Surface & Coatings Technology 200 (2006) 6808 – 6814

www.elsevier.com/locate/surfcoat

The physical and electrochemical properties of electroless deposited

nickel–phosphorus black coatings
Guofeng Cui ⁎, Ning Li, Deyu Li, Jian Zheng, Qinglong Wu
Department of Applied Chemistry, Harbin Institute of Technology, Harbin 150001, PR China
Received 14 June 2005; accepted in revised form 15 October 2005
Available online 23 November 2005

Abstract

The manufacture of electroless black nickel surfaces had been obtained, through etching electroless nickel deposits by oxidizing acid
solution. The morphology, chemical composition and reflectance of pre-etch and post-etch coatings were compared to examine influence of
phosphorus and sulfur content on preparation of black surfaces. The non-metallic elements content of electroless nickel deposits was greatly
improved after black treatment. It indicated the etching treatment was a selective dissolving process. The nickel atoms can be preferentially
removed during the period. Optimum phosphorus content range to produce low reflectance black surface was proposed, after reflectance
measurement of black surfaces. Additionally, the effect of co-deposited phosphorus and sulfur atoms on corrosion resistance of electroless
nickel deposits was evaluated by electrochemical impedance spectroscopy (EIS). The fitting results indicated that corrosion resistance of high-
phosphorus electroless nickel deposits will be significantly reduced after black treatment. However, that of low-phosphorus deposits will be
improved.
© 2005 Elsevier B.V. All rights reserved.

Keywords: Electroless nickel; Phosphorus content; Black treatment; Electrochemical impedance spectroscopy; Corrosion resistance

1. Introduction decorative coatings, photo-thermal conversed material, ab-

The electroless deposition of nickel in bath containing
hypophosphite was first noted by Wurtz in 1844 [1], but it
was not applied on an industrial scale until an accidental
rediscovery of the technique by Brenner and Riddell in 1946
[2–4]. Nowadays, electroless nickel plating coatings have
been well-known as a hard coating for industrial application,
due to their excellent hardness, corrosion and wear resistance
properties [5–7].
Black nickel coatings can be accompanied by electro- [8–
10] and electroless [11] depositions. In general, metallic
brown/black appearance of electroless nickel black parts were
obtained by blackened treatment, after they were electroless
plated with nickel. Super black or black electroless nickel
coating, as it is based on a nickel–phosphorous compound, is
set to have a major application in fields, such as black
⁎ Corresponding author. Tel.: +86 631 568 7232.
E-mail address: cuiguofeng@hit.edu.cn (G. Cui).
0257-8972/$ - see front matter © 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.surfcoat.2005.10.015
sorbing material, and within aerospace and defense industries
[11].
The phosphorus element can co-deposit with nickel,
resulting in the formation of an Ni–P alloy, during electroless
plating process [12–14]. The phosphorous content can reach
between 1% and 15% by weight. According to ASTM 733B-04
standard, electroless Ni–P films can be classified as low (1–4
wt.% P), medium (5–9 wt.% P) and high (10 wt.% P and more)
phosphorus layer, based on their phosphorus content. The
incorporation of phosphorus greatly affects physical and
chemical properties of the coating, such as density, hardness,
corrosion resistance, etc.
The electroless plating bath is a typical metastable system.
Spontaneous decomposition of baths can be virtually
eliminated or controlled by the addition of a small amount
of stabilizers. But, the decomposition of stabilizers can bring
the third element co-deposition, such as sulfur element, with
thiourea added in baths. Those impurity elements can also
greatly impact the properties of coatings, especially corrosion
resistant property. However, there were few papers to report
 G. Cui et al. / Surface & Coatings Technology 200 (2006) 6808–6814 6809

influences of chemical composition of deposits on physical
and corrosion resistant property of electroless Ni–P black
coatings.
In this work, comparison of the chemical composition and
physical characteristics of the pre-etched and post-etched Ni–
P alloy were investigated. Moreover, corrosion resistance of
the coating was evaluated by electrochemical impedance
spectroscopy (EIS), which had been extensively used to eval-
uate the corrosion performance of electroless nickel coatings
[15,16].

