Chemical Papers (2023) 77:4399–4407

https://doi.org/10.1007/s11696-023-02790-8

ORIGINAL PAPER

Effect of limiting current density on corrosion performance of Ni–Mo,

Ni–Cd and Ni–Mo–Cd alloy coatings
Akshatha R. Shetty1 · A. Chitharanjan Hegde2

Received: 2 January 2023 / Accepted: 13 March 2023 / Published online: 23 March 2023
© The Author(s) 2023

Abstract
In this article an attempt was made to increase the corrosion resistance of Ni–Mo alloy coatings with the addition of small
quantity of C­ dCl2 into its bath. The limiting of limiting current density (iL) of Ni in both Ni–Mo and Ni–Cd baths due to
inherent induced and normal type of codeposition has been successfully alleviated by addition of 1 g/L of ­CdCl2. The advent
of induced and normal type of codeposition of individual binary baths has been used to optimize the Ni content of the ter-
nary deposit for better corrosion stability. The composition vs. current density plots of all coatings have been studied, and
thereby optimal iL of Ni in all baths were assessed. The content of Mo was found to be decreased with the small addition of
Cd to the bath. Results revealed that (Ni–Mo–Cd)6.0 Adm−2 coating showed better corrosion resistance by reducing iL of Ni,
on addition of ­Cd+2 ions into the bath and was explained in the light of diffusion limited deposition of ­Ni+2 ions. The results
were supported by SEM (scanning electron microscopy), XRD (X-ray diffraction) and AFM (atomic force microscopy) study
of Ni–Mo, Ni–Cd and Ni–Mo–Cd coatings at optimal current densities.

Keyword Ni–Mo · Ni–Cd · Ni–Mo–Cd · Corrosion study

Introduction is electroplating technology to enhance corrosion resistant

Corrosion is the deterioration of materials due to chemical
reactions with their environment. It is a significant prob-
lem in many industries, as it can cause structural failure
and equipment malfunction, leading to costly repairs and
potential safety hazards. Additionally, corrosion can also
lead to environmental pollution, as corrosion products can
leach into soil and water. It is important to prevent and con-
trol corrosion in order to maintain the integrity of structures
and equipment and to protect the environment. There are
several methods used to protect materials from corrosion,
such as environmental control, material selection (Uygur
et al. 2015; Gerengi et al. 2019, 2020) and inhibitors (Rizvi
et al. 2021) and coatings. One of the best methods followed
* Akshatha R. Shetty
Shetty.akshatha@manipal.edu
1
Department of Chemistry, Manipal Institute of Technology,
Manipal Academy of Higher Education, Manipal,
Karnataka 576104, India
2
Electrochemistry Research Lab, Department
of Chemistry, National Institute of Technology Karnataka,
Surathkal, Srinivasnagar 575025, India
properties of the base materials.
Ni–Mo alloy coating is of great interest due to their good
corrosion resistance (Yang et al. 2022) and their ability to
catalyse the hydrogen evolution reaction in alkaline solu-
tions (Goveas et al. 2018; Li et al. 2020; Huang et al. 2015).
Owing to their high corrosion resistance, they are consid-
ered to be a potential replacement for hard chrome coating
at lesser cost (Hu and Weng 2000; Wasekar et al. 2019).
Similarly, Ni–Cd coatings finds its extensive applications in
decorative finishing of metals and anticorrosive protection of
metals (Rao and Hegde 2014; Sriramana et al. 2021; Brenner
1963). It is well known that Ni–Mo and Ni–Cd alloys fol-
low induced and normal type of codeposition, respectively.
In both type of alloy deposition, change in the composi-
tion of coatings is negligible, or unpredictable with plating
variables. From a theoretical point of view, in Ni–Mo alloy
coating pure molybdenum (Mo) having EMo 0
= − 0.20 V
cannot be electrodeposited from their aqueous solution,
and it can be codeposited easily with iron group metals
such as nickel (Ni) forming an alloy. In Ni–Mo coatings,
Ni stimulate the deposition of reluctant metal Mo, which
do not deposit by itself. Ni–Cd coatings follows normal
type of codeposition, where Ni deposits preferentially than

