the CuCrZr alloy plate
were termed as GS Ni–P/Cu I, GS Ni–P/Cu II, MS Ni/Cu, and MS
Ni–P/Cu, respectively.
2.2. Material characterization
Cross-sectional morphologies of various coatings were characterized
by scanning electronic microscope (SEM Phenom XL G2) in the back-
scattered electron (BSE) imaging mode. The P content profile was
determined using SEM equipped with an energy dispersive X-ray de­
tector. Microstructures of the as-deposited GS Ni–P coating and the
coating/substrate interface were further investigated by transmission
electron microscope (TEM), high-resolution TEM (HRTEM), and energy-
dispersive X-ray spectroscopy (EDS) (FEI Talos F200). The cross-
sectional TEM foils for microstructure characterization were prepared
using focused ion beam (FIB) (FEI Helios NanoLab DualBeam 650). The
microhardness along the thickness direction of various coatings was
measured by a microhardness (Qness Q10 A+) tester using a Vickers
indenter with a load of 50 g and a dwell time of 10 s. To characterize and
verify the hardness gradient profile of the coating, one microhardness
measurement was made at each point with appropriate spacing between
any two neighboring indentations (~50 μm), and the through-thickness
hardness profile was validated by repeated measurement.
2.3. Mechanical characterization
The interface shear strength of coatings was determined using a
home-made testing set-up shown in Fig. 1a. All the specimens have an
identical dimension of ~5.5 (width) × 10 (length) × 1 (thickness) mm3.
For shearing testing, two specimens were symmetrically clamped be­
tween two rectangular fixture blocks, where the coating/substrate
interface and the long edge of the lower block were positioned in one
plane, and the coating parts sandwiched between two blocks were
forced with a loading rate of 2 mm/min (Fig. 1a). The nominal shear
strength was calculated by formula F = P/S (where P is the maximum
load, and S is the total interface area). At least three tests were con­
ducted for each coating.
The adhesion performance of the coating/substrate was also tested
by a three-point bending test at room temperature with a loading rate of
0.5 mm/min (Zwick-Z020 mechanical system). The bending specimen
(as illustrated in Fig. 1b) has a total thickness (h) of ~5.8 mm (including
the coating thickness (hc) of ~0.5 mm), a width (b) of 6 mm, a total
length of 35 mm, and the span (l) between two supporting points is 30
mm. The bending strength was calculated using the equation as follows
[34]:
( )
4h Pf l 1 Ec (hc + ζ)
σ b = 0.8 ⋅ 1 − ⋅ ⋅ ⋅ (1)
3πl 4 M0 Es (hs − ζ)
where M0 = b(h3s - 3h2s ζ + 3hsζ2)/[3(ζ – hs)] + (EC/ES)b(h3c - 3h2c ζ +
3hcζ2)/[3(hs - ζ)], ζ= (ECh2s – ESh2c )/[2(EShs+ EChc)]. EC, ES, hc and hs are
Young’s modulus of the coating, Young’s modulus of the substrate,
coating thickness and substrate thickness, respectively. Here, ES = 130
GPa, EC for MS Ni–P and MS Ni coatings are 178 GPa [35] and 200 GPa,
respectively; while EC for GS Ni–P coatings was calculated by a simple
rule-of-mixture type of relationship [36].
Y. Lin et al. Materials Science & Engineering A 844 (2022) 143170

Fig. 1. (a) Schematic diagram illustrating a measure of interface adhesion strength for the coating under shearing. (b) Schematic diagram illustrating the three-point
bending test of the specimen with coating and substrate.

2.4. Fractographic characterization
To discern the failure mode for different coatings under shearing and
bending loads, the fracture surfaces and crack patterns were examined
using an optical microscope (OM, Leica DFC 450) and SEM.
3. Results
3.1. Microstructure of GS coatings
Backscattered-electron (BSE) images taken from MS Ni–P and MS Ni
coatings clearly show a uniform fine grain structure (Fig. 2a) and a
coarse columnar grain structure (Fig. 2b), respectively. For the GS Ni–P
coatings (i.e., GS Ni–P I and GS Ni–P II), a typical grain size gradient
with microstructure varying from coarse columnar grains to fine grains
along the thickness direction is presented (Fig. 2c and d). These two GS
Ni–P coatings display distinct gradient profiles, where the grain size
change in the GS Ni–P I coating is gentler than that in the GS Ni–P II
coating. This result implies that the gradient profile of Ni–P alloys can
also be manipulated in a fashion similar to that of pure Ni reported
previously [27,28].
