ISSN 20702051, Protection of Metals and Physical Chemistry of Surfaces, 2015, Vol. 51, No. 2, pp. 234–239.

© Pleiades Publishing, Ltd., 2015.

NANOSCALE AND NANOSTRUCTURED

MATERIALS AND COATINGS

Electroless Ni–P/Ni–B–B4C Duplex Composite Coatings

for Improving the Corrosion and Tribological Behavior
of Ck45 Steel1
Mohsen Rezagholizadeha, Mohamad Ghaderia, Azam Heidarya, and Seyed Mahmood Monir Vaghefib
a
Young Researcher and Elite Club, Najafabad Branch, Islamic Azad University, Isfahan, Iran
bMaterials Engineering Department, Isfahan University of Technology, Isfahan, Iran

email: gholizadeh.mohsenreza@gmail.com
Received January 27, 2014

Abstract—Ni–P/Ni–B–B4C duplex composite coatings were deposited on Ck45 by electroless plating pro
cess, and their structure, morphology, micro hardness and corrosion resistance were evaluated. The duplex
coatings were prepared using dual baths (acidic hypophosphite– and alkaline borohydridereduced electro
less nickel baths) with Ni–P as the inner layer. The coatings were amorphous in asplated condition and
nanocrystallized, and produced nickel borides upon heattreatment. SEM observations showed that the
duplex interface on the Ck45 was uniform, and the compatibility between the layers was good. The Ni–
P/Ni–B–B4C coating’s microhardness and corrosion resistance of Ni–B–B4C coating as the outer layer
were higher than Ni–P coatings. The Ni–P/Ni–B–B4C duplex composite coatings with high hardness and
good corrosion resistance properties would expand their scope of applications.
DOI: 10.1134/S207020511502015X

1
1. INTRODUCTION
Wear and corrosion are the main failure modes for
many engineering components, and result in high
costs [1]. To improve surface hardness and wear resis
tance, many treatments are adopted, such as electro
plating, carbon case hardening, nitrogen hardening,
PVD, CVD, ion implantation, etc. [1–3]. Every tech
nology has its limitations; however, some have poor
feasibility, and some are expensive. With the develop
ment of industry demands for improved performance,
better surface coatings have become more difficult to
attain, such as higher wear resistance and self lubricat
ing properties [3]. Electroless nickel is an engineering
coating normally used because of excellent corrosion
and wear resistance as well as other functional proper
ties [3–5].
Hypophosphitereduced electroless nickel plating
has received widespread acceptance, and attention has
shifted towards borohydride reduced electroless nickel
deposits in recent years. As boron is one of the most
important amorphous elements, various boroncon
taining alloys have been prepared in a search for supe
rior characteristics. The formation of an amorphous
solid is extremely difficult by a liquid quenching
method whereas electroless deposition offers available
alternative. For electroless plating of NiB alloy
deposits, boroncontaining reducing agents such as
sodium borohydride or ethylenediamine are com
1 The article is published in the original.
monly used. The reduction efficiency of sodium boro
hydride is much higher than that of ethylenediamine
and sodium hypophosphite. It can provide up to eight
electrons for reduction of some metals in contrast to
two electrons that can be provided by sodium hypo
phosphite for the same reaction [6]. Besides the high
reduction efficiency, borohydridereduced baths are
preferred to dimethyl amine boranebased baths in
terms of costeffectiveness of operation [7]. However,
borohydride ions hydrolyze readily in acid or neutral
solutions and will spontaneously yield nickel boride in
presence of nickel ions in the plating bath [6–8].
The use of a duplexlayer or multilayer coating
with layers having different corrosion potential Ecorr
was an effective solution to improve the corrosion
resistance of the anodic substrate [9–11].
In the past years, many investigations have been
developed with the aim of incorporating inert particles
in a nickel matrix to enhance some of its properties
[12–15]. Incorporation of hard composites such as
Al2O3 [16–18], TiO2 [19], ZrO2 [20, 21], ZnO [22],
etc., considerably improves some properties of con
ventional electroless nickel plates.
The unique properties of boron carbide (B4C) such
as its very high hardness (about 9.3 Mohs scale), excel
lent chemical resistance, very high neutron absorp
tion, melting point of about 2350°C and low density of
2520 kg/m3, make it extremely suitable for both room
and hightemperature applications. Thus, B4C is an
excellent candidate for producing electroless nickel
composite coatings, which have different applications

