Journal of Alloys and Compounds 630 (2015) 189–194

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Journal of Alloys and Compounds

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

Duplex Ni–P–ZrO2/Ni–P electroless coating on stainless steel

Yuxin Wang a, Xin Shu a,b, Shanghai Wei a, Chuming Liu b, Wei Gao a,⇑, R.A. Shakoor c, Ramazan Kahraman c
a
Department of Chemical & Materials Engineering, The University of Auckland, PB 92019, Auckland 1142, New Zealand
b
School of Materials Science and Engineering, Central South University, Changsha, China
c
Department of Chemical Engineering, College of Engineering, Qatar University, P.O. Box 2713, Doha, Qatar

a r t i c l e i n f o a b s t r a c t

Article history: Duplex Ni–P–ZrO2/Ni–P coating was electroless deposited onto stainless steel substrates. High phospho-
Received 4 November 2014 rus Ni–P coating was plated as the inner layer to improve the corrosion resistance and low phosphorus
Received in revised form 9 January 2015 sol-enhanced Ni–P–ZrO2 coating was on the top to strengthen the mechanical property. The microstruc-
Accepted 10 January 2015
ture, mechanical property, corrosion resistance and hydrophobic property of coating were investigated
Available online 17 January 2015
systematically. The results show that this novel duplex coating possesses both excellent mechanical
property and good corrosion resistance. The microhardness was further improved from 648 HV100 of
Keywords:
Ni–P/Ni–P coating to 752 HV100 of Ni–P–ZrO2/ Ni–P coating, while the hardness of stainless steel is
Duplex coatings
Electroless plating
below 200 HV100. The duplex coatings have very good corrosion resistance due to the different corrosion
Sol-enhanced method mechanism compared with the single Ni–P coating. This duplex coating also shows hydrophobic
Ni–P coating property.
Ó 2015 Elsevier B.V. All rights reserved.

1. Introduction phosphorus content in the deposit. Low phosphorus Ni–P coating

The lifetime of working parts and components largely depend
on the action of external factors and the operating environment.
The surface of a material is the most vulnerable site for various
forms of attack [1]. Therefore, in order to extend the service life
of working parts and cut the costs of materials, surface modifica-
tion is an effective and economical way [2,3]. In many industrial
applications, components, tools, machines or entire plants with
high corrosion resistance and wear resistant surface are essentially
required [4].
Electroplating and electroless plating have been widely used for
surface modification in industry [5]. Comparing with electroplating
which requires complex filtration system and electricity, electro-
less plating relies on a chemical reaction and can provide a uniform
coating layer on irregularly shaped work pieces. It can coat the
whole surface of item evenly, unlike electroplating which have
difficulty depositing onto recessed and internal areas without
excessive buildup on points and corners [6].
Although a variety of metals can be electrolessly plated,
electroless Ni–P coatings have been widely used in many indus-
tries due to their superior properties [7,8]. The microstructure
and properties of electroless Ni–P coatings mainly depend on the
⇑ Corresponding author. Tel.: +64 9 3737599x88175; fax: +64 9 3737463.
E-mail addresses: ywan943@aucklanduni.ac.nz (Y. Wang), w.gao@auckland.ac.
nz (W. Gao).
possesses a mixture of amorphous and microcrystalline
microstructure with relatively high mechanical properties. High
phosphorus Ni–P coating exhibits intrinsically high corrosion resis-
tance due to its homogeneous amorphous microstructure. How-
ever, its mechanical property is comparatively poor [9,10]. In
order to achieve both good corrosion and mechanical properties,
multilayer coatings with a high phosphorus Ni–P coating as the
inner layer were developed in recent years. Different kinds of hard
coatings such as Ni–B [11], Ni–P–ZrO2 and Ni–P–TiO2 [12] were
deposited as the outer layer in order to improve both mechanical
and corrosion properties.
The traditional way to fabricate metal–ceramic composite coat-
ings is mixing hard-solid particles into electrolyte. People use
nano-sized particles to synthesize Ni–P nanocomposite coatings
recently [13–16]. However, it is hard to achieve a good suspension
of nanoparticles in the coating matrix due to their small size and
high surface energy. To avoid particle agglomeration, we devel-
oped a novel sol-enhanced plating technology, which combines
the sol–gel method with electroplating or electroless plating meth-
ods. Highly dispersed nano-particles entered coatings, resulting in
significant improvement in mechanical properties [17–19].
Stainless steels have wide applications including those in chem-
ical plants, construction industry, food processing, automobile
industry and household hardware [20–22]. However, they generally
have low surface hardness and wear resistance. Developing an
effective coating system to have good wear property and maintain

