Applied Surface Science 242 (2005) 326–332

www.elsevier.com/locate/apsusc

Microstructure and tribological properties of

electrodeposited Ni–Co alloy deposits
Liping Wanga,b, Yan Gaoa,b, Qunji Xuea, Huiwen Liua, Tao Xua,*
a
State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics,
Chinese Academy of Sciences, Lanzhou 730000, PR China
b
Graduate School of the Chinese Academy of Sciences, Beijng 100039, PR China
Received in revised form 24 August 2004; accepted 30 August 2004
Available online 20 October 2004

Abstract

Ni–Co alloys with different compositions and microstructures were produced by electrodeposition. The effects of Co content
on the composition, surface morphology, phase structure, hardness and tribological properties of Ni–Co alloys were investigated
systemically. Results showed that the morphology and grain size of alloys are mainly influenced by the Co content and the phase
structure of Ni–Co alloys gradually changed from fcc into hcp structure with the increase of Co content. The hardness of Ni–Co
alloys with a maximum around 49 wt.% Co followed the Hall–Petch effect. It was found that the improvement of wear resistance
of Ni-rich alloys with hardness increase fits Archard’s law. In addition, the Co-rich alloys exhibited much lower friction
coefficient and higher wear resistance when compared with Ni-rich alloys. It has been concluded that hcp crystal structure in Co-
rich alloys contributed to the remarkable friction–reduction effect and better anti-wear performance under the dry sliding wear
conditions.
# 2004 Elsevier B.V. All rights reserved.

Keywords: Ni–Co alloy; Electrodeposition; Structure; Tribological properties

1. Introduction activity [1–5]. Additionally, the use of Ni–Co alloys

Ni–Co alloys have been investigated as important
engineering materials for several decades because of
their unique properties, such as high-strength, good
wear resistance, heat-conductive, electrocatalytic
* Corresponding author. Tel.: +86 931 496 8169;
fax: +86 931 496 8169.
E-mail address: lpwang@lsl.ac.cn (T. Xu).
has been extended to the production of three-
dimensional, complex-shaped finished components
by the electroforming technique [6,7]. The investiga-
tions on the electrodeposited Ni–Co alloys have
shown that their microstructure and properties were
found to depend strongly on the Co content, which can
be controlled by the experimental parameters, such as
bath composition, temperature, pH value, and current
density, etc. [1,3,8]. The effects of plating parameters

0169-4332/$ – see front matter # 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.apsusc.2004.08.033
 L. Wang et al. / Applied Surface Science 242 (2005) 326–332
on the composition and morphology of Ni–Co
deposits were compared in many literatures [4,5,9].
Golodnitsky et al. recently studies the effects of Co
content on the tensile strength, internal stress and
high-temperature oxidation of Ni–Co alloys [3]. Their
activities for the oxygen evolution reaction and
hydrogen evolution reaction were also studied on
electrodeposited Ni–Co ultramicroelectrodes [10,11].
Moreover, much interest is focused on the magnetic
properties of Ni–Co alloys due to the application of
these alloys in various magnetic devices, especially in
microsystem technology for manufacture of sensors,
actuators and inductors [12,13]. It is reported that the
magnetic properties of Ni–Co alloy are greatly
influenced by the composition and phase structure
of Ni–Co alloy [14]. Unfortunately, there are very
limited studies focused on the friction and wear
properties of Ni–Co alloys as a function of their
microstructure and composition.
In the present paper, Ni–Co alloys with different Co
content were electrodeposited on AISI-1045 steel
substrates. The composition, microstructure, mechan-
ical, and tribological properties of Ni–Co alloys were
compared systemically in order to specifically
correlate the structure and tribological properties of
Ni–Co alloys.
2. Experimental
Ni–Co alloys were electrodeposited from a typical
Watts-type electrolyte, containing Nickel sulfate
(200 g/l), sodium chloride (20 g/l), boric-acid (30 g/
l), sodium lauryl sulfate (0.1 g/l) and cobalt sulfate (0–
80 g/l). In addition, pure Ni was also produced for
comparison purpose. The Ni–Co alloys were depos-
ited on AISI-1045 steel substrates by choosing a
current density of 3 A/dm2 at a bath temperature of
45 8C. The anode was a pure Ni plate. The pH of the
bath was kept at 4.0 adjusted by ammonia water or
dilute sulfuric-acid. Before deposition, the substrates
were mechanically polished to a 0.10–0.12 mm
surface finish, the substrate was then degreased in
acetone with ultrasonic cleaning for 5 min, rinsed in
the running water to remove contamination on the
substrate surface. After than, the steel substrates were
activated for 20 s in the 20 vol.% HCl solution, and
finally rinsed with distilled water.
327
The surface morphology and microstructure of the
alloy deposits were investigated using a JSM-5600Lv
scanning electron microscopy (SEM). The composi-
tions of Ni–Co alloys were determined with energy
dispersive X-ray spectroscopy (EDS) analysis tool
attached to SEM. The crystal structure and phase
composition of alloy deposits were studied by X-ray
diffraction (XRD). Microhardness of the deposits was
determined using a Vicker’s microhardness indenter
with a load of 50 g for 10 s, indentations were made on
the 50 mm thick deposits. The final value quoted for
the hardness of a deposit was the average of 10
measurements.
The tribological behavior was tested on a
reciprocating ball-on-disk UMT-2MT tribometer
(Center for tribology, Inc., California, USA) at room
temperature with a relative humidity of 45–55% under
dry sliding conditions. AISI-52100 stainless steel ball
(diameter 4 mm with hardness of RC 62) was used
as the counter body; all tests were performed under a
load of 3 N with a sliding speed of 55 mm s
1. The
friction coefficient and sliding time were recorded
automatically during the test. The wear volume loss
was measured using a surface profilometer, wear rates
of all the alloy deposits were calculated using the
equation of K ¼ V=SF, where V is the wear volume
loss in mm3, S the total sliding distance in m and F the
normal load in N.
3. Results and discussion
3.1. Composition of Ni–Co alloys
The dependence of the composition of Ni–Co alloys
on the concentration of Co2+ ions in the electrolyte at a
fixed concentration of Ni2+ ions is presented in Fig. 1. It
is clearly observed that the Co content in alloy deposits
increased gradually with the increase of Co2+ con-
centration in the electrolyte. Note that the percentage of
Co in the alloys was always higher than in the
electrolyte in agreement with [3,5], which is confirmed
by the anomalous codeposition of Ni–Co alloy. Namely,
the less noble metal (Co) is preferentially deposited. A
generally accepted explanation for these anomalous
phenomena was the change of the near-electrode pH,
the formation of metal hydroxyl and their competitive
adsorption [15,16].
328 L. Wang et al. / Applied Surface Science 242 (2005) 326–332

