JMEPEG (2021) 30:2409–2421 ASM International

https://doi.org/10.1007/s11665-021-05462-4 1059-9495/$19.00

Effect of Electrolyte pH on Microstructure, Corrosion

Behavior, and Mechanical Behavior of Ni-P-W-TiO2
Electroplated Coatings
Sajjad Sadeghi and Hadi Ebrahimifar

Submitted: 25 April 2020 / Revised: 20 December 2020 / Accepted: 29 December 2020 / Published online: 24 February 2021

Ni-P-W composite coatings are resistant to wear and corrosion. TiO2 particles are used as a reinforcing
phase in the matrix of alloy coatings for abrasive applications. In this study, Ni-P-W-TiO2 coating was
precipitated on the AISI 304L steel substrate using an electroplating method. Electroplating was performed
at pH levels of 1, 2, and 3, and the effect of bath pH on microstructure, corrosion behavior, and wear
behavior was investigated. The coatings were characterized by scanning electron microscopy. In order to
investigate corrosion resistance, potentiodynamic polarization and electrochemical impedance spectroscopy
(EIS) tests were used in 3.5 wt.% NaCl aqueous solution. The mechanical behavior of the coated samples
was investigated by examining wear resistance and micro-hardness. The results of potentiodynamic
polarization and EIS tests demonstrated the coating formed at pH = 2 had the highest corrosion resistance
(7058 X cm2) compared to the coated sample at pH = 1 (57 X cm2) and pH = 3 (10.59 X cm2). Also, the
results of the wear and micro-hardness test showed composite coating formed at pH = 2 had the highest
wear resistance and micro-hardness (677 Vickers) compared to the coated sample at pH = 1 (403 Vickers)
and pH = 3 (511 Vickers).

In another study, Ni-W-P coatings were electrodeposited on

Keywords electrochemical impedance spectroscopy,
Ni-P-W-TiO2 coating, pH, potentiodynamic copper substrates by pulse electroplating. Effects of electrolyte
polarization, wear resistance pH (1-3), temperature (40-80 C), average current density (1-7
A/dm2), and pulse frequency (200-1000 Hz) on deposition rate,
structure, and corrosion resistance performance of Ni-W-P
coatings were studied by single-factor method. The results
showed the optimized parameters of pulse electroplating Ni-W-
P coatings were as follows: pH 2.0, temperature 60 C, average
1. Introduction current density 4 A/dm2, and pulse frequency 600 Hz. The Ni-
W-P coating prepared under the optimized parameters had
Among oxidation and corrosion-resistant alloys as well as superior corrosion resistance (276.8 kX) and compact surface
chromium-based alloys, especially austenitic stainless steels, without any noticeable defect (Ref 5).
are preferred due to their low cost and high ductility (Ref 1). Simultaneous deposition of solid particles in the matrix of
One of the weaknesses of these steels is their low wear nickel-phosphorus coating can improve mechanical and corro-
resistance, which is considered as the main threat to the life of sion properties of coating. Secondary particles of TiO2, Al2O3,
the part, energy consumption, and performance (Ref 2). One of SiC, CeO2, and Fe2O3 can be used to improve the wear
the best effective ways for improving wear resistance and high resistance and increase the stiffness of nickel-based coatings
hardness is to apply surface coatings. These coatings include (Ref 3). The coating created by TiO2 particles has good wear
nickel-based alloy and composite coatings (Ref 3). resistance, low coefficient of friction, high hardness, and heat
Nickel-phosphorus coatings are preferred over other coat- resistance; it also creates a surface with solid lubrication (Ref 6,
ings due to their high hardness, good corrosion resistance, good 7).
wear resistance, and lower cost. Adding tungsten can improve Saravanan et al. investigated the wear behavior of electro-
the properties of the coating. Kundu et al. evaluated the effect less Ni-P and Ni-P-TiO2 composite coatings on En8 steel. Their
of operating temperature on the tribological behavior of results showed adding TiO2 ceramic particles to Ni-P coating
electroless Ni-P-W coating developed over mild steel. Their improved the wear resistance (Ref 8).
results showed the incorporation of tungsten increased the as- Also, corrosion resistance of electroless Ni-P-SiC/Ni-P-
deposit hardness (670 HV0.1) of Ni-P coatings besides improv- TiO2-ZrO2 nano-coatings was investigated by Ram et al. Their
ing its crystallinity (Ref 4). results exhibited resistance against corrosion in the following
order: Ni-P-TiO2-ZrO2 as-plated > Ni-P-SiC as-plated >
Sajjad Sadeghi, Department of Materials Engineering, Faculty of SS316L (Ref 9-14).
Mechanical and Materials Engineering, Graduate University of In the present study, the Ni-P-W-TiO2 composite coating on
Advanced Technology, 7631133131 Kerman, Iran; and the AISI 304L austenitic stainless steel was deposited by
Hadi Ebrahimifar, Department of Materials Engineering, Faculty of electroplating. Afterward, the effect of bath pH on the amount
Mechanical and Materials Engineering, Graduate University of
Advanced Technology, 7631133131 Kerman, Iran. Contact e-mail:
of particles in coating, microstructure, corrosion behavior, and
H.Ebrahimifar@kgut.ac.ir. wear behavior of the coating was investigated. Scanning