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Vol.:(0123456789)
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Cd, which characterized by the preferential deposition of
noble Ni ( ENi
0
= − 0.25 V) instead of Cd ( ECd0
= − 0.40 V). In
induced type of electroplating, plating variables, like current
density (c.d.), temperature, agitation, pH etc. has vagarious
dependency on the composition of the bath compared to
other normal types of codeposition (Brenner 1963; Xu et al.
2016; Mousavi et al. 2016).
In preliminary study on electrodeposition of Ni–Mo and
Ni–Cd alloy coatings showed two peculiarities, in terms of
their Ni content: (i) Change of Ni content in Ni–Mo coat-
ing with c.d. is insignificant due to induced type of codepo-
sition, and (ii) Ni content of Ni–Cd alloy increases with
increase of c.d., due to normal type of codeposition. Even
at higher concentration of Ni in the bath, Ni content of the
alloy decreased with increase of current density, pH and
temperature, reasoned by the preferential deposition of less
noble metal (Cd). In other words, Ni content of the coating
is extremely low compared its content in the bath. In gen-
eral, corrosion protection ability of both Ni–Mo and Ni–Cd
alloy coatings depends upon their Ni (noble metal) content
(Eliaz and Gileadi 2008, Huang et al. 2015; Podlaha et al.
1996; Abd El Rehim et al. (1984); Liu and Anderson (1996;
Parthasaradhy 1989) and in alloy plating, the metal con-
tent depends on the liming current density (iL) of the metal.
Hence, it is very unlikely to develop coatings of high corro-
sion protection from both Ni–Mo and Ni–Cd alloy baths, by
changing the c.d. Hence, to alleviate the problem associated
with limiting c.d. of Ni in baths of Ni–Mo and Ni–Cd to
develop coatings of high corrosion resistance, electrodepo-
sition of their ternary alloy coating, i.e. Ni–Mo–Cd coating
have been tried. The advent of induced and normal type of
codeposition that the individual binary baths followed have
been used advantageously to optimize the Ni content of the
ternary alloy for better corrosion stability. The experimen-
tal results are presented, with an account responsible for
improved corrosion resistance of ternary alloy coatings. The
optimal Ni content of the alloy coatings have been identified.
Experimental observations are compared, in relation to its
binary alloy coatings, and results are discussed. The effect of
limiting current density on deposition mechanism of Ni–Mo,
Ni–Cd and Ni–Mo–Cd was studied.
Table 1  Composition and Chemical constituents (­ gL−1)
processing parameters of baths
used for electrodeposition of Nickel sulphate ­[NiSO4.6H2O]
Ni–Mo, Ni-Cd and Ni–Mo–Cd
Sodium molybdate
alloy coatings under constant
[Na2MoO4]
condition of temperature and
pH Sodium citrate
[Na3C6H5O7]
Cadmium chloride
[CdCl2]
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Chemical Papers (2023) 77:4399–4407
Experimental
Two binary alloy baths, namely Ni–Mo and Ni–Cd, were
optimized using conventional Hull method as described
elsewhere (Ganesan et al. 2006). The composition and pro-
cessing parameters of Ni–Mo, Ni–Cd and Ni–Mo–Cd alloy
baths are given in Table 1. Electrolytic baths were prepared
using LR grade (Merck, Mumbai, India) chemicals, as they
are purchased without further purification, using double dis-
tilled water. The desired pH’s were maintained using Micro
pH Meter (Systronics, 362), by proper addition of either
­NH4OH or HCl depending on the requirement. Table 1—
Composition and processing parameters of baths used for
electrodeposition of Ni–Mo, Ni–Cd and Ni–Mo–Cd alloy
coatings under constant condition of temperature and P ­ H.
All depositions reported here were carried out at constant
temperature (303 K), under condition of constant agitation
on copper substrate (7.5 × 3.0 cm), used as cathode. The cop-
per substrates, polished metallurgically to get mirror finish
were used for electroplating. It is degreased (trichloroethyl-
ene), and then pickled (1:1 H ­ NO3) before to immersing it
into electrolyte.
The depositions were carried out on known active surface
area (3.0 × 3.0 cm), leaving the other region covered by cel-
lophane tape. Both binary and ternary alloy electrodeposi-
tions were carried out under same geometric conditions of
anode and cathode, using 300 mL capacity cubic customized
electrochemical cell as shown in Fig. 1. Electrodepositions
were made at desired c.d.’s using DC power source (Power
Analyzer, N6705A, Agilent Technologies, USA). The pure
nickel plate was used as anode. All depositions were carried
out for 10 min. The cathode and anode were placed parallel
at 5 cm distance, during deposition. After electrodeposition,
all coatings were washed using distilled water followed by
air drying. The coatings were then analysed for its corrosion
behaviors.
The rate of corrosion was studied using controlled
Potentiostat/Galvanostat (VersaSTAT3, Princeton Applied
Research, USA). The three-electrode set up was used to
perform corrosion experiments. The corrosion tests were
carried in 5% NaCl solution at room temperature by
Ni–Mo bath Ni–Cd bath Processing parameters
16.0 16.0 Anode: nickel plate
46.0 – Cathode: copper
102.0 102.0 c.d. range:1.0–6.0 ­Adm−2
– 1.0 Temperature: 303 K
pH: 9.0
Duration: 10 min
Chemical Papers (2023) 77:4399–4407 4401