To provide the microstructure evolution in detail, the representative

Fig. 2. Typical backscattered-electron (BSE) images taken from the coating revealing the various grain structures: (a) MS Ni–P, (b) MS Ni, (c) GS Ni–P I, and (d) GS
Ni–P II, respectively.

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Y. Lin et al.
microstructure of the GS Ni–P II coating at various locations along the
thickness direction was examined, as shown in Fig. 3. In the vicinity of
the interface (i.e., normalized distance is ~0), columnar grains with a
width of ~5 μm are characterized (Fig. 3a). As the normalized distance
shifts to ~0.91, elongated ultrafine grains, ~300 nm in short axis, are
seen in the bright-field TEM image (Fig. 3b). With a further increase in
normalized distance (~0.94), nanograins with a size of ~30 nm emerge
(Fig. 3c). The elongated diffraction in the selected area electron
diffraction patterns (SAED) indicates the formation of textured struc­
ture, even in the ultrafine-grained regions (insets in Fig. 3b and c). For
the topmost layer (i.e., normalized distance is approximately 1), tiny
grains with a size of ~10 nm are embedded in an amorphous matrix,
showing an amorphous/nanocrystalline hybrid structure (Fig. 3d and e).
In addition to the grain size gradient, there is also a chemical gradient
along the deposition direction, as shown in Fig. 3f. As the normalized
distance shifts from 0 to 1, P content gradually increases from 0 to ~9 at.
% for the two GS Ni–P coatings. The P content in the topmost layer of the
coating falls into the composition range (i.e., 9–15 at.%) for forming an
amorphous phase [37], which is consistent with the TEM observation in
Fig. 3e. For the MS Ni–P coating, the P content varies slightly from ~8 to
~4 at.% in thickness direction due to the excessive consumption of
phosphorous acid and sodium hypophosphite during the long-time
deposition.
3.2. Hardness and grain size profiles of GS coatings
Fig. 4a presents the microhardness profiles of the two GS Ni–P
coatings. For comparison, the data obtained from MS Ni–P and MS Ni
coatings are also included. The microhardness of the MS Ni–P and MS Ni
coatings are 6.91 ± 0.25 GPa and 1.62 ± 0.13 GPa, respectively. Note
there is a slight fluctuation of hardness values along the thickness di­
rection in MS Ni–P coating, mainly due to the moderate variation of P
content (Fig. 3f).
For both GS Ni–P I and II coatings, the microhardness continuously
increases from a minimum value of ~1.8 GPa at the interface (normal­
ized distance of ~0) to a maximum value of ~7.2 GPa at the outmost
surface (normalized distance of ~1). Apparently, the upper and lower
Fig. 3. (a) Representative SEM image of coarse columnar grains on the CG side. TEM images at various normalized distances in the GS Ni–P II coating: (b) ~0.91, (c)
~0.94, and (d, e) ~1.0 (i.e., the topmost layer). Insets in (b) and (c) are the corresponding SAED patterns. (f) The P content profiles of MS Ni–P, GS Ni–P I, and GS
Ni–P II coatings.
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Materials Science & Engineering A 844 (2022) 143170
bounds of hardness for the two GS Ni–P coatings are comparable to that
of MS Ni–P and MS Ni coatings, respectively. Although the two GS
coatings have the same maximum and minimum hardness values, the
hardness gradient profiles are quite different. The hardness gradient of
GS Ni–P II is much steeper, reminiscent of the depictions of micro­
structure evolution (Fig. 2b and c) and P content distribution (Fig. 3f).
Fig. 4b shows the grain size profiles as a function of the normalized
distance in various coatings. The width of coarse columnar grain was
regarded as grain size and measured using the BSE image, while the size
of fine grain was estimated based on the Hall-Petch relation [38]. It is
clear that both MS Ni–P and MS Ni coatings exhibit a homogeneous
grain size distribution with the average grain size of ~8 nm and ~7 μm,
respectively. For the two GS Ni–P coatings, the grain size continuously
decreases from ~6 μm to ~8 nm, covering three orders of magnitude in
size. The upper and lower bounds of grain size in GS Ni–P coatings are
comparable to the average grain sizes of MS Ni and MS Ni–P coatings,
respectively. Moreover, the grain size change in the fine grain region is
much gentler in GS Ni–P I than that in GS Ni–P II, leading to a higher
fraction of nano-grains (i.e., grain size is less than 100 nm). Specifically,
the volume fraction of nano-grains is up to ~70% in the GS Ni–P I, while
it is less than 10% in the GS Ni–P II.