Fig. 1. The alloy compositions as a function of Co2+ concentrations

in the baths.

3.2. Morphology and phase structure of Ni–Co alloys

Typical surface morphologies of Ni–Co alloys with

different Co content are shown in Fig. 2b–f,
respectively. Fig. 2a shows a typical morphology of
a Watt Ni deposit, which has relatively large grain size
(3–10 mm) and showed polyhedral crystallites.
Sequentially increasing Co content from 7 to
49 wt.% (Fig. 2b–d) results in a gradual decrease in
the grain size of the Ni–Co alloy down to a sub-micron
grain size. When the Co content reached the 49 wt.%,
close observation of SEM morphology at high-
magnification (Fig. 2g) revealed that the Ni–Co alloys
have spherical cluster surface piled with a large
number of equally sized grains with spherical-shape.
At above 49 wt.% Co, the grain size of Ni–Co
deposits, however, increased with the increase of Co
content in alloys. When increasing Co content up to
81 wt.%, the morphology of the Ni–Co alloys changes
dramatically, and with less compact structure, the
Ni–Co alloy showed a rather regularly branched
structure with extended acicular 3–6 mm length
crystallites (Fig. 2f).
The phase composition and structure of pure Ni and
Ni–Co alloys with different Co contents were
investigated using XRD shown in Fig. 3. As can be
seen from Fig. 3a, the pure Ni deposit exhibits face-
centered cubic (fcc) lattice with remarkable (2 0 0)
growth orientation, which can be attributed to the
Fig. 2. SEM morphologies of Ni–Co alloy deposits with their Co
contents of (a) 0 wt.%, (b) 7 wt.%, (c) 27 wt.%, (d) 49 wt.%, (e)
66 wt.%, (f) 81 wt.%, (g) high-magnification of Ni–49 wt.% Co
alloy.
largest grain size of pure Ni. With the codeposition of
Co, the Ni–Co solid solution was formed. As can be
seen in Fig. 3b–f, both the crystal structure and phase
composition are mainly dependent on the Co contents
in alloys. For the Ni-rich alloys with Co content lower
than 49 wt.%, the Ni–Co alloys show complete fcc
phase structure, which is in agreement with previously
reported results [2,3]. Furthermore, the (1 1 1) growth
orientation gradually increased with the increase of Co
content, and the FWHM of the Bragg line for the
(1 1 1) peak also increased correspondingly, which is
in accordance with the gradual reduction of grain size
when increasing the Co content from 0 to 49 wt.% in
Ni–Co alloys as shown in Fig. 2b–d. Moreover, when
 L. Wang et al. / Applied Surface Science 242 (2005) 326–332
Fig. 3. XRD patterns of Ni–Co alloy deposits with their Co contents
of (a) 0 wt.%, (b) 7 wt.%, (c) 27 wt.%, (d) 49 wt.%, (e) 66 wt.%,
(f) 81 wt.%.
the Co content was increased to 66 wt.%, the presence
of (1 0 0) peak demonstrated the initial formation of a
hexagonal close packed (hcp) lattice, indicating that
the crystal structure of the Ni–Co alloy changed from
complete fcc lattice into a mixed (majority of fcc) +
(minority of hcp) phase as shown in Fig. 3e. At above
Fig. 4. Microhardness as function of Co content (a) and d
0.5 (b) of the Ni–Co deposits.
329
81 wt.%, as shown in Fig. 3f that a very strong hcp
(0 0 2) texture with pronounced (1 0 0) and (1 1 0)
peaks were observed, which is commonly observed in
both conventionally electrodeposited Co and nano-
crystalline Co [17,18]. Therefore, it can be concluded
that the phase structure of Ni–Co alloys gradually
changed from fcc into hcp with the increase of Co
content as shown in Fig. 3.
3.3. Microhardness of Ni–Co alloy deposits
Fig. 4a presented the microhardness of Ni–Co
alloys as a function of Co content in alloys. It is clearly
that microhardness of Ni–Co alloys increased initially
with Co content varying from 0 to approximately
49 wt.%, and then gradually decreased as Co content
increased further above 49 wt.%. The explanation to
this gradual reduction of microhardness is the gradual
increase of grain size with the increase of Co content
in Co-rich alloys as shown in Fig. 2e–f. Note that the
microcrystalline Ni–Co alloys show the maximum
hardness at approximately 49 wt.% Co, which can be
associated with the smallest grain size as mentioned in