Fig. 1. Typical AFM morphologies of pre-etch (left) and post-etch (right) electroless nickel surfaces, with pre-etch phosphorus content at (A) 2.87 wt.%, (B) 8.39 wt.%,
(C) 10.10 wt.% and (D) 12.91 wt.%, respectively.
6810 G. Cui et al. / Surface & Coatings Technology 200 (2006) 6808–6814
2. Experimental
Medium carbon steel sheets (20 × 50 mm2 and 0.5 mm thick)
were used as substrates for electroless nickel deposition. The
substrates were firstly degreased with 10% NaOH and acetone.
Subsequently, they were deoxidized in 5% H2SO4 solution.
After rinsing with deionized water, the substrates were
introduced into the plating bath. The compositions and
operation parameters of plating baths were listed in Tables 1
and 2. The plating load capacity was kept at 100 cm2 l− 1. The
substrates were immersed into bath in 2 h at 85 ± 2 °C. All
reagents were of analytical grade. Solutions were prepared by
Mill-Q ultrapure water with resistance of 17 MΩ or higher.
Electroless plating nickel coatings were etched as follows.
The samples were immersed into 5.5 M sulfuric acid and 4.1 M
sodium nitrate solution at 50 °C after 10 s. After rinsing with
deionized water and drying by electric dryer, they were
introduced into etching solution again for 5 s. The similar
black treatment method was described in the literatures [5,6,11].
The morphology of electroless nickel and black nickel
surfaces were observed by a PicoPlus™ atomic force
microscope (AFM) from Molecular Imaging Corp. (USA).
AFM measurement is in contact mode using ultra-lever tips with
nominal spring constant at 25 N m − 1 . The chemical
composition of Ni–P alloys were analyzed by X-ray fluores-
cence spectrometer (XRF) model S4-Explorer from Brukeraxs
(Germany). The XRF spectra were evaluated by automatic
analysis program Spectraplus. Visible reflectance measurements
on the electroless black nickel surfaces were carried out using a
300 mm diameter integrating sphere and a 30 mW He–Ne laser
operating at 633 nm.
The electrochemical impedance measurements were per-
formed in a conventional three-compartment Pyrex cell, using
an EG&G potentiostat/galvanostat Model 273 coupled with
EG&G PAR lock-in amplifier model 510. An ac voltage (sine
wave) with amplitude of 10 mV was used as imposing signal,
and the measurement frequency range was set from10,000 to
0.01 Hz. The software of ZsimDemo version 3.11d written by
Dr. Bruno Yeum was used for ac impedance data analysis.
Defined sample area of 2 cm2 was exposed to the electrolyte. A
Luggin capillary was placed near the working electrode to
minimize ohmic drop. A saturated calomel electrode and a
platinum sheet were used as reference and auxiliary electrodes,
respectively. All electrode potentials are referred to SCE if not
otherwise stated. The corrosion electrolyte was 3.5 wt.% NaCl
solution, prepared by Milli-Q grade ultrapure water.
3. Results and discussion
3.1. Effect of pre-etch phosphorus content on preparation of
electroless black nickel coatings
The phosphorus content of electroless plating Ni–P alloy are
known to have a great influence on both chemical [17–19] and
electrochemical [20–23] properties. In general, with greater P
content, the coatings are more resistant to acid etching. Brown
et al. had found that none of blacken methods can be employed
to etch electroless Ni–P alloys with phosphorous content more
than 14 wt.% [11]. This is consistent with a general finding that
mid and low phosphorous coatings can obtain lower reflectance
of black nickel surface.
The comparison of AFM morphology for pre-etch and post-
etch electroless nickel surfaces at various phosphorus content
alloys can be clearly observed in Fig. 1. There are many nodular
structures as characteristic structure on pre-etch electroless
nickel surfaces. The morphology difference between pre-etch
surfaces containing from low to high phosphorous Ni–P alloys is
not obvious in AFM images. This may be attributed to elec-
troless nickel baths without any additive to act as leveling and
bright effect on the surfaces, as shown in Table 1. However, the
surfaces became smoother, and those nodular structures evolved
into smaller convex closure-like structure after black treatment.
The phosphorus contents of pre- and post-etch electroless
Ni–P alloy obtained by XRF measurement are shown in Table
3. The phosphorous content of the coatings is greatly improved
after black treatment. It indicated that preferential dissolution of
nickel atoms on the electroless nickel coatings occurred in the
etching process.
The reflectances at 633 nm of electroless black nickel surfaces
at various phosphorus contents of pre-etch alloys are shown in
Fig. 2. The measurement results were similar to data obtained by
Brown et al. in Ref. [11]. We found electroless black nickel
surfaces existed in lower reflectance, which occurred on lower
phosphorous content of pre-etch coatings. It may be caused by the
etching treatment that is less complete with improving phospho-
rous content. Optimum phosphorus content range to prepare low
reflectance black nickel coatings is from 3 to 7 wt.%.
3.2. The effect of impurity element on preparation of electroless
black nickel coatings
Commercial electroless nickel solutions usually contain some
stabilizers to prolong lifetime of the baths. Stabilizers can
prevent the homogeneous reactions, which trigger spontaneous
1.0
Average Reflectance at 633 nm [%]
0.9
0.8
0.7
0.6
0.5
0.4
2 3 4 5 6 7 8 9 10 11 12 13 14
Pre-etch phosphorus content / wt%
Fig. 2. The average reflectance at 633 nm of electroless black nickel surfaces at
various pre-etch phosphorus content.
 G. Cui et al. / Surface & Coatings Technology 200 (2006) 6808–6814 6811