Journal of Materials Engineering and Performance Volume 30(4) April 2021—2409

electron microscopy (SEM) was used to observe the morphol- ments were performed using an AutoLab PGSTAT302N
ogy. To investigate the abrasive behavior of these coatings, a Potentiostat. Before any testing, each sample was connected
pin on disk test was performed. to a copper wire and, then, sealed with epoxy resin. The sample
surface was then prepared to be exposed to the solution, and the
samples were thoroughly rinsed with distilled water and dried
with acetone. Also, before performing the electrochemical tests,
2. Materials and Methods the samples were immersed in the 3.5 wt.% NaCl solution for 1
h in order to establish the equilibrium potential conditions.
In this research, AISI 304L stainless steel with chemical The open-circuit potential of the samples was recorded for
composition of 19.7% Cr, 2% Mn, 0.85% Si, 0.031% C, 0.04% 60 min. After 60 min of immersion and reaching the steady
S, and 0.04% P with Fe as remaining, was used. potential, electrochemical impedance spectroscopy (EIS) test
First, AISI 304L stainless steel sheet was cut using a wire was carried out.
cutter with the dimensions of 3mm910mm910mm. A 0.7- EIS measurements in the corrosion potential, Ecorr, and in
mm-diameter wire was connected to one side of the sample, the 102-105 frequency range were plotted with the excitation
and the connection was insulated using thermal glue. In the amplitude of 5 mV per sample. Nova and Zview software were
next step, SiC sandpaper with numbers 60, 120, 200, 500, 800, used in the impedance tests. Nova software is used as an
1000, and 1200 was employed to polish the samples. In order interface between an impedance device and a computer, and the
for dehydration, the sample was first washed with soap and information obtained by the device is converted into numerical
water solution and, then, placed in the acetone solution. To information. To analyze the results obtained from Nova, the
activate the surface, the samples were electropolished in a information obtained from this software was transferred to
solution containing 10% phosphoric acid for 2 min at the Zview software and Zview was employed to analyze the data.
current density of 80 mA cm-2. After removing the samples The impedance spectra were analyzed by Zview software and,
from the electropolish solution, the surface was thoroughly finally, the equivalent circuit of the corrosion process was
washed with distilled water and immediately placed in a plating proposed.
bath for coating. To prepare the bath, the metal salts were first Potentiodynamic polarization test was performed on the
poured into water and dissolved by a full magnetic stirrer. samples 15 min after EIS test in the potential range of 100 mV
Sodium citrate, sodium hypophosphite, boric acid, and phos- less than the open-circuit potential up to 100 mV above the
phoric acid were added to the bath, respectively. TiO2 was open-circuit potential with the potential sweep rate of 1 mV/s.
eventually added to the bath. Afterward, the solution was All the electrochemical tests were performed in the laboratory
stirred for 6 h to stabilize by a magnetic stirrer. Sodium at 25 C. To determine the electrochemical parameters of the
hydroxide and sulfuric acid were used to adjust the pH. All the polarization test and calculate the corrosion current density
experiments were performed on 100 ml of plating solution. A (Icorr), Tafel extraction method was used. For this purpose, the
nickel plate measuring 2 mm 9 20mm 9 20 mm was used as linear parts of the anodic and cathode branches were used in
the anode, which was connected to the positive pole. Samples polarization diagrams and the values of Ecorr and icorr were
were electroplated in a Watts bath at the pH of 1, 2, and 3. After extracted directly from the intersection of these two branches.
plating, the samples were rinsed twice with distilled water and In order to investigate the wear resistance of the coatings,
dried using hot air flow. The composition of the plating bath is the wear test was performed through the pin on disk method
given in Table 1. according to the ASTM G99 standard. The pin was uncoated or
The SEM model of Cam scan MV 2300 equipped with EDS coated sample, and the used disk was made of 5100 carbon
analysis was used for morphological and microstructural steel with the hardness of 64 rockwell and radius of 5 mm. Prior
analyses. to the wear test, the loading test began with the force of 2
In order to perform electrochemical experiments, a common Newton and increased by 2 Newton every 50 m. The
three-electrode cell, including a working electrode (coated or experiment continued until a significant reduction in mass
uncoated specimens), a saturated calomel electrode (SCE) as was observed in the samples. The wear test was performed at
the reference electrode and a platinum electrode as auxiliary the speed of 0.03 m/s and distance of 120 m. The amount of
electrode was used. All the experiments were performed in weight loss of the samples was weighed with the electronic
distilled water solution containing 3.5 wt.% NaCl at the balance, and the results of the friction coefficient were
ambient temperature. Potential control and current measure- calculated using CDT125 software. In order to obtain valid

Table 1. Chemical composition and bath conditions for Ni-P-W-TiO2 composite coating
Coating mixtures Electrodeposition parameters/materials

NiSO4Æ6H2O 180.00 g/L Current density 20 mA cm2

NiCl2Æ6H2O 20.00 g/L pH 1, 2, 3
Na2WO4 20.00 g/L Plating time 30, 45, 60 min
TiO2 (<1lm) 20 g/L Plating temperature 60 C
H3BO3 30.00 g/L Cathode AISI 304L stainless steel
H3PO4 50 g/L Anode Nickel plate
Na3C6H5O7 40 g/L
NaPO2H2H2O 30 g/L