3.3. Interface characterization of GS coatings
One of the keys to the adhesion performance of the coatings is the
interface structure. No flaws, such as nano-voids and cracks, are
observed in the TEM image taken from the interface of the GS Ni–P II
and Cu alloy substrate, as displayed in Fig. 5a. Fig. 5b–d shows a typical
high angle annular dark-field (HAADF) image and the corresponding
EDX mapping around the interface. Apparently, the interface is tortuous
and sharp at the nanometer level, without a chemical intermixing layer.
A typical HRTEM image in Fig. 5e reveals that the interface is
atomically bonded. The lattice planes run continuously across the in­
terfaces, indicating the epitaxial growth of the GS Ni–P coating on the Cu
alloy substrate. The GS Ni–P coatings have a gradient structure tran­
sitioning from pure Ni to Ni–P alloy. The initial pure Ni deposits can
epitaxially grow on the (111) lattice plane of the Cu substrate because
Y. Lin et al. Materials Science & Engineering A 844 (2022) 143170

Fig. 4. (a) Microhardness profiles of various coatings as a function of the normalized distance ranging from 0 to 1, i.e., from the substrate/coating interface to the
surface of the coating. (b) Grain size profiles of MS Ni–P, GS Ni–P I and GS Ni–P II coatings. Here the width of coarse columnar grain in the pure Ni regime was
determined using the BSE image, while the size of fine grain in the Ni–P alloy regime was calculated based on the Hall-Petch relation reported in Ref. [38].

Fig. 5. (a) TEM observation of the as-deposited interface between the GS Ni–P and Cu alloy substrate. (b) HAADF imaging of an enlarged area around substrate/
coating interface, and EDS mapping of (c) Cu and (d) Ni. (e) Cross-sectional HRTEM image showing the atomistic characteristics of the interface.

Cu and Ni have the same face-centered cubic structure and almost
identical atomic size (atomic radii of Ni and Cu are 0.124 nm and 0.128
nm, respectively) [39,40]. This epitaxial growth enables an excellent
metallurgical bonding for the GS Ni–P coatings in this study.
3.4. Shear-adhesion properties of various coatings
Fig. 6a presents the load-displacement responses of the various
coatings upon shear testing. For MS Ni–P coating, a maximum load
reaches about ~2890 N and then drops rapidly as interface fracture
ensues. This result indicates that the interface region of the MS Ni–P
coating cannot accommodate any plastic strain. Conversely, MS Ni
coating exhibits a large plastic displacement beyond yielding. The
maximum load is ~5820 N, ~100% higher than that of the MS Ni–P
coating. For both GS Ni–P coatings, the load-displacement responses are
analogous to the MS Ni coating, i.e., the load slowly ascends with a
remarkable plastic displacement beyond yielding. In particular, the
maximum loads for GS Ni–P I and II coatings are ~5960 and ~6490 N,

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Y. Lin et al. Materials Science & Engineering A 844 (2022) 143170

Fig. 6. (a) Typical load-displacement curves and (b) the corresponding interface shear strengths of the MS Ni–P/Cu, GS Ni–P/Cu I, GS Ni–P/Cu II, and MS Ni/Cu
obtained from shearing tests at room temperature.

respectively, which is close to that of the MS Ni coating (the slight dif­

ference is due to the specimen geometry). Based on the maximum load,
the interface shear strength of various coatings is calculated and sum­
marized in Fig. 6b and Table 2. The MS Ni–P coating has a low interface
shear strength of 154.7 ± 44.3 MPa, approximately half of that of the MS
Ni coating (289.3 ± 7.6 MPa). In contrast, GS Ni–P I and II coatings
exhibit the interface shear strengths of 280.1 ± 24.3 MPa and 282.6 ±
36.3 MPa, respectively, much higher than the MS Ni–P coating and
comparable to that of the MS Ni coating. These interface shear strengths
are even approximately equal to the shear strength of Cu alloy (~261.5
± 6.7 MPa). For the two GS Ni–P coatings, the gradient profile has no
influence on the interface shear strength, as both coatings have an
identical initial pure Ni deposit contiguous to the interface.