microstructure analysis sector.
Normally, strengthening of polycrystalline materi-
als by grain size refinement is technologically
attractive because it generally does not adversely
affect ductility and toughness [19], which can be
represented by the classical Hall–Petch effect:
H ¼ H0 þ kd
0:5 (1)
where H0 is hardness constant, k constant, and d
diameter of grain. The hardness change with average
grain size (d) of the Ni–Co deposits is shown in Fig. 4b
330 L. Wang et al. / Applied Surface Science 242 (2005) 326–332
in the form of a Hall–Petch plot. It is obvious that the
Ni–Co alloy deposits exhibit a nearly constant Hall–
Petch gradient; such a relationship has also been
observed on pure Ni, pure Co and pure Zn from other
studies [20,21].
3.4. Friction and wear properties
The effect of Co content on friction coefficient of Ni–
Co alloys were shown in Fig. 5. It is observed that the
friction coefficient of pure Ni and Ni–Co alloys with Co
content lower than 49 wt.% (Ni-rich alloys) were quite
close. With the further increase of Co content, the Co-
rich alloys showed excellent friction–reduction beha-
vior. The Co-rich alloy deposit with Co content higher
than 81 wt.% exhibited the smallest friction coefficient
(more than two times lower than Ni and Ni-rich alloys),
followed by Ni–66 wt.% Co alloy (a litter lower than Ni
and Ni-rich alloys) under identical wear test conditions.
In addition, the friction coefficients of Co-rich alloys
were much more stable than that of Ni-rich alloy
deposits (see Fig. 6). Combined with the XRD analysis,
the close friction coefficient for Ni and Ni-rich alloy can
be attributed to the same fcc crystal structure they have.
In case of Ni–66 wt.% Co alloy, a mixed fcc/hcp phase
with smaller ratio of hcp phase structure led to the
gradual reduction of friction coefficient. Furthermore, as
for the Ni–81 wt.% Co alloy, dramatic reduction of
friction coefficient was observed due to the higher ratio
of hcp phase structure. Hence, we can conclude that the
reduction in friction coefficient of Co-rich alloys with
Fig. 5. Friction coefficient as function of Co content in the Ni–Co
alloy deposits.
Fig. 6. The comparison of friction coefficients vs. sliding time
between Ni-rich and Co-rich alloy deposits.
the increase of Co content can be associated with the
change of crystal structure from fcc to hcp crystal phase.
The variation of the wear rates of Ni–Co alloys as a
function of Co content and microhardness of alloys are
shown in Fig. 7. It is observed that all Ni–Co alloy
deposits in this study have lower wear rates when
compared with pure Ni deposit. Moreover, the wear
rate of Ni–Co alloys slowly decreased with the
increase of Co content from 6 to 49 wt.%. It is clear
that when the Co content is lower than 49 wt.%, the
gradual decrease of wear rates with the increase of Co
content was attributed to the microhardness increase
from 315 to 462 HV. Above improvement of wear
resistance with hardness increase, in this study due to
the grain size reduction, could be expressed using
Archard’s law mostly used in adhesive wear condi-
tions [22,23], since the wear mechanism of Ni and
Fig. 7. Wear rates as function of Co content in the Ni–Co alloy
deposits.
 L. Wang et al. / Applied Surface Science 242 (2005) 326–332
Ni-rich deposits is mostly the adhesive wear as
evidenced by SEM morphology of worn surface in
Fig. 8a and b. Thus, the Archard’s law can be
expressed as:
LN
Q¼K (2)
H
where Q is the volumetric wear loss, N the applied
load, L the total sliding distance, K the wear coefficient
and H the hardness of the wear surface. Under the
same wear conditions, the wear rate is proportional to
the inverse microhardness of materials. The data of
wear rate for microcrystalline Ni–Co alloys with Co
content lower than 49 wt.% fit Archard’s law very
well. However, with further increase in Co content
above 49 wt.%, the wear rates of Co-rich alloys
decreased rapidly in spite of the fact that the hardness
also decreased. The wear rate of Co-rich alloy with
approximately 81 wt.% Co content is more than one