234
 ELECTROLESS Ni–P/Ni–B–B4C DUPLEX COMPOSITE COATINGS
in aerospace industry, nuclear technology, mining and
automotive industry [1, 23]. The aim of this investiga
tion is to examine the heat treatment effect and also
the distribution of B4C nanoparticles on corrosion and
abrasion resistance of Ni–P/Ni–B–B4C doublelayer
electroless coating.
2. EXPERIMENTAL
CK45steel discshaped samples with a thickness
of five mm and a diameter of 50 mm were prepared,
and sand blasted by 100micro silicon particles. After
the sand blasting operations, the samples were coated
with composite duplex electroless coating of nickel
phosphorus/nickelboron containing boron carbide
nanoparticles (Ni–P/Ni–B–B4C). The commercial
SLOTONIP 70A electroless solution made by the
Shloter Company of Germany was used to provide
nickelphosphorus electroless coating on the samples.
The pH of this bath was 4.6 with a coating temperature
of 80°C. To coat with nickelboron containing boron
carbide nanoparticles, the boronnickel electroless
bath was first constructed. 20 g/L nickel chloride,
1 g/L sodium hydride, 56 g/L ethylenediamine,
40 g/L (Pb2+) formed the chemical combination of
this bath. Then, 1.5 g/L of boron carbide powder
(B4C) was added to the bath, placed in an ultrasonic
bath for two hours so that these particles were uni
formly distributed inside the bath. The pH of the bath
was considered to be 12.5 with the coating tempera
ture of 85°C. After the particles were distributed
evenly, coating operations started. In order to study
the role of nickelphosphorus electroless coating in
the Ni–P/Ni–B–B4C composite duplex coating, cor
rosion studies were performed on this coating and com
pared with Ni–P/Ni–B duplex layer and Ni–P single
layer coatings (with similar thickness of 25 microns).
Studies related to corrosion resistance of coatings were
performed by Tafel polarization test in 3.5% NaCl
solution by PARSTAT 2273 device. The samples from
the surface area of 1 cm2 were put in contact with elec
trolyte. The platinum electrode and the saturated
calomel electrode (SCE) were employed as the stan
dard and reference electrodes, respectively. Using
Tafel extrapolation method, the potential and corro
sion current densities were extracted from Tafel curves.
To investigate the effect of heat treatment temperature
on composite duplex coating, some of the samples
were coated, and heat treated 400°C for one hour in
the inert atmosphere. Ultimately, scanning electron
microscope and Xray diffraction device were used for
the study on the morphology on the surface of the
samples and for phase analysis on the surface of the
samples, respectively. The hardness of the samples was
also measured at micro scale with the initial weight of
1 N through Vickers’s method. The pinondisc wear
ing machine was used to evaluate and compare the tri
bological behavior of the samples. In all the wearing
tests, 52100 steel pin with a hardness of about 65RC
PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES Vol. 51 No. 2 2015
235
(b) 20 μm (a) 20 μm
Fig. 1. SEM micrographs of surface morphology (a) Ni–B
and (b) Ni–B–B4C.
and a diameter of six mm was used as the abrasive. The
wearing test was performed in air atmosphere at the
slippage rate of 0.1 m s–1 under 5 N force and maxi
mum slippage distance of 1000 m.
3. RESULT AND DISCUSSION
3.1. Examination Coating Morphology
Figure 1 shows the morphology of created Ni–
P/Ni–B–B4C electroless coating on a steel substrate.
This figure shows that the surface of coating has a
spherical shape like a cauliflower that is very usual for
Ni–B electroless coatings [24]. Ni–B electroless coat
ings have high porosity, B4C particles lead to the cre
ation of a new germination area, which result in
reducing porosity of coating and reducing grain size of
structure [25], also the structure of Ni–P/Ni–B
duplex coating is like Ni–B coating.
3.2. Examination CrossSection of Coating
Figure 2 shows crosssection of Ni–P/Ni–B
duplexlayer coatings, Ni–P/Ni–B–B4C composite
and Ni–B singlelayer. This shape shows that coatings
created in this investigation are very uniform and have
good connectivity with the substrate. In electroless
method, external current isn’t used. Therefore, thick
ness of coating is uniform and all the corners, angles
and holes have this uniform ability [24]. Thickness of
Ni–B and Ni–P layer in duplexlayer coatings is
almost 12.5 micron. Also, thickness of Ni–B single
layer coating is about 25 microns.
3.3. Examinetin Corrosion Behavior of Coating
Figure 3 shows Tafel polarization curve of Ni–B
coating, Ni–P/Ni–B duplexlayer, Ni–P/Ni–B–
B4C composite and steel without coating in 3.5% NaCl.
Corrosion parameters, corrosion potential (Ecorr),
corrosion current density (icorr) and polarization resis
tance, gained from extrapolation of Tafel polarization
curves are represented in Table 1.
Nanoparticles of B4C lead to changing the place of
corrosion potential for composite coatings to positive
236 MOHSEN REZAGHOLIZADEH et al.