http://dx.doi.org/10.1016/j.jallcom.2015.01.064
0925-8388/Ó 2015 Elsevier B.V. All rights reserved.
190 Y. Wang et al. / Journal of Alloys and Compounds 630 (2015) 189–194

its corrosion resistance is therefore highly desirable. In the present
research, a duplex Ni–P–ZrO2/Ni–P coating was developed on stain-
less steels. High phosphorus Ni–P coating was plated as the inner
layer to ensure good corrosion resistance, while low phosphorus
sol-enhanced Ni–P–ZrO2 coating was deposited as the outer layer
to strengthen the mechanical property. The microstructure,
mechanical property, corrosion resistance and hydrophobic prop-
erty of coatings were systematically investigated.
The microhardness of coating surface was measured using a load of 100 g with a
holding time of 10 s. The results for the hardness were the average of 5
measurements. The wettability of the coatings was tested using static water contact
angle (CA) on a goniometer (KSV CAM-101) at room temperature with 3 lL water
droplets. Salt spray test was carried out following ASTM B117 standard to examine
the corrosion resistance. The samples were exposed in the SALTRON salt spray
cabinet; and 5 wt.% NaCl solution was used at 35 °C in ambient atmosphere. The cor-
rosion potential of each layer were measured by CHI604D electrochemical worksta-
tion using a classical three-electrode cell with platinum as the counter electrode, Ag/
AgCl as reference electrode, and the coating samples with 1 cm2 exposed area as the
working electrode.

2. Experimental

2.1. Sample preparation

3. Results and discussion

Duplex Ni–P–ZrO2/Ni–P coatings were electroless deposited onto the brush fin- 3.1. Phase structure of coatings
ished 316 stainless steel samples (30  10  5 mm3). The standard chemical com-
position of is listed in Table 1 [22]. Before electroless plating, the specimens were
The XRD patterns of the substrate, duplex Ni–P/Ni–P and Ni–P–
thoroughly degreased and rinsed with deionized water. In order to get good adhe-
sion between coating and substrate, Ni strike was used to electroplate a thin Ni ZrO2/Ni–P coatings are shown in Fig. 1. After electroless plating for
layer (<1 lm), followed by the high phosphorus Ni–P coating and sol-enhanced 2 h, the stainless steel substrate was fully covered by the coatings.
low phosphorus Ni–P–ZrO2 coating. The bath composition and plating parameters Only a single broad peak at 44.5° which assigned to the fcc Ni (1 1 1)
are given in Tables 2 and 3. ZrO2 sol was prepared as reported in the previous
plane can be observed in the diffraction patterns. No ZrO2 peaks
papers [17,23]. For comparison purposes, a duplex Ni–P coating without adding
sol was prepared with the identical plating parameters.
could be detected from the duplex Ni–P–ZrO2/Ni–P coatings,
probably due to the low quantity of ZrO2 and high intensity of Ni
diffraction peaks.
2.2. Sample characterization