Table 2  Composition and corrosion performance of Ni–Mo, Ni–Cd

and Ni–Mo–Cd alloy coatings deposited from their optimal baths at
different c.d.’s

Coating configura- wt% Ni wt% Mo wt% Cd CR × ­10–2(mmy−1)

tion

Induced type of codeposition

(Ni–Mo ) 1.0 Adm−2 70.0 30.0 – 51.6
(Ni–Mo ) 2.0 Adm−2 69.0 29.0 – 40.5
(Ni–Mo )4.0 Adm−2 68.2 31.8 – 36.5
(Ni–Mo ) 6.0 Adm−2 67.0 33.0 – 30.7
Normal type of codeposition
(Ni–Cd)1.0 Adm−2 21.0 – 78.0 44.74
(Ni–Cd)2.0 Adm−2 56.9 – 43.1 42.94
Fig. 1  Schematic representation of set up used for electrodeposition (Ni–Cd)4.0 Adm−2 79.5 – 20.5 28.72
of alloy coatings (Ni–Cd)6.0 Adm−2 76.7 – 23.3 39.70
Anomalous Ternary alloy deposition
(Ni–Mo– 37 5.8 58.0 29.2
exposing a ­1cm2 surface area of the alloy coatings. The Cd)1.0 Adm−2
corrosion behaviours of alloy coatings were studied by (Ni–Mo– 27.0 5.4 60.8 24.4
electrochemical impedance spectroscopy (EIS) and poten- Cd)2.0 Adm−2
tiodynamic polarization methods. The surface morphol- (Ni–Mo– 17.1 4.9 68.6 16.5
Cd)4.0 Adm−2
ogy, composition and phase structure of Ni–Mo, Ni–Cd
(Ni–Mo– 13.9 4.4 70.7 15.4
and Ni–Mo–Cd alloy coatings were analysed using scan- Cd)6.0 Adm−2
ning electron microscopy (SEM), interfaced with energy Metal content in the bath
dispersive X-ray spectroscopy (EDS) (Oxford EDS(X- Wt of M in the 17.2 80.2 2.6 –
act), and X-ray diffraction study (XRD) (Rigaku- mini- bath
Flex 600), respectively. The surface roughness of the
coatings was measured using Atomic Force Microscopy
(AFM, Innova SPM Atomic Force Microscope). Binary Results and discussion
and ternary alloy coatings deposited at different c.d.’s are
conveniently represented as (Ni–Mo)x and (Ni–Cd)y and Electrodeposition of alloy coatings
(Ni–Mo–Cd)z alloys, with subscription x, y, z on right hand
side, indicating the c.d. at which they are deposited. Electrodeposition of binary (Ni–Mo and Ni–Cd) and ternary
Ni–Mo–Cd alloy coatings were done at different current
densities (ranging from 1.0 to 6.0 ­Adm−2) using electrolytic
Corrosion behaviour baths, shown in Table 1. The composition and corrosion
protection efficacy of alloy coatings corresponding to dif-
The corrosion rates were calculated by Tafel extrapolation ferent c.d.’s is given in Table 2. The actual metal contents in
methods, by scanning the test electrode in a potential ramp Ni–Mo, Ni–Cd and Ni–Mo–Cd baths, calculated from the
of ± 250 mV, at scan rate of 1 mV/sec. The Nyquist plots weight of Ni, Mo and Cd salts, are also shown in Table 2.
were drawn, using data corresponding to AC frequency in
the range of 100 kHz–10 mHz, with perturbing sine wave of Induced codeposition of Ni–Mo alloy
10 mV amplitude. The corrosion rate (CR) in millimetre per
year (mm y−1) was calculated using Eq. (1). To begin with, of Ni–Mo alloy deposition was carried out at
­ dm−2), using
four different c.d.’s (ranging from 1.0 to 6.0 A
E
CR = K × ×i (1) the bath shown in Table 1. From the composition data,
D Corr
shown in Table 2 it may be noted that there is no signifi-
Here, CR is expressed of milli meter per year (­ mmy−1), cant change in the Ni content of alloy with c.d. However,
Where K = 0.00327, E = Equivalent weight of the alloy, a small decrease of Ni content with c.d. clearly shows that
D = density of alloy under study and, icorr = corrosion cur- the bath followed the induced type of codeposition. It may
rent density in µAcm−2. be further noted that wt% Mo in the deposit is in the range
of ~ 30% at different c.d’s. studied as compared to its 80.2%
in the bath. At the same time, the deposit is having wt% of