(а) 20 μm (b) 20 μm (c) 20 μm

Fig. 2. Scanning electron microscopy from crosssection of coating (a) Ni–P/Ni–B–B4C, (b) Ni–P/Ni–B, and (c) Ni–B.

0 Ni–P/Ni–B–B4C
–100 Ni–P/Ni–B
Ni–B
–200 Ck45
E , mV SCE

–300
–400
–500
–600
–700
–800
1/E–11 1/E–09 1/E–07 1/E–05 1/E–03
1/E–10 1/E–08 1/E–06 1/E–04
i, A/cm2)

Fig. 3. The Tafel polarization curves of the coatings in 3.5% NaCl solution.

value, also corrosion current density in comparison to
Ni–B coating and Ni–B/Ni–P duplex coating is
remarkably reduced. This matter shows that corrosion
resistance of composite coatings was improved. Distri
bution of nano particles of B4C in coatings improved
cathodic and anodic slops. Furthermore, by addition
of nano particles corrosion current density and polar
ization resistance was improved. Regarding the above
cases, it is clear that B4C nano particles have an impor
tant role in increasing corrosion resistance of compos
ite coating. From the revised literature, increase in
corrosion resistance can be due to the formation of
B4C compact layer with great corrosion resistance and
low chemical reaction in interface of coatingelectro
lyte that can act as a physical barrier against corrosion
[26]. In addition, uniform distribution of B4C particles
can help the improvement of corrosion resistance with
limiting region corrosion [26]. B4C particles with
cracks and grooves in Ni–B coating lead to a decrease
in the susceptible region of corrosion, and therefore,
an increase in corrosion resistance. Regarding Tafel
curves in Fig. 3, it is marked that existence of Ni–P
layer in Ni–P/Ni–B coating has to lead to the
improvement of corrosion resistance of this coating in
comparison to Ni–B coating. Existence of Ni–P
coating used as a substrate, with regard to the higher
corrosion resistance and also its contiguous structure
in comparison to Ni–B coating lead to the improve
ment of corrosion resistance in duplex coating [26].

Table 1. Corrosion resistance of the coatings in 3.5% NaCl solution, evaluated by potentiodynamic polarization technique

Solution Coating Ecorr (mV) icorr (A cm–2) Rp(Ω)

Ck45 –420 2.73 × 10–5 9.15 × 102

3.5% NaCl Ni–B –362 5.12 × 10–6 4.88 × 103
Ni–P/Ni–B –306 9.66 × 10–7 2.58 × 104
Ni–P/Ni–B–B4C –270 4.2 × 10–9 586 × 106

PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES Vol. 51 No. 2 2015

 ELECTROLESS Ni–P/Ni–B–B4C DUPLEX COMPOSITE COATINGS 237

Intensity, a.u. (a) 16 (а)

Ni 14 R2 = 0.9592
Ni–P/Ni–B–B4C
12

Mass loss, mg
Ni–B
10 Ni–P/Ni–B R2 = 0.9952
Ni–P/NiPB–B4C R2 = 0.9764
8
6
Ni–B 4
2
30 40 50 60 70 80 90 0 200 400 600 800 1000
2θ, deg Silding distance, m
(b) Ni3B 14 (b)
Intensity, a.u.

Ni2B
B4C
12 R2 = 0.8977

Ni–P/Ni–B–B4C 10 R2 = 0.9632

Mass loss, mg
Ni–B
8 Ni–P/Ni–B
Ni–P/NiPB–B4C
6 R2 = 0.9888

Ni–B 4
2
20 30 40 50 60 70 80 90
0 200 400 600 800 1000
2θ, deg
Silding distance, m
Fig. 4. Xray differaction pattern of coatings: (a) befor heat Fig. 5. Weight loss at slippage distance for electroless coat
treatment (b) after heat treatment. ings (a) before heat treatment and (b) after heat treatment.