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values, each test was carried out three times and the reported the plating bath, due to the presence of high hydrogen on the
values are the average of results of each test. In order to cathode and their accumulation, hydrated compounds were
investigate the wear mechanization, the wear path was exam- formed, which led to the formation of cavities in the coating.
ined using SEM images. But at higher pH, due to less hydrogen, these compounds
appeared less frequently; so, the coating surface was free from
any cavities (Ref 12, 13).
Figure 2 demonstrates the EDS analysis of Ni-P-W-TiO2
3. Results and Discussion composite-coated samples at pH = 1 (Fig. 2a), 2 (Fig. 2b), and
3 (Fig. 2c). For the coated sample at pH = 1, only peaks of Ni,
3.1 Effect of Electrolyte pH on the Microstructure P, W, and O were observed. No Ti peak was observed, which
of Ni-P-W-TiO2 Coating indicated TiO2 at this pH did not deposit. For the coated sample
To study the effect of pH on the microstructure of Ni-P-W- at pH = 1 and pH = 2, the peaks of Ni, P, Ti, W, and O were
TiO2 composite coating, baths with different pH (1, 2, and 3) observed. The existence of Ti peak in these coated samples
were used. The effect of bath pH on the morphology of Ni-P- emphasized the deposition of TiO2. Table 2 shows the chemical
W-TiO2 composite coating surface is shown in Fig. 1. Accord- composition of the composite coating created at pH of 1, 2, and
ingly, the coating obtained at pH = 1 (Fig. 1a) was non-uniform 3. The coated sample at pH = 1 was without TiO2, and the
and the number of cavities was seen in it, while the coating amount of titanium deposited in the sample coated in the bath
obtained at pH = 2 was uniform and continuous (Fig. 1b). with pH = 3 was equal to 0.94 wt.%.
Also, some areas of the coating surface created at pH = 3 were The deposition process involves the application of electric
agglomerated (Fig. 1c). potential by a pulse or direct current source between a
In a study, Tian et al. applied Ni-Co coating at pHs of, 1, 2, positively charged anode and a negatively charged cathode
3, 4, and 5 on a same substrate with the same parameters and (metal matrix), which results in an electric current between the
examined the sample surface. The results showed, at low pH in

Fig. 1 SEM surface morphology of Ni-P-W-TiO2 coating formed at (a) pH = 1, (b) pH = 2, and (c) pH = 3

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Fig. 2 EDS analysis of Ni-P-w-TiO2 composite coated samples at (a) pH = 1, (b) pH = 2, and (c) pH = 3

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Table 2. Chemical analysis of Ni-P-W-TiO2 composite over longer periods of time (Ref 14). The deposited surface at
coating deposited under different pHs pH = 1 is uncoated in some areas (Fig. 1a). In concentrated
baths, deposition of insoluble nickel is slow or does not
pH Ni, wt.% P, wt.% W, wt.% Ti, wt.% O, wt.% precipitate (Ref 19, 20). Low deposition of insoluble nickel
crystals and unwanted reactions lead to non-uniform coating at
1 88.61 5.93 0.22 … 5.24
low pH; so, pH must be increased to create uniform deposition.
2 68.97 7.28 2.08 7.46 14.21
3 74.95 8.18 1.91 5.12 9.84
Also, the release of hydrogen and formation of brittle
hydroxide compounds are the reason for the formation of
bubbles in the coating created at pH = 1 (Ref 21).
At high pH (pH = 3 and above), unwanted reactions lead to
the formation of hydroxide and oxide compounds. Blurring of
anode and the cathode as well as the transfer of ions in the color of the bath solution is a reason for unwanted reactions
electrolyte. They complete the circuit. that can lead to the production of unwanted and brittle
During the deposition process, nickel ions are first converted compounds. Also, at high pH, due to the formation of
into cation and react with the hydroxide ions according to unstable compounds on the surface, some parts remain
reaction (1). Then, during the two reduction steps according to uncoated or agglomeration occurs (Ref 22).
reactions (2) and (3), they are converted into single-atom Figure 3 demonstrates SEM cross-sectional image of the
nuclei. These single atoms are then placed in the right places coated samples at pH of 1 (Fig. 3a), 2 (Fig. 3b), and 3 (Fig. 3c).
and produce a deposited layer. For the coated sample at pH = 1, the thickness of the coating
was about 3.5 lm. The coating layer was non-uniform and
Ni2þ þ OH  ! NiðOHÞþ ðEq 1Þ
some cracks were observed. The concentration profiles of Ni, P,
W, Ti, and O are also presented in Fig. 3(a). The elemental
NiðOHÞþ ! NiðOHÞþ
ads ðEq 2Þ distribution across the coating layer was determined using an
EDS analyzer. The concentration of Ti in this sample was
NiðOHÞþ 
ads þ 2e ! Ni þ OH