Fig. 7 presents fracture morphologies of the MS Ni–P, GS Ni–P II, and
MS Ni coatings after shearing testing. Due to the significant differences
in microstructure/property between the coating and the substrate and
the brittleness of the MS Ni–P alloy, neither the interface region nor the
coating could accommodate shear strain. As a result, local interface
delamination and cracking within the coating occurred in the MS Ni–P/
Cu after shear testing (Fig. 7b). Unlike the rupture of the MS Ni–P
coating, the replication of gradient structure can keep the integrity of
coating after shear testing (Fig. 7c), similar to that of MS Ni coating
(Fig. 7d). Furthermore, a thin film of Cu alloy substrate adheres to the
sheared-off coating (Fig. 7c), suggesting failure occurs within the Cu
alloy instead of the interface of the GS Ni–P and Cu alloy substrate. Fig. 7. (a) OM image showing the interface region between the coating and
substrate before shearing. Fracture morphologies for the (b) MS Ni–P, (c) GS
3.5. Bending behaviors of various coatings Ni–P II, and (d) MS Ni coatings after shearing testing. Insets in (b) show the
coating cracking and interface delamination.
To evaluate the adhesion performance of the coatings suffering from
more complicated and harsh load-bearing conditions, the three-point coating. The subsequent load increment is mainly due to strain-
bending test was also performed at room temperature. Fig. 8a shows hardening of the Cu alloy substrate upon plastic deformation. There­
the corresponding load-displacement curves of various coating/sub­ fore, the determined failure load for the MS Ni–P/Cu is ~2500 N. In
strate system (i.e., coating + substrate). For the MS Ni–P/Cu (i.e., the MS contrast, no load drop is detected in the load-displacement curve of the
Ni–P coating + the Cu alloy substrate, similarly hereinafter), a signifi­ MS Ni/Cu (Fig. 8a), which manifests that no coating failure occurred
cant load drop is observed at a displacement of 0.35 mm beside the small even after large plastic deformation. The load at the maximum
serrations at the early stage, indicating the cracking/failure of the displacement (~3800 N) is thus determined as the failure load.
The GS Ni–P/Cu I and II have distinct load-displacement curves
Table 2 under bending (Fig. 8a). The load-displacement curve of the GS Ni–P/Cu
Coating adhesion properties measured by shearing and three-point bending I is slightly serrated, and the magnitude of load serration is much smaller
tests. than that in MS Ni–P/Cu. The load increases firstly and then starts to
Specimens Shear strength Bending strength Surface hardness decline slowly, thus the peak load (~3610 N) is regarded as the failure
(MPa) (MPa) (GPa) load. Conversely, the load-displacement curve of the GS Ni–P/Cu II is
MS Ni–P 154.7 ± 44.3 534.5 6.72 ± 0.11
smooth without noticeable serrations. The load increases monotonously
MS Ni 289.3 ± 7.6 812.8 1.62 ± 0.13 during loading, thus the load at the maximum displacement (~4010 N)
GS Ni–P I 280.1 ± 24.3 736.7 7.04 ± 0.24 is the failure load. In addition, the load to sustain bending of the GS
GS Ni–P II 282.6 ± 36.3 868.4 6.91 ± 0.25 Ni–P/Cu II exceeds that of the MS Ni/Cu, implying a higher bending
Note that the surface hardness was measured at the normalized distance of 1.0. strength.

6
Y. Lin et al.
Fig. 8. (a) Typical load-displacement curves and (b) bending strengths of the MS Ni–P/Cu, GS Ni–P/Cu I, GS Ni–P/Cu II, and MS Ni/Cu obtained from three-point
bending tests at room temperature.
Based on Eq. (1), the bending strength of the coating/substrate is
calculated and presented in Fig. 8b and Table 2. Clearly, the MS Ni–P/Cu
exhibits a low bending strength of 534.5 MPa, ~50% lower than that of
the MS Ni/Cu (812.8 MPa). The GS Ni–P/Cu exhibits high bending
strength, but depending on the gradient profile. In particular, the
bending strength of the GS Ni–P/Cu II is 868.4 MPa, which not only far
surpasses that of the MS Ni–P/Cu but exceeds that of the MS Ni/Cu.