The crystal structure of the coatings was characterized by X-ray diffraction

3.2. Surface morphology and cross-section of coatings
(XRD) with Cu Ka radiation (Bruker D2, V = 30 kV, I = 10 mA). Diffraction patterns
were recorded in the 2h range from 20° to 80° at a scanning step of 0.02°. Both sur-
face morphology and cross-section microstructure of the coating were analyzed Fig. 2 presents the SEM surface morphology of duplex Ni–P/Ni–
using a FEI Quanta 200 field emission environmental scanning electron microscope. P and duplex Ni–P–ZrO2/Ni–P coatings. All coatings show a typical
The morphologies and distribution of the ZrO2 particles in the plating solution were
morphology of a spherical top shape. A plough can be observed on
characterized by FEI Tecnai F20-ST field emission microscope (HRTEM). The ZrO2
particle size in the electrolyte after adding sol was characterized by a laser diffrac-
the coating surface due to the brush polishing. Duplex Ni–P/Ni–P
tion particle analyzer (Malvern Mastersizer Hydro 2000S). coating has a relatively large grain size with an average diameter
of 1.8 lm as shown in Fig. 2(a). The grains of the sol-enhanced
Ni–P–ZrO2/Ni–P coating are smaller, with a mean size of 1.2 lm
Table 1 (Fig. 2b). The grain refinement of sol-enhanced coating should
Chemical composition of 316 stainless steel.
attribute to the highly dispersed ZrO2 nanoparticles. The
Element Percentage (wt.%) incorporated ZrO2 nanoparticles provide more nucleation sites
C 0.08 and distribute in the grain boundary areas to hinder the grain
Mn 2.00 growth.
Si 0.75 Fig. 3 shows the cross-section microstructure of Ni–P–ZrO2/Ni–
Cr 16.00
P coating. The duplex coating has a total thickness of 22 lm. The
Ni 10.00
Mo 2.00 thickness of low P Ni–P–ZrO2 outer layer is 16 lm, indicating a
P 0.045 deposition speed of 16 lm/h. Correspondingly, the thickness of
S 0.030 inner layer is 6 lm, giving a relatively low deposition rate. The
N 0.10 coating exhibits a good adhesion to the substrate as no defects or
Fe Bal.

Table 2
Bath composition and plating parameters for high phosphorus Ni–P coating.

Bath constituents Quantity Conditions

NiSO4–6H2O 15 g/L PH: 4.5–5.0
NaH2PO2–H2O 30 g/L Agitation: 200 rpm
Lactic acid 20 mL/L Temperature: 80 °C
Citric acid 20 g/L Time: 60 min
Pb2+ 1 mg/L

Table 3
Bath composition and plating parameters for low phosphorus Ni–P–ZrO2 coating.

Bath constituents Quantity Conditions

NiSO4–6H2O 15 g/L PH: 6.0–6.4
NaH2PO2–H2O 14 g/L Agitation: 200 rpm
CH3COO Na 13 g/L Temperature: 80 °C
Thiourea 1 mg/L Time: 60 min
ZrO2 sol 25 mL/L
Fig. 1. XRD spectra of duplex Ni–P coatings and substrate.
 Y. Wang et al. / Journal of Alloys and Compounds 630 (2015) 189–194
Fig. 2. SEM micrographs of coating surface: (a) duplex Ni–P/Ni–P coating and (b) duplex Ni–P–ZrO2/Ni–P coating.
Fig. 3. Cross-section images and EDS line analysis of duplex Ni–P–ZrO2/Ni–P
coating.
cracks could be observed at the interfaces, although a clear
boundary can be seen between low P and high P layers.
According to the EDS line analysis, the phosphorus contents of
low P and high P layers are 5 wt.% and 10 wt.%, respectively.
The low P Ni–P–ZrO2 composite coating exhibits a homogeneous
structure without any visible ZrO2 particles, evidence of the extre-
mely small size and good dispersion.
3.3. Mechanical property of coatings
3.3.1. Microhardness
Fig. 4 shows the microhardness of duplex Ni–P/Ni–P coating
and duplex Ni–P–ZrO2/Ni–P coating. The microhardness of 316
stainless steel is below 200 HV100. After depositing duplex Ni–P/
Ni–P coating, the microhardness was increased to 648 HV100, a
typical value of low phosphorus Ni–P coating. The microhardness
191
Fig. 4. The microhardness of (a) duplex Ni–P/Ni–P coating and (b) duplex Ni–P–
ZrO2/Ni–P coating.
has been further improved to 752 HV100 by applying sol-enhanc-
ing technology.
The strengthening mechanism of sol-enhanced duplex Ni–P–
ZrO2/Ni–P coating can be mainly attributed to two parts: grain
refinement strengthening and dispersion strengthening. The grain
refinement strengthening from Hall–Petch relationship can be
described as below [23]:
HV ¼ 3ry ð1Þ
ry ¼ r0 þ kd1=2 ð2Þ
where ry and r0 is the yield stress and friction stress respectively, k
is a constant and d is the grain size. Eqs. (1) and (2) suggested that
the microhardness of coating increases when the grains are refined.
The grain refinement of coatings has already been confirmed in
Fig. 2. After adding the sol into the plating solution, the average
grain size of duplex coating was decreased from 1.8 lm to
1.2 lm. The incorporated ZrO2 nano-particles refined the grain
size, resulting in a grain refinement strengthening effect.
Fig. 5 shows the particle size distribution of the plating solution
with ZrO2 sol. It can be seen that the particle size was distributed in
the range of 10–30 nm. The mean value of particle size for the TiO2
sol was 22.5 nm. Fig. 6 presents the TEM images of ZrO2 nano-
particles separated from the plating solution of low phosphorus
Ni–P–ZrO2 coating. Apparent particle agglomeration can be seen
in Fig. 6a. High magnification bright images (Fig. 6b and c) show
that these particles agglomeration or clusters was composed of
small ZrO2 nano-particles with a size of 25 nm, which is consis-
tent with the results of particle size distribution. The apparent par-
ticle agglomeration should form in the TEM sample preparation
192 Y. Wang et al. / Journal of Alloys and Compounds 630 (2015) 189–194