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Ni in the range of (~ 70%) and was found to be higher, com-
pared to that in the bath (17.2%). A small variation of Ni and
Mo content in Ni–Mo alloy coatings, over the range of c.d.
studied was found (Table 2). It is the testimony for induced
type of codeposition, enabled due to possible complexation
of Mo and Ni ions with citrate ions (Parthasaradhy 1989).
Thus, from Table 2, it may be noted that a bright and uni-
form coating of Ni–Mo alloy coating corresponding to 6.0
­Adm−2, represented as (Ni–Mo)6.0 Adm−2 coating is the most
corrosion resistant, among others.
Normal codeposition of Ni–Cd alloy
Similarly, Ni–Cd alloy coatings depositions were carried
out at four c.d.’s, like 1.0, 2.0, 4.0 and 6.0 ­Adm−2, using
Ni–Cd bath shown in Table 1. The composition of the coat-
ings obtained at different c.d.’s are reported in Table 2, with
their corrosion rates. It is important to note that over entire
range of c.d. studied, wt% of Cd (less noble metal) in the
deposit is much more than that in the bath (Ganesan et al.
2006), compared to only 2.6% in the bath (Table 2). The
composition data of Cd in the bath indicates that the bath
follows normal type of codeposition with preferential depo-
sition of noble metal (Ni) with increase c.d (Kanani 2006).
The corrosion data reported in Table 2 reveals that cor-
rosion rate of Ni–Cd alloy coatings decreases with increase
of Ni content, affected at higher c.d. In other words, corro-
sion rate decreased with increase of Ni content. However, at
6.0 ­Adm−2, i.e. corresponding to (Ni–Cd)6.0 Adm−2 CR was
found to increase once again. It may be attributed to the
fact that applied c.d. has exceeded the limiting c.d. of Ni,
for bath under operation. Thus, a bright and uniform Ni–Cd
alloy coating corresponding to 4.0 A ­ dm−2, represented as
−2
(Ni–Cd)4.0 Adm showed better corrosion resistant property
as compared to all other coatings.
Anomalous codeposition of Ni–Mo–Cd alloy
Based on the corrosion performance of Ni–Mo and Ni–Cd
alloy coatings, and their dependency with c.d., an attempt
was made develop ternary alloy coatings of higher corro-
sion resistance by proper manipulation of its Ni content.
In this direction, a ternary Ni–Mo–Cd alloy coating was
attempted by adding small quantity (1.0 g/L) of ­CdCl2
into optimized Ni–Mo bath. The composition and oper-
ating variables used for deposition of Ni-Mo, Ni-Cd and
Ni–Mo–Cd alloy coating is as shown in Table 1. Ternary
alloy coatings were electroplated at various c.d.’s, like 1.0,
2.0, 4.0 and 6.0 ­Adm−2, and their corrosion performance
were evaluated. The composition and corrosion rates of
ternary Ni–Mo–Cd alloy coatings corresponding to differ-
ent c.d.’s are reported in Table 2. Hence, from corrosion
data reported in Table 2, it may be inferred that Ni–Mo–Cd