ðEq 3Þ approximately negligible, which indicated no TiO2 existed in
the coating. The thickness of the coating for the coated sample
Reactions (1) and (2) are the determinants of reaction rates at pH = 2 was approximately 5 lm. The coating layer was
(Ref 15, 16). uniform in thickness, and no cracks were observed in the
At low pH (pH = 1), Ni2+ is mainly present as nickel coating and at the interface of coating and substrate. The
hydrate and, at higher pH (pH = 2), it is present as complex concentration profiles measured by EDS revealed a single-layer
compounds of nickel hydrate (Ref 17, 18). Therefore, at phase structure a cross the thickness of the coating layer
pH = 2, the formation of suitable complexes for nickel (Fig. 3b). The concentration profiles showed peaks of Ni, P, W,
deposition leads to an increase in nickel deposition in the Ti, and O. The Ni concentration varied from about 70 at.% at
composite coating. In addition, the concentration of sodium the depth just below the surface to about 11 at.% at the depth of
hydroxide is affected by the pH of the bath. At pH higher than about 5lm from the surface of the coating. The elemental
2, in the presence of nickel hydroxide, the color of the bath is distribution across the coating for other elements of P, W, Ti,
dark, which is due to the formation of sludge that leads to a and O demonstrated uniform distribution across the coating
decrease in the efficiency of the bath (Ref 14). Another reason layer. The concentrations of P, W, Ti, and O decreased at the
for the increased quality of the coating due to the increase in pH depth of about 5 lm from the surface of the coating.
and subsequent decrease in the quality of the coating with a Coated sample at pH = 3 had thickness of about 4.5 lm.
further increase in pH is related to the concentration of H+ ions This sample was also non-uniform in thickness, and some
in the bath. As the pH increases, the release of hydrogen cracks in the coating layer were observed. Also, elements of P,
decreases and, therefore, the efficiency of the bath and the rate W, Ti, and O showed uniform distribution across the coating
of deposition increase. The formation of such compounds leads layer.
to a reduction in bath efficiency and deposition rate, which is Figure 4 shows the XRD results of the Ni-P-W-TiO2
consistent with microscopic images (Fig. 1). composite coated samples at pH of 1 (Fig. 4a), 2 (Fig. 4b), and
pH is one of the most important and controlling factors in 3 (Fig. 4c). XRD results of the coated sample at pH = 1 showed
Watts baths (Ref 12). Excessive dilution of the bath reduces the the presence of Ni and Ni3P phases. No TiO2 phase was
acid concentration too much and, thus, reduces the deposition detected in this coated sample. For the coated samples at pH of
of nickel cations. On the other hand, in highly concentrated 2 (Fig. 4b) and 3 (Fig. 4c), TiO2 was detected which improved
baths (low pH baths), the deposition of insoluble nickel crystals the deposition of TiO2 particles in the composite coating. These
occurs or does not take place after a long time. Thus, excessive results were in agreement with the EDS results (Fig. 2).
concentrations in the baths lead to decreased deposition rate
(Ref 19). At low pH (pH = 1 and below), the formed bubbles in 3.2 Effect of Electrolyte pH on Corrosion BEHAVIOR
some parts of the sample is due to the low rate of reactions and of Ni-P-W-TiO2 Coating
unwanted reactions. The formation of these bubbles can be due
to the growth of brittle hydride compounds on the surface and Figure 5 shows the potentiodynamic polarization curves for
the reduction of the adhesion of the coating on the substrate. As uncoated and Ni-P-W-TiO2 composite coatings at different pH
the pH increases from 1 to 2, the reaction rate increases and a of electroplating (pH = 1, pH = 2, and pH = 3) in 3.5 wt.%
uniform coating is deposited on the surface. Also, at low pH, NaCl solution. The corrosion parameters obtained from these
due to the high concentration of H+ ions and H2 reduction in graphs were obtained by linear polarization of anodic and
cathodic sites, the pH increases in the interface of steel/elec- cathodic Tafel curves in the ± 100 mV open-circuit potential.
trolyte; this leads to the deposition of insoluble nickel crystals

Journal of Materials Engineering and Performance Volume 30(4) April 2021—2413

Fig. 3 SEM cross-sectional image of coated samples at (a) pH = 1, (b) pH = 2, and (c) pH = 3

2414—Volume 30(4) April 2021 Journal of Materials Engineering and Performance

Fig. 4 XRD analysis of coated samples at (a) pH = 1, (b) pH = 2, and (c) pH = 3

The polarization resistance was also obtained using Stern- electrochemical parameters from the polarization test are given
Geary relation (Ref 24, 25): in Table 3.
The results showed that the coated specimen at pH = 2 had
ba bc
Rp ¼ ðEq 4Þ the highest polarization resistance and the lowest current
2:303iCorr ðba þ bc Þ corrosion. As a result, the coating formed at this pH had higher
In this regard, Rp is the resistance of polarization, ba and bc corrosion resistance. At pH = 1, the corrosion current was
are the slopes of anodic and cathodic Tafel curves, respectively, greatly increased due to the lack of uniform coating on the
and iCorr is the current density of corrosion. The obtained substrate surface and the presence of cavities in the coating

Journal of Materials Engineering and Performance Volume 30(4) April 2021—2415

structure. In addition, at pH = 1, due to the higher rate of products, which precipitated on the metal surface, a passive
hydrogen regeneration and, consequently, the presence of large surface was formed, causing corrosion reactions to occur
amounts of hydrogen on the surface, the deposition of the severely (Ref 24). The Nyquist curves from the electrochemical
composite coating was prevented and it was not possible to impedance for the uncoated and coated samples at pH 1, 2, and
completely coat the surface of steel (Ref 23). As the pH 3 in 3.5 wt.% NaCl solution are shown in Fig. 6. Figure 7a and
increased from 2 to 3, the polarization resistance decreased b also demonstrates the Bode and Bode-phase diagrams for the
sharply, indicating an increase in corrosion rate in this case. tested samples, respectively. All the curves are drawn in the
This could be related to an increase in the amount of sludge in frequency range 0.1 Hz to 10 kHz.
the solution at pH = 1 due to higher H+ consumption and, thus, Data on these charts were extracted by Nova software and
the formation of insoluble compounds. sent to Zview software for analysis. The equivalent circuit
It has been reported that, when the nickel-based coatings proposed by the software for the coated samples is given in
corrode, the nickel begins to dissolve preferably (Ref 24). One Fig. 8.
of the cathode reactions that occur in nickel coatings in the In this Fig., Rs is the solution resistance between the
environment in contact with chlorine ions is the reduction of reference electrode and the specimens, Rct is the charge transfer
dissolved oxygen. The reduction process leads to the increase resistance of the substrate, Rcoat is the corrosion resistance of
of local pH at the surface of the coating, forming a protective, the coating in corrosive environment, Cdl is the capacity of the
thin film of nickel-TiO2. double layer, and CPE is the constant phase element used,
instead of the simple capacitor, and for the steel substrate and
NiðsÞ ! Ni2þ ðaqÞ þ 2e ðEq 5Þ coating shown with CPE1 and CPE2, respectively. The
obtained results from the analysis of Nyquist curves using
1=2O2 ðgÞ þ H2 OðLÞ þ 2e ! 2OH ðaqÞ ðEq 6Þ Zview software are given in Table 4. The reason for using a
constant phase element, instead of an ideal capacitor, is to
Ni2þ ðaqÞ þ 2OH ðaqÞ ! NiðOHÞ2 ðSÞ ðEq 7Þ consider the surface roughness of the electrode, the non-
homogeneous reactions on the electrode surface, and the non-
The TiO2 layer is the prelude to the further growth of uniform distribution of current during the corrosion process
corrosion products, a phenomenon dependent on corrosive (Ref 18). The constant phase element consists of two compo-
solutions. Corrosion products can include NiCO3, Ni5(OH)6 nents, the admittance (CPE-T), and the power index number
(CO3)2, Ni5(OH)8Cl2H2O, and a mixture of these (Ref 25). Li
reported that due to the very low solubility of the produced