tion will lead to the polymerization reaction of sol, forming well

dispersed ZrO2 nano-particles under the effect of ethanol and
DEA. The nano-particles can be absorbed into the freshly deposited
surface with the help of van der Waals forces and mechanical
movement driven by continuous agitation. Finally, Ni–P–ZrO2
nano-composite coating with highly-dispersed ZrO2 nano-particles
was electroless deposited [18,24,25].
The highly-dispersed ZrO2 nano-particles in the coating will
take the effect of particles dispersion hardening which is known
as Orowan mechanism. The Orowan mechanism indicates that
the parameters including spacing between particles, particle size

Fig. 5. Particle size of the plating solution with ZrO2 sol.

Fig. 7. Wear track images of (a) duplex Ni–P/Ni–P coating and (b) duplex Ni–P–
ZrO2/Ni–P coating.

Fig. 6. TEM bright field images of ZrO2 nano-particles separated from the plating
solution of sol-enhanced Ni–P–ZrO2 coating.

process as no such big particles or clusters were found in the coat-

ings under SEM examinations.
In the present experiment, the ZrO2 sol consists of Zr (IV) n-
propoxide, anhydrous ethanol and DEA. When the ZrO2 sol solution Fig. 8. Wear depth and wear volume of (a) duplex Ni–P/Ni–P coating and (b) duplex
is added into the plating solution, the hydrate Ni ions in the solu- Ni–P–ZrO2/Ni–P coating.
 Y. Wang et al. / Journal of Alloys and Compounds 630 (2015) 189–194
Table 4
Salt spray results of duplex coatings and corrosion potential of each layer.
Duplex coating sample Failure type (after 480 h)
Ni–P/Ni–P Controlled pitting corrosion with substrate unaffected
Ni–P–ZrO2/Ni–P Controlled pitting corrosion with substrate unaffected
and particle volume fraction dominate the effect of dispersion
strengthening [26]. When the matrix carries a load, the highly dis-
persed ZrO2 nanoparticles impede the mobility of dislocations,
increasing the hardness of coating.
3.3.2. Tribological properties
The wear track images, wear track width and wear volume loss
of duplex Ni–P/Ni–P coating and duplex Ni–P–ZrO2/Ni–P coating
were shown in Figs. 7 and 8. The wear track width, depth and
volume loss of duplex Ni–P/Ni–P coating was 368 lm, 5.65 lm
and 3.00  1013 m3, respectively. After co-depositing the ZrO2
nanoparticles into the low phosphorus Ni–P coating matrix by
using sol-enhancing technology, The wear track width, depth and
volume loss was decreased to 317 lm, 4.19 lm and
1.65  1013 m3.
Considering the depth of wear track on coatings is smaller than
10 lm, the wear was conducted on the outer layer. The improve-
ment of wear resistance could be mainly attributed to the
improved hardness and the incorporated ZrO2 nanoparticles. The
Fig. 9. Water contact angles of (a) duplex Ni–P/Ni–P coating and (b) duplex Ni–P–
ZrO2/Ni–P coating.
193
Sample Corrosion potential (v)
Low phosphorus Ni–P coating outer layer 0.24
High phosphorus Ni–P coating inner layer 0.18
highly dispersed hard ZrO2 nanoparticles in the coatings can
reduce the wear loss of the outer coating layer, and may also play
a role of solid lubricant during the wear process.
3.4. Corrosion property of coatings
The two types of duplex coatings were exposed in the salt spray
chamber for 480 h. All samples show a light pitting with substrate
unaffected, evidence of very good corrosion resistance as shown in
Table 4. For a single layer of Ni–P coating, corrosion usually devel-
ops vertically from the coating surface to the substrate matrix