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Chemical Papers (2023) 77:4399–4407
alloy coating corresponding to 6.0 A ­ dm−2, represented as
−2
(Ni–Mo–Cd)6.0 Adm is the most corrosion resistant coating.
The data from Table 2 indicates that, with increase of current
density the content of less noble metal (cadmium) increases
and it inhibits the deposition of more noble molybdenum.
This proves that (Ni–Mo–Cd) coatings follows anomalous
type of electrodeposition.
Surface morphology and XRD study
The microstructure of (Ni–Mo) 6.0 Adm−2, (Ni–Cd) 4.0 Adm−2
and (Ni–Mo–Cd) 6.0 Adm−2 alloy coatings, showing the high-
est corrosion resistance of respective baths are shown in
Fig. 2. The poor corrosion resistance behavior of (Ni–Mo)
6.0 Adm
−2
alloy coating may be due to its rough surface, hav-
ing a granular structure as may be seen in Fig. 2a. The bet-
ter corrosion resistance of (Ni–Cd) 4.0 Adm−2 alloy coating,
compared to that of (Ni–Mo) 6.0 Adm−2 coating is due to a
decrease of surface roughness, seen in Fig. 2b. The least cor-
rosion rate of (Ni–Mo–Cd) 6.0 Adm−2 coating may be attrib-
uted to increased smoothness of coating, compared to both
binary alloys as seen in Fig. 2c. The surface morphology of
the corroded (Ni–Mo) 6.0 Adm−2 sample is given in Fig. 2d.
From the composition data (Table 2), it may be noted that
the smoothness of coatings has an inverse dependency on Ni
content of the alloy. Thus, the high corrosion resistance of
(Ni–Mo–Cd) 6.0 Adm−2 alloy coating is not attributed by its
Ni content of the alloy.
The phase analysis of optimal coatings was carried out
using XRD technique and is given in Fig. 3. The XRD peaks
corresponding to (Ni–Mo) 6.0 Adm−2, (Ni–Cd) 4.0 Adm−2 and
(Ni–Mo–Cd) 6.0 Adm−2 coatings, may be seen Fig. 3. The
plane of reflection (211), (310), (420) and (501) corresponds
to ­MoNi4 phase of Ni–Mo coatings (JCPDS no. 03-065-
1533). The plane of reflections (111), (200), (112) and (862)
confirms the formation of Ni–Cd coatings (Xu et al. 2016).
The plane of reflections (211) (130) (112) and (501) con-
firms the formation of Ni–Mo–Cd coatings.
Atomic force microscopy study
The atomic force microscopy (AFM) technique was used to
find the surface roughness of optimal coatings. The AFM
images corresponding to optimal (Ni–Mo) 6.0 Adm−2, (Ni–Cd)
−2
4.0 Adm and (Ni–Mo–Cd) 6.0 Adm−2 coatings as shown in
Fig. 4. From Fig. 4, it is clear that the surface roughness
of (Ni–Mo–Cd) 6.0 Adm−2 alloy coating is lesser than that of
(Ni–Mo) 6.0 Adm−2, (Ni–Cd) 4.0 Adm−2.
The average surface roughness (­ Ra) of (Ni–Mo) 6.0 Adm−2,
(Ni–Cd) 4.0 Adm−2 and (Ni–Mo–Cd) 6.0 Adm−2 coatings was
found to be 35.6, 27.7 and 23.0 nm, respectively. From the
AFM data, it is clear that coating (Ni–Mo–Cd) 6.0 Adm−2 was
Chemical Papers (2023) 77:4399–4407 4403