3.4. Effect of Heat Treatment on Coating Structure
Figure 4 shows diffraction of Xray pattern of cre
ated coatings in this investigation. This figure shows
that created coatings have a mixture of amorphous fine
structure and crystalic phase [27]. Peaks shown in Fig. 4
were gained from over stand together of a wide base
peak in diffraction angle between 35 and 55 and a nar
row peak. Narrow peak is related to nanocrystal (111)
diffraction, and wide peak is related to coating amorph
phase. Ni (200) and Ni (220) peaks appeared because
of nanocristalic phase. Figure 5 shows XRD pattern of
heat treatment coatings. This figure explains the com
plete change of structure into the crude state, meaning
that instead of amorph effects in diffraction curves,
obvious peaks from Ni3B were observed.
for 1h, its hardness was greatly increated. Studies show
that the increate in hardness is related to the sedimen
tation of the intermetallic Ni3B resistant phase during
the crystallization of amorphous phase [25]. It has
been reported that Ni3B phase has a high strength and
shear module, which causes the effectiveness on these
coatings’ hardness [25]. These observations are in
good agreement with XRD analysis resut. The hard
ness of the coatings created before and after the heat
treatment has been mentioned in Table 2.
The reason for an increase in Ni–P/Ni–B–B4C
coating hardness is due to the presence of B4C as a sec
ondary phase in coating. With the creation of a com
posite coating, the coating hardness has also been
increased.

3.5. Effect of Heat Treatment on Hardness of Coating 3.6. The Effect of Heat Treatment
On the Wear Behavior of Coating
Heat treatment temperature has a great effect on
coatings’ hardness. After the Ni–P/Ni–B–B4C With regard to the result obtained from loading
duplex composite coating was heat treated at 400°C test, wear tests were carried out 5 N force. The curves

Table 2. The effect of heat treatment of coatings hardness

Coating Temperature, °C Average of microhardness, V
Ni–B Asplated 510
Ni–P/Ni–B Asplated 640
Ni–P/Ni–B–B4C Asplated 870
Ni–B 400 850
Ni–P/Ni–B 400 1085
Ni–P/Ni–B–B4C 400 1420

PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES Vol. 51 No. 2 2015

238 MOHSEN REZAGHOLIZADEH et al.
(а) 20 μm (b) 20 μm
Fig. 6. The worn surface morphology of the Ni–P/Ni–B–
B4C coatings (a) before and (b) after heat treatment in
400°C for 1 h.
for the weight loss in coatings have been shown in terms
of slippage distance at room temperature in Fig. 5.
As can be seen, samples, which have been heat
treated at 400°C, experience the least weight loss, and
those without heat treatment experience the most
weight loss. This conclusion is related to the sedimen
tation of intermetallic Ni3B resistant phase during the
crystallization of the amorphous phase, which can also
be proved with regard to the XRD test results [26].
This figure (Fig. 5) shows that the most resistance
to wear is related to the heattreated Ni–P/NiB–B4C
composite coating. The increase in resistance to ero
sion in this coating is due to its crystallization and dis
tribution of B4C nanoparticles in its matrix.
Figure 6 illustrates pictures taken by scanning elec
tron microscope of the eroded surfaces of Ni–P/Ni–
B–B4C coating before and after heat treatment.
As soon in Fig. 6a, in the eroded surface of the sam
ple before heat treatment a plastic transformation has
occurred because the crystal phase has not been
formed in it. The result of this plastic transformation is
the creation of load joints in contact areas and their
disconnection when the slippage continues. There
fore, the dominant mechanism in the erosion in this
sample is the adherent erosion mechanism [24].
Figure 6b shows that heat treatment at 400°C for 1h
has caused the decomposition of the amorphous struc
ture to crystalized Ni and Ni3B, and that the erosion
surface has decreased. The SEM picture of this sample
showed that the Ni–P/Ni–B–B4C duplex composite
coating has remained on the surface of this sample
even after 1000 m of slippage distance.
With regard to the results obtained in this research,
it can be said that the creation of Ni–P/Ni–B–B4C
duplex electroless coating on Ck45 simple carbon steel
can expand the applications of this steel with regard to
a concurrent improvement in resistance to erosion and
corrosion.
PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES Vol. 51 No. 2 2015
4. CONCLUSION
In this study, electroless Ni–P/Ni–P–B4C duplex
composite coating of, coated on a substrate of Ck45
steel, and the following results were obtained:
1. Morphology of created coatings is cauliflower
shape. Furthermore, created coatings are very uniform
and have good connection to the substrate.
2. Moreover, B4C nanoparticles have been evenly
distributed in the electroless coating matrix.
3. Heat treatment at 400°C for onehour leads to
nanocrystalic structure and therefore, an increase
strength and abrasion resistance of coating because of
structure changing and creating Ni3B hard phase.
Maximum abrasion resistance is related to composite
duplex coating that was heat operated.
4. Existence of Ni–P electroless layer and B4C par
ticle’s distribution lead to an improvement in the cor
rosion resistance of Ni–P/Ni–B–B4C coating. Add
ing B4C nano particles lead to filling grooves and holes
and therefore, this leads to a decrease in corrosion sus
ceptible regions and an increase in corrosion resis
tance of coating.
ACKNOWLEDGMENTS
This research has been supported financially by
Najafabad Branch, Islamic Azad University.
REFERENCES
1. Ge, J.P., Che, R.X., and Wang, X.Z., Plat. Surf. Finish.,
1998, vol. 85, no. 10, p. 69.
2. Izzard, M. and Dennis, J.K., Trans. Inst. Mater. Finish.,
1987, vol. 65, p. 85.
3. Yongjun, L., Plat. Surf. Finish., 1997, vol. 84, no. 11,
p. 77.
4. Riedel, W., Electroless Nickel Plating, London: Finish
ing Publ., 1991.
5. Matsuda, H., Yae, S., Iwagishi, T., and Matsuo, H.,
Trans. Inst. Mater. Finish., 1998, vol. 76, p. 241.
6. Bulbul, F., Met. Mater. Int., 2011, vol. 17, p. 67.
7. Pal, S., Verma, N., Jayaram, V., et al., Mater. Sci. Eng., A,
2011, vol. 538, p. 8269.
8. Prusov, Yu.V. and Makarov, V.F., Russ. J. Appl. Chem.,
2005, vol. 78, p. 193.
9. Zhang, W.X., Jiang, Z.H., Li, G.Y., et al., Appl. Surf.
Sci., 2008, vol. 254, p. 4949.
10. Jehn, H.A., Surf. Coat. Technol., 2000, vol. 125, p. 212.
11. Tyler, J.M., Met. Finish., 1995, vol. 93, p. 11.
12. Taheri, R., Saskatoon, 2003.
13. Sankara Narayanan, T.S.N., Baskaran, I., Krishnaveni, K.,
and Parthiban, S., Surf. Coat. Technol., 2006, vol. 200,
p. 3438.
14. Tomlinson, W.J., Surf. Coat. Technol., 1983, vol. 20,
p. 149.
15. Balaraju, J.N., Sankara Narayanan, T.S.N., and
Seshadri, S.K., Mater. Res. Bull., 2006, vol. 41, p. 847.
 ELECTROLESS Ni–P/Ni–B–B4C DUPLEX COMPOSITE COATINGS 239