Fig. 9 shows fracture morphologies of the bending-tested coating/
substrate specimens. For the MS Ni–P/Cu, there is only one vertical
crack crossing through the coating (Fig. 9a), without any plastic defor­
mation (Fig. 9b). With a further increase in bending strain, the stress
concentration around the vertical crack tip also results in interfacial
crack initiation and propagation, responsible for the coating delamina­
tion (Fig. 9a). Conversely, the MS Ni/Cu could bear a high bending
strain without cracking at the interface or within the coating (Fig. 9c),
showing excellent interface adhesion. What is visible are multiple slip
bands at coating sides (Fig. 9c) and surface (Fig. 9d), indicating that the
ductile MS Ni coating experienced a large plastic deformation.
For the two GS Ni–P/Cu, cracks with a V-shaped profile are also
observed in the coatings (Fig. 9e and g), akin to the MS Ni–P coating.
However, the crack depths in the GS Ni–P I and GS Ni–P II coatings are
~430 and ~50 μm, respectively, indicating the evading through-
thickness cracking. The crack tips locate at the CG region with a grain
size of ~3 μm and ~1 μm for the GS Ni–P I and II coatings, respectively
(see Figs. 2 and 4b), implying that the propagation of cracks is arrested
Fig. 9. Side-view and plan-view fracture morphologies of the (a, b) MS Ni–P/Cu, (c, d) MS Ni/Cu, (e, f) GS Ni–P/Cu I, and (g, h) GS Ni–P/Cu II under bending. Insets
in (a, b, e, f, g, h) showing the morphology neighboring crack path. Inset in (c) is an enlarged SEM image showing slip bands left by plastic deformation of MS
Ni coating.
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Materials Science & Engineering A 844 (2022) 143170
in the CG region of the GS coatings. More importantly, the interface of
GS coating/substrate keeps intact, showing the good adhesion perfor­
mance under bending.
4. Discussion
The present work reveals that conventional electrodeposition can
yield a practical advance in creating gradient architecture with a broad
grain-size span and accurate control over gradient profile in Ni–P
coatings. Introducing the gradient structure in the coating could
significantly improve interfacial adhesion while maintaining high sur­
face hardness, and tailoring the gradient profile could further enhance
the adhesion performances. In the following, how gradient structure and
gradient profile affect the adhesion performances under shearing and
bending will be discussed. Moreover, given that our GS metallic coatings
combine the excellent interface adhesion and the superior coating sur­
face properties, we offer a brief prospect for the engineering application
of the GS Ni–P coatings.
4.1. Effect of gradient structure on the interface shear strength
According to the experimental results, the following reasons could
contribute to the improved adhesion performance in the GS coatings. (1)
There is excellent metallurgical bonding between the GS Ni–P coating
and the Cu alloy substrate. Epitaxial growth was allowed for our GS Ni–P
Y. Lin et al.
coatings electrodeposited on the Cu alloy substrate due to the unique
gradient structure design (i.e., transitioning from pure Ni to Ni–P alloy)
and the low lattice mismatch between the initial pure Ni deposits and
the Cu substrate. (2) Gradient structure has an advantage in accom­
modating stress/strain incompatibility between the coating and the
substrate during deformation. For the MS Ni–P coating, a larger hard­
ness difference (the hardness of substrate and coating are ~1.5 GPa and
~7.2 GPa, respectively, at two sides of the interface) causes the stress/
strain incompatibility at the interface during shearing and bending,
resulting in the crack initiation at the interface or interface delamina­
tion. Conversely, for the GS Ni–P coating, minor hardness discontinuity
across the interface (the hardness of substrate and coating are ~1.5 GPa
and ~1.8 GPa, respectively, at two sides of the interface) is beneficial for
accommodating the deformation of the interface region during shearing
and bending. (3) The deformation ability of Ni–P alloy is improved due
to the gradient structure, contributing to keeping the intactness of the
coating during deformation. This item will be further discussed below.