Fig. 2  SEM image of opti-

mal a (Ni–Mo) 6.0 Adm−2, b
(Ni–Cd) 4.0 Adm−2, c (Ni–Mo–
Cd) 6.0 Adm−2 and d (Ni–Mo)
−2
6.0 Adm coatings before and
after corrosion study, respec-
tively

The corrosion rates of electrodeposited coatings are

reported in Table 2. The polarization behavior of Ni–Mo,
Ni–Cd and Ni–Mo–Cd coatings, deposited only under
optimal conditions are shown in Fig. 5, for comparison
purpose. From the nature of the polarization plot, it may
be noted that (Ni–Mo–Cd)6.0 Adm−2 coatings is more cor-
rosion resistant than binary alloy coatings. This is further
supported by its highest Ecorr values as seen in Fig. 5. The
nature of the anodic curves of all three alloy coatings indi-
cates that the corrosion is more an anodic controlled (Elias
et al. 2016).

Electrochemical impedance spectroscopy (EIS) study

EIS technique is used for ranking coatings, quantifying coat-

Fig. 3  XRD analysis of (Ni–Mo) 6.0 Adm−2, (Ni–Cd) 4.0 Adm−2 and
(Ni–Mo–Cd) 6.0 Adm−2 coatings deposited under optimal conditions of
respective baths
found to be more resistant having a lower average surface
roughness value.
Potentiodynamic polarization study
The corrosion behavior of electroplated binary and ternary
alloy coatings were studied by the potentiodynamic polariza-
tion method and corresponding plots are as shown in Fig. 5.
ing breakdown, assessing interfacial reactions and for pre-
dicting the lifetime of coating and/or metal systems (Yaun
et al. 2010). The EIS responses of electrodeposited Ni–Mo,
Ni–Cd and Ni–Mo–Cd coatings, corresponding to their opti-
mal conditions are shown in Fig. 6. The equivalent circuit
has been simulated, and is shown in inset of Fig. 6. A close
agreement between the observed and simulated impedance
responses for (Ni–Mo–Cd)6.0A dm−2 coating was found. The
equivalent circuit diagram corresponding to coatings are
given in inset of Fig. 6 and values are listed in Table 3. It
may be seen confirmed from larger diameter of the (unfin-
ished) semicircle corresponding to (Ni–Mo–Cd)6.0Adm−2
coatings is more corrosion resistant than binary alloys.
Increased diameter of the semicircle suggests its better

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Fig. 4  AFM image of a

(Ni–Mo) 6.0 Adm−2, b(Ni–Cd)
−2
4.0 Adm and c (Ni–Mo–Cd)
−2
6.0 Adm coatings deposited
under optimal conditions of
respective baths

Fig. 6  Electrochemical impedance responses of electrodeposited (Ni–

Mo) 6.0 Adm−2, (Ni–Cd) 4.0 Adm−2 and (Ni–Mo–Cd) 6.0 Adm−2 coatings
Fig. 5  The Tafel plots of (Ni–Mo) 6.0 Adm−2, (Ni–Cd) 4.0 Adm−2 and deposited from their optimal baths at 303 K
(Ni–Mo–Cd) 6.0 Adm−2 coatings deposited from their optimal baths