decomposition of an entire plating process [24,25]. Thiourea can
be used as an effective stabilizer for electroless plating nickel
bath [26,27]. During electroless nickel deposition process, sulfur
atoms can co-deposit with nickel by secondary reactions [26].
Meanwhile, they can greatly affect corrosion resistant property
of Ni–P alloys, although sulfur content is rather low.
The chemical composition and reflectance of pre- and
post-etch electroless nickel alloys were shown in Table 4. The
measured samples were obtained in Table 2. The XRF
patterns of sulfur element for electroless nickel deposits on
as-plated and blacken states were shown in Fig. 3, because
sulfur content is too low inffi this measurement. All coalescing
pffiffiffi
peaks centered around E ¼ 5:982 and the peak amplitudes
corresponding to sulfur content in alloys. The peak
amplitudes and sulfur content of post-etch samples were
greatly higher than those of pre-etch ones, as illustrated in
Table 4 and Fig. 3. It indicated that the selective nature of the
etching process, in which the nickel atoms can be preferential,
dissolved, but non-metallic atoms will be left in the alloys.
Additionally, the reflectance of black nickel surface de-
creased, with sulfur content increasing, although phosphorous
content of three samples were similar.

A B

Post-etch
Sqr (kcps)

Sqr (kcps)

Post-etch

Pre-etch Pre-etch

SqE- Scale SqE- Scale

C
Post-etch
Sqr (kcps)

Pre-etch

SqE- Scale

Fig. 3. The XRF patterns of single sulfur element in electroless nickel and black nickel alloys obtained in bath as described in Table 2.
6812 G. Cui et al. / Surface & Coatings Technology 200 (2006) 6808–6814

A A
3000
P=2.89%
P=8.39% 2400 A
2700
P=9.13% B
2400 P=10.10% 2100 C
P=12.90%
2100 1800
-Zim / (Ω .cm2)

-Zim / (Ω .cm2)
1800
1500
1500
1200
1200
900
900
600 600

300 300
0 0
0 1000 2000 3000 4000 5000 6000 0 500 1000 1500 2000 2500 3000 3500 4000 4500 5000
Zre / (Ω .cm2) Zre / (Ω .cm2)
B B
1400 1100
P=2.89%
P=8.39% A
1000
1200 B
P=9.13%
P=10.10%
900 C

1000 P=12.90%
-Zim / (Ω .cm2) 800
-Zim / (Ω .cm2)

700
800 600
500
600
400
400 300
200
200 100
0
0 0 200 400 600 800 1000 1200 1400 1600 1800 2000 2200
0 500 1000 1500 2000 2500
Zre / (Ω .cm2)
Zre / (Ω .cm2)
Fig. 6. Nyquist plots of electroless nickel coatings on as-plated (A) and blacken
Fig. 4. Nyquist plots of electroless nickel coatings on as-plated (A) and blacken conditions (B) at various sulfur content on samples obtained in Table 2 in 3.5%
conditions (B) at various phosphorus content on the pre-etch coatings in 3.5% sodium chloride solution.
sodium chloride solution.