As revealed in the thin film/substrate system [41,42], the deforma­
tion capability of the interface region is vital to interface adhesion and
interface fracture resistance. The unique characteristic of the GS Ni–P
coatings is that their gradient structure transitions from soft-yet-ductile
Ni to hard-yet-brittle Ni–P alloy. The initial soft Ni layer can be
co-deformed well with the soft substrate, giving rise to the notable strain
hardening during deformation and ductile shearing in the Cu alloy side
(Fig. 7c). In contrast, no plastic deformation occurs in the interface re­
gion of MS Ni–P coating during shearing (Fig. 7b) because of the brit­
tleness of nanocrystalline/amorphous Ni–P alloy, leading to the failure
of MS Ni–P coating and interface delamination. In a word, the failure
mode transits from cracking or interface delamination to ductile tearing,
enabling the GS Ni–P coatings to evade poor adhesion of the MS Ni–P
coating and achieve the same strong adhesion as the MS Ni coating
during shearing.
For the coatings under bending, the brittleness of MS Ni–P coating
leads to easy initiation of cracks at the surface, followed by the through-
thickness cracking and interface delamination (Fig. 9a). For the GS Ni–P
coating, although bending-induced cracking occurs, the interface keeps
intact as all the cracks are not able to pass through the entire GS Ni–P
coatings (Fig. 9e and g). The crack arrest is attributed to the crack
blunting induced by plastic deformation of the CG region. This positive
role of gradient structure in arresting crack contributes to the excep­
tional damage tolerance for GS Ni–P coatings under bending [28,30,43,
44].
4.2. Effect of gradient profile on adhesion performances
The formation of gradient structure is the only first step while
patterning gradient profile plays a more significant role in manipulating
properties or functions. Regarding the shear loading, the interface
strength is mainly governed by the interface region. Recall that both GS
Ni–P I and II coatings have a ~100 μm thick layer of CG Ni that is
contiguous to the substrate, the shear strengths of two GS coatings are
identical and analogous to that of the MS Ni coating (Fig. 6). Therefore,
the gradient profile has no impact on the interface shear strength of GS
Ni–P coatings.
Conversely, gradient profile makes a significant difference in the
bending performance of GS Ni–P coatings. The interface region of two
GS coatings remains intact; however, the deformation behavior of the
coating is completely different. In contrast to the few deep cracks and
smooth surface presented in the bending-tested GS Ni–P I coating
(Fig. 9e and f), numerous shallow cracks and multiple shear bands near
the crack are observed in the GS Ni–P II coating (Fig. 9g and f), implying
that the surface layer has undergone plastic deformation before crack
initiation. Combining the excellent interface adhesion and the superior
plastic deformability, GS Ni–P/Cu II exhibits a bending strength larger
than that of the GS Ni–P/Cu I, and even surpasses that of the MS Ni/Cu.
In short, the GS Ni–P coating with proper regulation of gradient profile
8
Materials Science & Engineering A 844 (2022) 143170
can have extraordinary adhesion performance, and is much better than
the MS Ni–P coating and even superior to the MS Ni coating.
4.3. Hardness-adhesion synergy of GS Ni–P coatings: implication for
engineering applications
Hardness is of great importance for most protective metal coatings;
however, the traditional hard coating with a homogeneous structure is
usually inclined to encounter poor adhesion. In other words, there is a
trade-off between hardness and adhesion performance in metallic
coatings. In the present work, the surface hardness of the MS Ni–P
coating is ~6.7 GPa, 400% higher than that of MS Ni coating. However,
the interface shear and bending strengths are 154.7 MPa and 534.5 MPa,
50% and 20%, respectively, lower than those of the MS Ni coating,
following the above trade-off (Fig. 10). In contrast, our GS Ni–P coatings
simultaneously possess a high surface hardness of ~7.2 GPa, an inter­
face shear strength of ~280 MPa, and a bending strength over 730 MPa.
These results show that the adhesion performances of the Ni–P coating
have significantly been improved by tailoring a gradient structure
without compromising its high hardness. Namely, the superior hardness-
adhesion synergy has been achieved in our GS Ni–P coatings.