Table 3  The charge transfer resistance (­Rct) value for obtained for
corrosion resistance. The charge transfer resistance (Rct) (Ni–Mo) 6.0 Adm−2, (Ni–Cd) 4.0 Adm−2 and (Ni–Mo–Cd) 6.0 Adm−2 coat-
ings
value of Ni–Mo–Cd coating is more as compared to Ni–Mo
and Ni–Cd coatings. This confirms that Ni–Mo–Cd coating Coating configuration Charge
is found be more corrosion resistant than binary coatings. transfer
resistance
(Rct) (Ohm)

(Ni–Mo )6.0A dm−2 190

(Ni–Cd)4.0A dm−2 398
(Ni–Mo–Cd)6.0A dm−2 454

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Chemical Papers (2023) 77:4399–4407
Fig. 7  Effect of current density on the composition of binary Ni–Mo
and Ni–Cd and ternary Ni–Mo–Cd alloy coatings, electrodeposited
from citrate bath at 303 K (horizontal lines represent the actual con-
tent of metal in the bath)
Effect of c.d. on the composition of deposited
coatings
Variation in wt% of M(metal) content (Ni, Mo and Cd) in
binary and ternary alloy coatings over a range of c.d. studied
is shown in Fig. 7. It may be noted that in Ni–Mo alloy coat-
ing, Ni content of the deposit is slowly decreasing with the
increase of c.d., as expected in induced type codeposition.
Corrosion data, reported in Table 2 clearly shows that c.d.
slightly effects the Ni content, and hence corrosion resist-
ance of the alloy coating as mentioned earlier. But in case of
Ni–Cd alloy coatings, Ni and Cd content has large depend-
ency with c.d. A sudden increase of Ni content was found
in the range of 2.0—4.0 ­Adm−2 (Fig. 7). The maximum Ni
(noble metal) content corresponding to 4.0 A ­ dm−2 indicates
that it is its approximate limiting current density for deposi-
tion of Ni in that bath.
Effect of addition of ­Cd+2
The essence of electroplating is charge transfer across the
electrode–electrolyte interface, and most importantly the
composition of deposit depends on the iL of ions involved.
Therefore, a profound understanding of the structure of dif-
fusion layer is important in electroplating, in terms the effect
of c.d. on the diffusion of ions and thickens of the diffusion
layer. The composition of deposit formed mainly depends
on concentration change of ions near the diffusion layer
and be explained by simple diffusion theory (Kanani 2006).
Therefore, at iL, the rate at which metal ions in Ni–Mo–Cd
alloy can deposit may be determined by diffusion and elec-
trical migration of the ions, and is proportional to their
4405
concentrations. Thus, by taking the advantage of diffusion
theory based iL of metal ions, it is possible to control the
Ni content of the alloy coatings, by proper modulation of
charge transfer process at EDL. In this study, the iL of Ni
was decreased to large extent by addition of small quantity
of ­Cd+2 ions into Ni–Mo bath. The C ­ dCl2 added in small
quantity (1 g/L) decreased the iL of Ni, and allowed the dep-
osition of ternary alloy coating of high corrosion resistance
as explained below.
It may be recalled that iL of a metal is the current density
at which rate of its deposition is maximum. At iL the con-
centration of metal ions near the electrode drops to zero,
and it depends only on the bulk concentration. Therefore,
iL of a metal in an electrolytic bath may be written in the
form of Eq. 2.
iL = nFDCB ∕ 𝛿 (2)
where n is the number of electrons per ion being trans-
ferred, F the Faraday constant (96,490 C/equivalent). CB is
the concentration of metal ions in bulk electrolyte and δ is
the thickness of diffusion layer. From the above relation, it
may be noted that in a given bath (as ­CB is constant), iL is
changing only by altering the thickness of the EDL. Thus, in
the light of above discussion, the inverse dependency of Ni
content with c.d. due to addition of ­Cd+2 ions into Ni–Mo
bath may be attributed to its decreased iL of Ni. Thus, ­Cd+2