order of magnitude lower than that of pure Ni and Ni-
rich alloys. This reverse-Archard law may be caused
by special hcp crystal structure of Co-rich alloys. This
agree well with the reduction in friction coefficient for
Co-rich alloys, namely, the lower and stable friction
coefficient of Co-rich alloys caused by hcp phase
structure resulted in the less wear loss, while the
Fig. 8. Worn surface of Ni–Co alloy deposits: (a) 0% Co; (b) 27% Co; (c) 81% Co.
331
higher friction coefficient of Ni-rich alloys due to
fcc phase structure led to the more wear loss. More
important is the fact that the Co-rich alloys exhibited
excellent wear resistance and anti-friction behavior.
The difference in the wear behavior of Ni–Co
alloys can be further verified by the worn surface
morphologies of Ni-rich and Co-rich deposit as shown
in Fig. 8a–c. For the pure Ni deposit and Ni-rich alloy
with completely fcc crystal structure, the wear track
(Fig. 8a and b) shows the larger extent of adhesion
wear and severe deformation in the sliding direction
under the combined stresses of compression and shear,
which results in larger wear rate of pure Ni and Ni-rich
alloys. Furthermore, larger tendency for plastic
deformation, this in turn increased the probability
of formation of asperity junctions resulting in higher
and unstable friction coefficient for Ni and Ni-rich
alloys. Compared with pure Ni and Ni-rich alloys, a
densification of the worn surface of Co-rich alloy
seems to take place, the worn surface of Co-rich alloy
with hcp crystal structure revealed slight adhesion
wear and rather smooth surface with smaller damaged
regions, only some light grooves and scars are noted
on the worn surface (Fig. 8c). This resulted in the
better wear resistance of Co-rich alloy than Ni-rich
alloys. That is also the reason why the friction
332 L. Wang et al. / Applied Surface Science 242 (2005) 326–332
coefficients of Co-rich alloys were much more stable
and more than two times lower than that of Ni and
Ni-rich alloys. It is evident that the high the amount of
hcp phase structure, the better the friction and wear
behavior will be. Above evidence suggests that the
crystal structure is indeed a dominant factor, which
influences the friction and wear behavior of Ni–Co
alloys. Hence, it clearly demonstrates that hcp crystal
structure in Ni–Co alloys contributed to the remark-
able friction–reduction effect and better anti-wear
performance of Co-rich alloys.
4. Conclusions
(1) The Co content in Ni–Co alloys increased
gradually with the increase of Co2+ concentration
in the electrolyte, which is confirmed by the
anomalous codeposition of iron group metals.
(2) Surface morphology of Ni–Co alloys changed
from regularly polyhedral crystallites into sphe-
rical cluster surface when increasing Co content
from 7 to 49 wt.% and the morphology of the
Ni–Co alloys with 81 wt.% Co showed a rather
regularly branched structure. Both the crystal
structure and phase composition are mainly
dependent on the Co content in alloys. The phase
structure of Ni–Co alloys gradually changed from
fcc into hcp with the increase of Co content.
(3) Microhardness of Ni–Co alloys increased initially
with Co content increasing from 0 to approxi-
mately 49 wt.%, and then gradually decreased as
Co content increased further above 49 wt.%. The
hardness change of Ni–Co with grain size follows
Hall–Petch effect.
(4) For the Ni-rich alloys, the improvement of wear
resistance with hardness increase fits Archard’s
law. In addition, the Co-rich alloys exhibited
much lower friction coefficient and higher wear
resistance than Ni-rich alloys. It has been
suggested that hcp crystal structure in Co-rich
alloys contributed to the remarkable friction–
reduction effect and better anti-wear performance.
Acknowledgements
The authors gratefully acknowledge the National
Natural Science Foundation of China (Grant No
50172052, 50271080 and 50323007), the 863 Program
of China (No. 2003AA305670), and ‘Top Hundred
Talents Program’ of Chinese Academy of Sciences for
financial support of this research work.
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