through the unavoidable pores of the coating. A micro circuit can
form between the coating and underneath substrate. The corrosion
grows fast because of the large cathode (coating) and relatively
small anode (exposed substrate).
On the other side, the corrosion of duplex Ni–P coating usually
develops horizontally. The outer layer of low phosphorus Ni–P
coating has a relatively low corrosion potential (0.24 V) for its
mixed amorphous and microcrystalline structure, while the inner
layer of high phosphorus Ni–P coating presents a relatively high
corrosion potential (0.18 V) for its amorphous structure. Due
to the corrosion potential difference of two layers, the low phos-
phorus Ni–P coating layer will act as the sacrificial anode while
the small exposed high phosphorus Ni–P coating layer will act as
the cathode. The corrosion rate therefore is much slower than
the single layered Ni based coatings [12,27].
3.5. Hydrophobic property of coatings
Fig. 9 shows the water contact angles of duplex Ni–P/Ni–P and
Ni–P–ZrO2/Ni–P coatings. All coatings have a similar contact angle
around 106° which means they both are hydrophobic. Hydropho-
bic property is important for stainless steel due to its applications
in such as food processing and building industries. Further study is
being conducted on the chemical modification of duplex coating
surface in order to achieve superhydrophobicity of the coating sur-
face without sacrificing other properties.
4. Conclusion
Duplex Ni–P–ZrO2/Ni–P coating was deposited on the stainless
steel substrate. The microhardness of duplex coating was
significantly increased comparing with that of stainless steel. By
virtue of sol-enhanced technology, the microhardness of duplex
Ni–P–ZrO2/Ni–P coating can further improved to 752 HV100. All
duplex coatings present excellent anticorrosion property due to
the special corrosion mechanism of two-layered coating structure.
These duplex coatings show hydrophobicity property. With further
modification, these coatings may find broad applications in such as
chemical plants, food processing, automobile industry, and
household hardware.
Acknowledgments
The project is funded by NPRP Grant #NPRP-4-662-2-249 from
the Qatar National Research Fund (a member of Qatar Foundation).
It is also supported by a New Zealand Marsden Grant and Auckland
UniServices project. The authors would like to thank the technical
194 Y. Wang et al. / Journal of Alloys and Compounds 630 (2015) 189–194
stuff in the Department of Chemical and Materials Engineering and
the Research Centre of Surface and Materials Science for various
assistances. We also express our gratitude to Glen Slater, Chris
Goode and technical stuff in Rigg Electroplating Ltd and Electroless
Coating Systems Ltd.
References
[1] Nasser Kanani, Electroplating, Elsevier Advanced Technology, Oxford, 2004.
[2] R.A. Shakoor, R. Kahraman, U. Waware, Y.X. Wang, W. Gao, Properties of
electrodeposited Ni–B–Al2O3 composite coatings, Mater. Des. 64 (2014) 127–
135.
[3] R.A. Shakoor, R. Kahraman, U. Waware, Y.X. Wang, W. Gao, Synthesis and
properties of electrodeposited Ni–B–CeO2 composite coatings, Mater. Des. 59
(2014) 421–429.
[4] S. Karthikeyan, B. Ramamoorthy, Effect of reducing agent and nano Al2O3
particles on the properties of electroless Ni–P coating, Appl. Surf. Sci. 307
(2014) 654–660.
[5] Arthur A. Tracton, Coatings Technology Handbook, CRC Press, Boca Raton,
2006.
[6] Glenn.O. Mallory, Juan.B. Hajdu, Electroless Plating: Fundamentals and
Applications, Noyes Publications, New York, 1990.