Fig. 6 Nyquist diagram of uncoated and Ni-P-W-TiO2 composite

Fig. 5 Potentiodynamic polarization curves of uncoated and Ni-P-
coating formed at different pH in 3.5 wt.% NaCl solution
W-TiO2 composite coating formed at different pH in 3.5 wt.% NaCl
solution

Table 3: The obtained information from the polarization curve of Ni-P-W-TiO2 composite coating formed at different
pHs
Sample Uncoated pH = 1 pH = 2 pH = 3

icorr , lA cm2 1.34 1.30 1.21 1.38

Ecorr , V  0.24683  0.38754  0.18780  0.30573
Corrosion rate, mm/year 0.015638 0.15109 0.014059 0.12069
ba , V/dec 0.15245 0.090576 0.13192 0.099195
bc ,V/dec 0.086673 0.069763 0.07125 0.093201

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(CPE-P). The index number of power is between 0.5 and 1; the not uniform. The power index number of the coated sample at
greater its deviation from 1, the greater the heterogeneity and pH = 2 was about 0.86, which indicated the formation of a
surface roughness would be (Ref 26, 27). The deviation of the relatively uniform coating and, therefore, the uniform SEM
Nyquist curves from the semicircular state indicates the cross section of coated sample at pH = 2 confirmed this subject
roughness and unevenness of the surface during the corrosion (Fig. 3b). For the coated sample at pH = 3, the power index
process (Ref 28, 29). The power index number coated sample at number was about 0.74. As can be deduced form SEM cross-
pH = 1 was about 0.64, which indicated the non-uniformity of sectional image of this sample (Fig. 3c), the coating layer was
the coating layer. This result was in accordance with the SEM relatively uniform. Higher levels of admittance indicated more
cross-sectional image (Fig. 3a) of this coated sample. As can be porosity in the coating. The higher admittance was related to
seen in this image (Fig. 3a), the thickness of coating layer was the coated sample at pH = 1, which demonstrated more porosity
in the coating than other coated sample. This was in agreement
with the results of SEM surface morphology of the coated
sample at pH = 1 (Fig. 1a). Also, the cross-sectional image of
this sample confirmed the existence of porosity and cracks
(Fig. 3a). Admittance had its lowest value at pH = 2, indicating
that the protective properties of the coating were better in this
case. SEM surface morphology (Fig. 1b) and cross-sectional
image (Fig. 3b) of the coated sample at pH = 2 also indicated
there was no crack or porosity in the coating. As the pH
decreased to 1, the amount of admittance increased, resulting in
reduced corrosion resistance. Higher solution resistance at
pH = 2 could be the reason for a better reaction to form
composite coatings, resulting in better coating at this pH. In
addition, the capacity of the double layer for the coating formed
at this pH was lower than that in other cases, which indicated
less penetration of corrosive solution into the metal/coating
interface (Ref 28). These results were in line with the results of
potentiodynamic polarization test.
The presence of a wide peak in the Bode diagrams of the
coated samples indicated the existence of two time constants,
one of which is not clearly seen. In other words, in these
samples, due to the discontinuity of the coating and, of course,
the contact of the corrosive environment with the coating layer,
two active electrochemical cells were formed on the surface of
the coating. The first time constant at high frequencies was
related to the response of the Ni-P-W-TiO2 composite coating
to the corrosive environment, while the second time constant at
low frequencies associated with the corrosion process occurred
in the metal/solution interface in the cavities in the Ni-P-W-
TiO2 composite coating (Ref 29, 30).
The presence of the peaks at high frequencies in phase angle
diagrams for the coated specimens confirmed the coating
formed at pH = 2 performed its protective role well even over
long periods of time. The impedance module can be measured
from Bode curves. Higher impedance module at lower
frequencies indicated better properties of the protective com-
posite coating. Since the impedance module had a higher value
for the coating formed at pH = 2 than other coatings, it can be
concluded that, at this pH, the coating showed more resistance
Fig. 7 Curves of (a) Bode and (b) Bode phase for uncoated and to the corrosive environment.
Ni-P-W-TiO2 composite coating formed at different pH in 3.5 wt.%
NaCl solution

Table 4: Electrochemical parameters obtained from electrochemical impedance for samples coated at different pHs
Sample RS, XÆcm2 Rp or Rc1, XÆcm2 CPE1-T, FÆcm2 CPE1-P, FÆcm2 Rc2, XÆcm2 CPE2-T, FÆcm2 CPE2-P, FÆcm2

Uncoated 6.09 3466 0.0002096 0.74228 … … …

pH = 1 4.013 57 0.007524 0.64385 … … …
pH = 2 4.922 7058 0.00017377 0.86069 … … …
pH = 3 3.238 10.59 0.00027302 0.75175 85.29 0.011179 0.81142