Regarding the coating structure design for practical application, the
findings in this study show that the gradient architecture has advantages
over the conventional MS nanocrystalline/amorphous and CG struc­
tures. For instance, the conventional hard chromium deposits have
relatively good adhesion (i.e., the interface shear is over 200 MPa [45]),
but are prone to suffer from interfacial cracking and through-thickness
cracking subjected to bending [46,47], significantly limiting their ap­
plications in the fields evolving bending impact. In contrast, our GS Ni–P
II coating, with a high surface hardness close to that of the hard chro­
mium deposit (~7–9 GPa [48,49]), can possess a superior adhesion
performance under shearing and bending, thus widening the application
fields.
It should be pointed out that the present work is only a starting point,
and the gradient structure of the GS Ni–P coatings can be further opti­
mized for withstanding more complicated service conditions. Taking the
GS Ni–P I coating as an example, it is still susceptible to the bending load
to some extent due to a higher volume fraction of brittle nanocrystalline
structure. This problem can be readily resolved by tuning the gradient
profile to that shown in the GS Ni–P II coating (i.e., a smaller volume
fraction of brittle nanocrystalline structure). The accurate control over
the gradient profile is one of the most attractive findings of this work.
Furthermore, the material class of the coating (e.g., Ni–W alloy [50,51],
Ni–W–P alloy [52], Ni–Co alloy [53] and Ni–Mo alloy [54, 55]) can be
readily enriched to acquire a more favorable surface function. As such,
we believe that our work provides a promising strategy for producing GS
metallic coatings with a combination of excellent surface properties (e.
g., high hardness) and strong interface adhesion. These GS metallic
coatings have the potential to replace hard chrome coatings and can be
used in various engineering fields (e.g., protective coatings of electro­
magnetic launching rail) that traditional coatings were incompetent.
5. Conclusions
In this work, the gradient-structured (GS) Ni–P coatings, with a wide
gradient spanning from the inner pure Ni to the outer Ni–P alloy, have
been successfully fabricated via electrodeposition. Based on the exper­
imental results of the adhesion performance for the coating/substrate (i.
e., the GS Ni–P coating on the CuCrZr alloy substrate), the main con­
clusions can be obtained:
1. A dual-gradient architecture was achieved in the Ni–P coatings, in
which the P content changes from 0 to ~9 at.%, and the corre­
sponding microstructure transitions from coarse columnar grains of
~6 μm to nanocrystalline/amorphous hybrids.
Y. Lin et al.
Fig. 10. Plots showing (a) the interface shear strength and (b) the bending strength as a function of the hardness of the coating surface.
2. Two measures of the adhesion performance showed that the GS Ni–P
II coating possessed an interface shear strength of ~280 MPa and a
bending strength of ~870 MPa, which are ~80% and ~60% higher,
respectively, than those of the MS Ni–P coating.
3. The generation of gradient structure can reduce stress/strain in­
compatibility and accommodate plastic deformation of the interface
region under shear loading, and can impart the exceptional crack
arrest capability to the coating, leading to enhanced adhesion per­
formances under both shearing and bending.
4. Gradient profile has no influence on the interface shear strength but
dramatically impacts the bending behavior of GS Ni–P coatings.
5. This work provides a promising methodology for producing GS
metallic coatings with the combinations of excellent surface prop­
erties (e.g., the high surface hardness) and strong interface adhesion,
and hence extends their engineering applications.
Data availability
Experimental data from this study are available from Prof. Lin Liu
and Prof. Jie Pan from Huazhong University of Science and Technology
upon reasonable request.
CRediT authorship contribution statement
Yan Lin: Investigation, Methodology, experiments, Writing – orig­
inal draft, Funding acquisition. Fenghui Duan: experiments, Writing –
original draft. Jie Pan: Formal analysis, Visualization, Writing – review
& editing, Funding acquisition. Cheng Zhang: Formal analysis, Visu­
alization. Qi Chen: Formal analysis, Visualization. Junyong Lu: Formal
analysis. Lin Liu: Resources, Supervision, Writing – review & editing,
Funding acquisition.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgement
This work is supported by the National Natural Science Foundation
of China (Nos. 92066202, 52001075, and 52022100), and funded by
China Postdoctoral Science Foundation (No. 2021M701290). Y. L. is also
grateful for support from GDAS’ Projects of the Construction of the
Domestic First-class Research Organization (2019GDASYL-0103074). J.
P. is also grateful for support from the Youth Innovation Promotion
Association of the Chinese Academy of Sciences (No. 2020194).
9
Materials Science & Engineering A 844 (2022) 143170
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