[7] T.S.N. Sankara Narayanan, I. Baskaran, K. Krishnaveni, S. Parthiban, Deposition
of electroless Ni–P graded coatings and evaluation of their corrosion
resistance, Surf. Coat. Technol. 200 (2006) 3438–3445.
[8] M. Sarret, C. Müller, A. Amell, Electroless NiP micro- and nano-composite
coatings, Surf. Coat. Technol. 201 (2006) 389–395.
[9] C.D. Gu, J.S. Lian, G.Y. Li, L.Y. Niu, Z.H. Jiang, High corrosion-resistant Ni–P/Ni/
Ni–P multilayer coatings on steel, Surf. Coat. Technol. 197 (2005) 61–67.
[10] P. Sahoo, S.K. Das, Tribology of electroless nickel coatings–a review, Mater.
Des. 32 (2011) 1760–1775.
[11] T.S.N. Sankara Narayanan, K. Krishnaveni, S.K. Seshadri, Electroless Ni–P/Ni–B
duplex coatings: preparation and evaluation of microhardness, wear and
corrosion resistance, Mater. Chem. Phys. 82 (2003) 771–779.
[12] E. Georgiza, J. Novakovic, P. Vassiliou, Characterization and corrosion
resistance of duplex electroless Ni–P composite coatings on magnesium
alloy, Surf. Coat. Technol. 232 (2013) 432–439.
[13] J.N. Balaraju, T.S.N. Sankara Narayanan, S.K. Seshadri, Electroless Ni–P
composite coatings, J. Appl. Electrochem. 33 (2003) 807–816.
[14] J. Novakovic, P. Vassiliou, Vacuum thermal treated electroless NiP–TiO2
composite coatings, Electrochim. Acta 54 (2009) 2499–2503.
[15] K. Zielińska, A. Stankiewicz, I. Szczygieł, Electroless deposition of Ni–P-nano-
ZrO2 composite coatings in the presence of various types of surfactants, J.
Colloid. Interf. Sci. 377 (2012) 362–367.
[16] P. Makkar, R.C. Agarwala, V. Agarwala, Chemical synthesis of TiO2
nanoparticles and their inclusion in Ni–P electroless coatings, Ceram. Int. 39
(2013) 9003–9008.
[17] W.W. Chen, W. Gao, Plating or coating method for producing metal–ceramic
coating on a substrate, Patent NZ578038, New Zealand, 2009.
[18] W.W. Chen, W. Gao, Y.D. He, A novel electroless plating of Ni–P–TiO2 nano-
composite coatings, Surf. Coat. Technol. 204 (2010) 2493–2498.
[19] Y.X. Wang, W.W. Chen, A. Shakoor, R. Kahraman, W. Lu, B. Yan, W. Gao, Ni–P–
TiO2 composite coatings on copper produced by sol-enhanced electroplating,
Int. J. Electrochem. Sci. 9 (2014) 4384–4393.
[20] K. Hari Krishnan, S. John, K.N. Srinivasan, J. Praveen, M. Ganesan, P.M.
Kavimani, An overall aspect of electroless Ni–P depositions–a review article,
Metall. Mater. Trans. A 37 (2006) 1917–1926.
[21] Q. Zhao, Y. Liu, Modification of stainless steel surfaces by electroless Ni–P and
small amount of PTFE to minimize bacterial adhesion, J. Food. Eng. 72 (2006)
266–272.
[22] J.R. Davis, ASM Specialty Handbook: Stainless Steels, ASM International, 1994.
[23] Y.J. Yang, W.W. Chen, C.W. Zhou, H.B. Xu, W. Gao, Fabrication and
characterization of electroless Ni–P–ZrO2 nano-composite coatings, Appl.
Nanosci. 1 (2011) 19–26.
[24] W.W. Chen, Y.D. He, W. Gao, Electrodeposition of sol-enhanced
nanostructured Ni–TiO2 composite coatings, Surf. Coat. Technol. 204 (2010)
2487–2492.
[25] Y.X. Wang, Y. Ju, S.W. Wei, W. Gao, W. Lu, B. Yan, Au–Ni–TiO2 nano-composite
coatings prepared by sol-enhanced method, J. Electrochem. Soc. 161 (2014)
D775–D781.
[26] Y.X. Wang, S.J. Wang, X. Shu, W. Gao, W. Lu, B. Yan, Preparation and property of
sol-enhanced Ni–B–TiO2 nano-composite coatings, J. Alloys Comp. 617 (2014)
472–478.
[27] W.X. Zhang, Z.H. Jiang, G.Y. Li, Q. Jiang, J.S. Lian, Electroless Ni–P/Ni–B duplex
coatings for improving the hardness and the corrosion resistance of AZ91D
magnesium alloy, Appl. Surf. Sci. 254 (2008) 4949–4955.