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 Fig. 9 Micro-hardness changes versus electrolyte pH for uncoated
Fig. 8 Equivalent electrical circuit used for (a) uncoated sample, and coated specimens
coated samples at pH = 1,2, and (b) pH = 3

3.3 Effect of Electrolyte pH on the Wear Resistance

of Ni-P-W-TiO2 Coating
Figure 9 shows the effect of electrolyte pH on the micro-
hardness of the Ni-P-W-TiO2 composite coating. As can be
seen, with increase in pH and increase in TiO2 concentration,
the micro-hardness value increased and, at pH = 2, the
maximum hardness value was obtained. At pH = 3, the amount
of TiO2 particle deposition decreased and micro-hardness
decreased.
As the pH increased, the precipitation of TiO2 particles
increased, resulting in an increase in the hardness of the coating
(Ref 31). Adding TiO2 ceramic particles to the coating created Fig. 10 Weight loss of uncoated and coated specimens at different
barriers to the movement of the dislocation, locked the pH after wear test
dislocations, and prevented the plastic deformation of the
coating. In the Orowan equation (s ¼ Gb k ), smaller distance
between the scattered particles leads to higher strength. k In Eq 8, w is the sample weight loss after the wear test, k is
depends on the distance between the scattered particles, G is the the wear coefficient, Pn is the normal pressure in the wear test,
shear stress, and b is the burger vector. As a result, increasing L is the sliding distance during the wear test, and H is the
the scattered particles reduced the value of k, which in turn sample hardness. According to Archhard’s equation (Eq 8), the
increased the amount of s. Increasing the value of s also rate of weight loss of the sample was directly related to the
increased the amount of hardness. In fact, the above equation normal pressure applied to the sample and the sliding distance,
states that, if moving dislocation collides with a ceramic and inversely to the sample hardness. Therefore, by increasing
particle, it needs minimal stress to move again, which is the micro-hardness of the sample, weight loss of the coating
inversely proportional to the distance between the particles (Ref decreased and, by decreasing the micro-hardness of the sample,
29). Therefore, as the number of hard particles in the coating the rate of weight loss of the sample increased. Another reason
increased and was uniformly distributed in the matrix, the is the Hall-patch mechanism based on grain size (Ref 31).
average distance between the particles decreased and the According to this mechanism, as the grain size decreases, the
amount of stress required for the motion of dislocation micro-hardness increases and the weight loss decreases.
increased. The ceramic particles created new germination sites Another reason that can be mentioned is that, according to
by their presence in the coating, prevented the growth of Orowan theory, the particles in the coating prevent the plastic
previous grains, and caused the coating to become finer and deformation of the coating by blocking the dislocations caused
hardness to increase (Ref 30). by the scattering of the particles in the coating; therefore,
Figure 10 shows the weight loss changes of the uncoated micro-hardness and wear resistance increase (Ref 30-32).
and coated samples with different pH values after the wear test. Changes in the friction coefficient of the uncoated and
With increase in pH, the deposition of TiO2 particles in the coated samples with different pH values during the wear test are
electrolyte had an upward trend and, then, a downward trend. shown in Fig. 11. By increasing pH (pH = 1 to pH = 2), the
The highest particle deposition occurred at pH = 2. coefficient of friction first decreased and, then (pH = 2 to pH =
As the pH of the solution increased, the precipitation of 3), increased. The lowest friction coefficient curve was related
TiO2 particles increased, resulting in a decrease in the weight of to the coated sample at pH = 2, and the highest was related to
the samples. The lowest weight loss occurred at pH = 2 the uncoated 304 steel.
(Figs. 8, 9, 10). One of the reasons for the decrease in friction coefficient is
This process follows Archhard’s law (Ref 31): its role in reducing the amount of abrasive particles between the
wear surfaces. These particles lead to the locking and conflict of
Pn L abrasive surfaces with each other and also reduce the durability
W ¼k ðEq 8Þ
H and stability of the coating (Ref 32). Therefore, by reducing

2418—Volume 30(4) April 2021 Journal of Materials Engineering and Performance

these abrasive particles, the friction coefficient decreased and, values in the coating reduced the friction coefficient of its
consequently, the wear resistance increased. As pH increased, coating. Therefore, due to the increased hardness and increased
the amount of TiO2 lubricant particles in the coating increased; deposition of TiO2 lubricants, the friction coefficient of the
since TiO2 was a lubricant, increasing these particles to certain coating decreased.
Gruszka et al. showed the presence of particles in the
composite coating reduced the residual stresses relative to pure
nickel. They reported a reduction in residual stresses and a
reduction in grain size and the presence of TiO2 ceramic
particles, which led to increased wear resistance (Ref 33).
Figure 12 shows the SEM image uncoated and Ni-P-W-TiO2
composite coated samples at different pH values. The wear path
for the uncoated sample was relatively deep and worn severely
(Fig. 12a). The formation of continuous wear grooves and some
damaged regions in this sample was detected. A large amount
of plastic deformation can be observed (Fig. 12a). In some
regions, surface microplowing is evident. The existence of
microcracks, as indicated by the arrows, is observed on the
surface. These microcracks tend to propagate parallel to the
wear direction. During sliding and plastic deformation, the
Fig. 11 Friction coefficient as a function of wear distance for worn surface cracks join together with the adjacent cracks (Ref
uncoated and coated samples at different pHs 34). When the length of the crack reaches a critical value, the

Fig. 12 SEM surface morphology after wear test for (a) uncoated and Ni-P-W-TiO2 coating formed at different pH; (b) pH = 1, (c) pH = 2,
and (d) pH = 3