16. Alirezaei, S., Monirvaghefi, S.M., Saatchi, A., et al.,
Tribo Int., 2013, vol. 62, p. 110.
17. Alirezaei, S., Monirvaghefi, S.M., Salehi, M., and
Saatchi, A., Wear, 2007, vol. 262, p. 978.
18. Balaraju, J.N., Sankara Narayanan, T.S.N., and
Seshadri, S.K., Mater. Res. Bull., 2006, vol. 41, p. 847.
19. Shibli, S.M.A. and Dilimon, V.S., Inter. J. Hydrogen
Energy., 2007, vol. 32, p. 1694.
20. Shibli, S.M.A., Dilimon, V.S., and Deepthi, T., Appl.
Surf. Sci., 2006, vol. 253, p. 2189.
21. Szczygiel, B., Turkiewicz, A., and Serafinczuk, J., Surf.
Coat. Technol., 2008, vol. 202, p. 1904.
22. Shibli, S.M.A., Jabeera, B., and Anupama, R.I., Surf.
Coat. Technol., 2006, vol., 200, p. 3903.
23. May, P.W., Rosser, K.N., Fox, N.A., et al., Diamond
Relat. Mater., 1997, vol. 6, p. 450.
24. EbrahimianHosseinabadi, M., AzariDorcheh, K.,
and Monirvaghefi, S.M., Wear, 2006, vol. 260, p. 123.
25. Chen, C.K., Feng, H.M., Lin, H.C., and Hon, M.H.,
Thin Solid Films, 2002, vol. 416, p. 31.
26. Alishahi, M., Monirvaghefi, S.M., Saatchi, A., and
Hosseini, S.M., Appl. Surf. Sci., 2012, vol. 258, p. 2439.
27. ASM International Handbook: Alloy Phase Diagrams,
ASM International, 1994, p. 1216, 9th ed.
28. Biestek, T., Galva Technol., 1997, vol. 88, p. 1488.

PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES Vol. 51 No. 2 2015