ions reduced the iL of Ni greatly in Ni–Mo–Cd bath, in rela-
tion to that in (Ni–Mo) bath. In the present study, it may be
concluded that wt% of Ni in the deposit has decreased due
­ d+2 ions, and allow-
to decrease of its iL, due to addition of C
ing the bath to undergo anomalous ternary alloy deposition.
The decrease of iL of Ni in Ni–Mo–Cd alloy bath is due to
change in the charge transfer process at the EDL, affected
due to different complexation of process compared to that
in binary baths.
Hence, least corrosion rate of ternary Ni–Mo–Cd coating
is due to decreased iL of Ni due to addition of Cd into bath.
Hence, it may be noted that the corrosion performance of
binary and ternary alloy coatings need not always depends
more on the iL of noble metal, rather than the wt% of noble
metal in the deposit. Therefore, it may be concluded that
­Cd+2 ions acted as such agency to decrease the iL of Ni by
increasing thickness of diffusion layer. Representational dia-
gram showing the decrease of iL of Ni in Ni–Mo–Cd bath
affected due to addition C­ d+2 ions into Ni–Mo bath is shown
in Fig. 8, in relation to its value in Ni–Cd bath, following
normal codeposition; and Ni–Mo bath, following induced
type of codeposition. It may be seen from Fig. 8 that the dif-
fusion layer thickness (δ) corresponding to Ni–Mo–Cd bath
is much larger than that for Ni–Mo and Ni–Cd baths. This
increase of δ is due to change in the charge/mass transfer
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4406
Fig. 8  Representational diagram showing the decrease of liming cur-
rent density (iL) of Ni responsible for anomalous type of codeposition
in ternary Ni–Mo–Cd alloy plating affected due to addition Cd into
Ni–Mo bath (induced type of codeposition), in relation to iL of Ni–Cd
bath (normal type of codeposition)
process at diffusion layer due to addition of ­Cd+2 ions into
the bath.
Conclusions
The experimental investigation to understand the effect of
addition of Cd into Ni–Mo bath on the corrosion protection
efficacy of Ni–Mo–Cd alloy coatings, following observa-
tions were made as conclusions:
(1) Ni–Mo–Cd alloy coatings of better corrosion perfor-
mance, than both Ni–Mo and Ni–Cd alloy coatings can
be developed on addition of small quantity C ­ dCl2 into
Ni–Mo bath.
(2) The limitation of high limiting current density (iL) of
Ni of both Ni–Mo and Ni–Cd baths, due to inherent
induced and normal type of codeposition has been suc-
cessfully alleviated by adding of ­CdCl2.
(3) The advent of induced and normal type of codeposition
of Ni–Mo and Ni–Cd baths, respectively, have been
used advantageously to optimize the Ni content of the
ternary alloy for better corrosion stability.
(4) The composition versus current density (c.d.) plots of
alloy coatings have been studied, and optimal iL of Ni
in three baths were assessed.
(5) Experimental investigation revealed that (Ni–Mo–
Cd)6.0 Adm−2 coating shows highest corrosion resistance
13
Chemical Papers (2023) 77:4399–4407
due to decrease of iL of Ni, affected due to addition of
­Cd+2 ions into the baths.
(6) The decrease of iL of is due to change of charge transfer
process at the electrical double layer (EDL), affected
by the addition of Cd ions into the bath.
(7) The corrosion performance of binary and ternary alloy
coatings always depends more on the iL of noble metal,
rather than the wt% of noble metal in the deposit.
Acknowledgements The authors are thankful to National Institute of
Technology, Karnataka for providing lab facility to carry out research
work.
Funding Open access funding provided by Manipal Academy of
Higher Education, Manipal.
Declarations
Conflict of interest The authors declare that they have no conflict of
interest.
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