Journal of Materials Engineering and Performance Volume 30(4) April 2021—2419

material between the crack and the surface delaminates in the 4. S. Kundu, S. KalyanDas and P. Sahoo, Friction and Wear Behavior of
form of plate-like debris (Ref 35). Electroless Ni-P-W Coating Exposed to Elevated Temperature, Surf.
Interfaces Anal., 2019, 14(1), p 192–207
The wear path for the coated sample at pH = 2 had smooth
5. H. Zhou, Z. Liao, C. Fang, H. Li, B. Feng, S. Xu, G. Cao and Y.
appearance and no signs of wear or cracking due to severe wear Kuang, Pulse Electroplating of Ni-W-P Coating and ITS ANTI-
were observed (Fig. 12c). In this case, a quiet wear occurred on corrosion Performance, Trans. Nonferr. Met. Soc. China, 2018, 28(1), p
the coating, which was due to the higher amount of TiO2 88–95
particles in the coating than the coatings created at lower and 6. M. Staia, Wear Performance and Mechanism of Electroless Ni-P
Coating, Surf. Coat. Technol., 1996, 86–87(2), p 598–602
higher pH values. It was also observed the width of the wear
7. G. Parida, Synthesis and Characterization of Ni-TiO2 Composite
path increased at pH = 1 (Fig. 12b) and pH = 3 (Fig. 12d). Coatings by Electro-Co-Deposition, Surf. Coat. Technol., 2011,
According to Fig. 12(b) and (d), the effects of plastic 205(21–22), p 4871–4879
deformation and wide grooves in the wear path were observed. 8. I. Saravanan, A. Elayaperumal, A. Devaraju, M. Karthikeyan and A.
The presence of these grooves as well as the created particles Raji, Wear Behaviour of Electroless Ni-P and Ni-P-TiO2 Composite
indicated severe wear with abrasive wear mechanism. In fact, Coatings on En8 Steel, Mater. Today Proceed, 2020, 22(3), p 1135–
1139
the uncoated and coated samples at pH = 1 and pH = 3 had less
9. M. Ram, M. Kumar, A. Ansari, S. Sharma and A. Sharma, Corrosion
hardness due to the lower precipitation of TiO2 particles and Resistance of Electroless Ni-P-SiC/ Ni-P-TiO2-ZrO2 Nano-Coatings in
underwent the plastic deformation during wear. Therefore, a Paper Mill Bleach Plant, Mater. Today Proceed, 2020, 21(2), p 1200–
deep wear path was created during this plastic deformation. The 1212
coating created at pH = 2 showed better wear resistance due to 10. S. Geng, S. Qi, Q. Zhao, S. Zhu and F. Wang, Electroplated Ni-Fe2O3
Composite Coating for Solid Oxide Fuel Cell Interconnect Application,
higher hardness and lower friction coefficient (Ref 34, 36).
Int. J. Hydrog. Energy, 2012, 37(14), p 10850–10856
11. H.K. Lee, H.Y. Lee and J.M. Jeon, Codeposition of Micro- and Nano-
sized SiC Particles in the Nickel Matrix Composite Coatings Obtained
by Electroplating, Surf. Coat. Technol., 2007, 201(8), p 4711–4717
4. Conclusions 12. L. Tian, J. Xu and S. Xiao, The Influence of pH and Bath Composition
on the Properties of Ni-Co Coatings Synthesized by Electrodeposition,
The Ni-PW-TiO2 composite coating was fabricated on the Vacuum, 2011, 86(1), p 27–33
AISI 304L stainless steel using electroplating method and the 13. H. Ebrahimifar and M. Zandrahimi, Influence of Electrodeposition
Parameters on the Characteristics of Mn-Co Coatings on Crofer 22
effects of different pH (1, 2, and 3) on the microstructure, APU Ferritic Stainless Steel, Bull. Mater. Sci., 2017, 40(6), p 1273–
corrosion behavior, and mechanical properties were investi- 1283
gated and the following results were obtained: 14. L. Chang, C.H. Chen and H. Fang, Electrodeposition of Ni-P Alloys
From a Sulfamate Electrolyte Relationship Between Bath pH and
1. By increasing the bath pH until pH = 2, the precipitation Structural Characteristics, J. Elctrochem. Soc., 2008, 155(1), p D57–
D61
of ceramic particles and tungsten in the coating increased
15. A. Cziraki, B. Fogarassy, I. Gerocs, E. Toth-kadar and I. Bakonyi,
and, then, decreased. The created coating at pH = 2 Microstructure and Growth of Electrodeposited Nanocrystalline Nickel
showed a uniform surface without cracks and cavities. Foils, J. Mater. Sci., 1994, 29, p 4771–4777
2. The created coating at pH = 2 showed the lowest corro- 16. E. Lee and J. Choi, A Study on the Mechanism of Formation of
sion current density and the highest corrosion resistance. Electrocodeposited Ni-Diamond Coatings, Surf. Coat. Technol., 2001,
148(2–3), p 234–240
In addition, the decrease in the coating capacity with in-
17. S. Spanou and E. Pavlatou, Pulse Electrodeposition of Ni/nano-TiO2
crease in concentration of TiO2 particles in the electro- Composites: Effect of Pulse Frequency on Deposits Properties, J. Appl.
chemical impedance test indicated a decrease in porosity Electrochem., 2010, 40(7), p 1325–1336
and pores due to the presence of TiO2 particles, which 18. S. Lajevardi and T. Shahrabi, Effects of Pulse Electrodeposition
reduced the penetration of electrolyte into the coating Parameters on the Properties of Ni-TiO2 Nanocomposite Coatings,
and increased the corrosion resistance of the coating. Appl. Surf. Sci., 2010, 256(22), p 6775–6781
19. A. Zimmerman, D. Clark, K. Aust and U. Erb, Pulse Electrodeposition
3. By increasing the bath pH until pH = 2, the hardness of of Ni-SiC Nanocomposite, Mater. Lett., 2002, 52(1–2), p 85–90
the composite coating increased and, then, decreased. 20. Y. Zhang, Y. Yang, P. Xiao, X. Zhang, L. Lu and L. Li, Preparation of
4. The created coating at pH = 2 showed the lowest weight Ni Nanoparticle-TiO2 Nanotube Composite by Pulse Electrodeposition,
loss and the highest wear after the wear test. The higher Mater. Lett., 2009, 63(28), p 2429–2431
presence of TiO2 in the coating and the reduction of the 21. K.A. Kumar, G.P. Kalaignan and V. Muralidharan, Direct and Pulse
friction coefficient led to an increase in hardness and Current Electrodeposition of Ni-W-TiO2 Nanocomposite Coatings,
Ceram. Int., 2013, 39(3), p 2827–2834
wear resistance. 22. B. Szczygieł and M. Kołodziej, Composite Ni/Al2O3 Coatings and Their
Corrosion Resistance, Electrochim. Acta., 2005, 50(20), p 4188–4195
23. A. Bund and D. Thiemig, Influence of Bath Composition and pH on
the Electrocodeposition of Alumina Nanoparticles and Nickel, Surf.
Coat. Technol., 2007, 201(16–17), p 7092–7099
24. Q. Li, X. Yang, L. Zhang, J. Wang and B. Chen, Corrosion Resistance
References and Mechanical Properties of Pulse Electrodeposited Ni-TiO2 Com-
posite Coating for Sintered NdFeB Magnet, J. Alloys Compd., 2009,
1. F. Riffard, H. Buscail, E. Caudron, R. Cueff, C. Issartel and S. Perrier, 482(1–2), p 339–344
The Influence of Implanted Yttrium on the Cyclic Oxidation Behaviour
25. A.C. Ciubotariu, L. Benea, M. Lakatos-Varsanyi and V. Dragan,
of 304 Stainless Steel, Appl. Surf. Sci., 2006, 252(10), p 3697–3706
Electrochemical Impedance Spectroscopy and Corrosion Behaviour of
2. M. Zandrahimi, J. Vatandoost and H. Ebrahimifar, Pack Cementation Al2O3-Ni Nano Composite Coatings, Electrochim. Acta., 2008, 53(13),
Coatings to Improve High-Temperature Oxidation Resistance of AISI p 4557–4563
304 Stainless Steel, J. Mater. Eng. Perform., 2012, 21(10), p 2074–2079
26. R. Sen, S. Das and K. Das, Effect of Stirring Rate on The
3. K. Hou and H. Chen, Preparation and Wear Resistance of Pulse Microstructure and Micro Hardness of Ni-CeO2 Nanocomposite
Electrodeposited Ni-W/Al2O3 Composite Coating, Appl. Surf. Sci., Coating and Investigation of The Corrosion Property, Surf. Coat.
2011, 257(15), p 6340–6346 Technol., 2011, 205(13–14), p 3847–3855

2420—Volume 30(4) April 2021 Journal of Materials Engineering and Performance

27. M.A. Amin, K. Khaled, Q. Mohsen and H. Arida, A Study of the 32. M.C. Chou, M.D. Ger, S.T. Ke, Y.R. Huang and S.T. Wu, The Ni-P-
Inhibition of Iron Corrosion in HCl Solutions by Some Amino Acids, SiC Composite Produced by Electro-codeposition, Mater. Chem. Phys.,
Corros. Sci., 2010, 52(5), p 1684–1695 2005, 92(1), p 146–151
28. N. Padhy, S. Kamal, R. Chandra, U.K. Mudali and B. Raj, Corrosion 33. A. Gruszka and A. Budniok, Production and Structure of Electrocoat-
Performance of TiO2 Coated Type 304L Stainless Steel in Nitric Acid ings Ni-P-TiO2-Al, Adv. Perform. Mater., 1999, 6(2), p 141–147
Medium, Surf. Coat. Technol., 2010, 204(16–17), p 2782–2788 34. A. Haseeb, U. Albers and K. Bade, Friction and Wear Characteristics of
29. J. Winiarski, A. Leśniewicz, P. Pohl and B. Szczygieł, The Effect of pH Electrodeposited Nanocrystalline Nickel-Tungsten Alloy Films, Wear,
of Plating Bath on Electrodeposition and Properties of Protective 2008, 264(1–2), p 106–112
Ternary Zn-Fe-Mo Alloy Coatings, Surf. Coat. Technol., 2016, 299, p 35. N.P. Suh, The Delamination Theory of Wear, Wear, 1973, 25, p 111–118
81–89 36. L. Chen, L. Wang, Z. Zeng and J. Zhang, Effect of Surfactant on the
30. A. Gupta, S. Barkam, D. Lahiri, R. Balasubramaniam and K. Balani, Electrodeposition and Wear Resistance of Ni-Al2O3 Composite
Effect of Alumina Dispersion on Microstructural and Nanomechanical Coatings, Mater. Sci. Eng. A., 2006, 434(1–2), p 319–325
Properties of Pulse Electrodeposited Nickel-Alumina Composite
Coatings, J. Mater. Sci. Technol., 2014, 30(8), p 808–813
Publisher’s Note Springer Nature remains neutral with regard to
31. D. Jeong, U. Erb, K. Aust and G. Palumbo, The Relationship Between
Hardness and Abrasive Wear Resistance of Electrodeposited Nanocrys- jurisdictional claims in published maps and institutional affilia-
talline Ni-P Coatings, Scr. Mater., 2003, 48(8), p 1067–1072 tions.

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