3.3. Corrosion resistant property of electroless black nickel various phosphorous contents were compared in Fig. 4.
coatings Those plots were fitted by the equivalent circuit as
illustrated in Fig. 5. The fitting results are shown in
The electrochemical impedance spectra of as-deposited Table 5. Similar corrosion behavior evaluated method for
and blackened electroless plating nickel coatings in 3.5% electroless plating nickel coatings was used in literatures
sodium chloride media were shown in Fig. 4(A) and (B), [15,16].
respectively. The Nyquist plots of pre-etch coatings at
Table 1
Bath compositions and operating conditions of electroless Ni–P depositions
Bath constituents and parameters Quantity (mol·L− 1)
Nickel sulfate (NiSO4·6H2O) 0.10
Sodium hypophosphite 0.08, 0.1, 0.13, 0.15, 0.20,
(NaH2PO2·H2O) 0.25, 0.3, 0.35, 0.40
Sodium acetate (CH3COONa) 0.15
D,L-Malic acid 0.03
Rs- Resistance of solution. Citrate acid 0.02
Rc- Corrosion resistance of the coating. Succinic acid 0.05
Q- Constant phase element. Lauryl sodium sulfate 8 mg·l− 1
Operating conditions
pH 5.8
Fig. 5. Equivalent circuit for electrochemical impedance measurement on
Temperature 85 ± 2 °C
corrosion resistance of electroless nickel deposits.
 G. Cui et al. / Surface & Coatings Technology 200 (2006) 6808–6814 6813

Table 2 There is a constant phase element (CPE) in the equivalent

Bath compositions and operating conditions of electroless Ni–P depositions circuit as shown in Fig. 5. It is mainly used to explain
containing various concentration of thiourea
inhomogeneous and some distribution (dispersion) of the real
Bath constituents and parameters Quantity (mol·L− 1) system. The CPE resembles a capacitor, because the value of
Nickel sulfate (NiSO4·6H2O) 0.10 CPEc-P approaches 1.0 in our experiment. The values of Rc
Sodium hypophosphite (NaH2PO2·H2O) 0.30 increased and values of CPEc-T decreased on as-plated coatings,
Sodium acetate (CH3COONa) 0.15
with phosphorous content in pre-etch deposits increasing. It
D,L-Malic acid 0.03
Citrate acid 0.02 indicated that corrosion resistant ability of coatings improved,
Succinic acid 0.05 with increasing phosphorous content. Comparing the fitted
Thiourea (TU) 2, 6, 8 mg·L− 1 parameters to the pre- and post-etch coatings at the same
Lauryl sodium sulfate 8 mg L− 1 phosphorous content, the values of Rc and CPEc-T reduced and
Operating conditions
improved, respectively, after black treatment, expected for the
pH 5.8
Temperature 85 ± 2 °C coating at pre-etch phosphorus content of 2.87 wt.%. That can be
attribute to the compact coatings change to porous and inho-
mogeneous structure after black treatment. The micro-scale
Table 3 surface morphologies can support this opinion as illustrated in
Chemical composition of pre- and post-etch electroless Ni–P alloys Fig. 1. For electroless nickel deposits, pitting corrosion is a main
Sample Element content of Element content of defect model [28]. These defects on deposits will lead to serious
pre-etch alloy (wt.%) post-etch alloy (wt.%) defect and reduce corrosion resistance (Table 6).
Ni P Ni P The phosphorus content of the three deposits approaches
A 97.13 2.87 94.24 5.76 the same value of 10.6 and 14.0 wt.% on pre-etch and post-
B 91.61 8.39 85.90 14.10 etch condition, respectively, as shown in Table 3. However,
C 89.90 10.10 83.74 16.26 there is a great difference in sulfur content of samples on as-
D 87.10 12.90 84.30 15.70
plated and blacken condition in Fig. 3. Fig. 6 showed Nyquist
plots of the three samples on different conditions at various
Table 4 sulfur content. Similar to the analysis in Fig. 4, the Nyquist
Chemical compositions and reflectance of pre- and post-etch electroless Ni–P plots were fitted by the equivalent circuit. The fitted results
alloys
were listed in Table 5. The values of corrosion resistance
Sample Element content of pre- Element content of Reflectance reduced greatly, with sulfur content increasing on as-plated
etch alloy (wt.%) post-etch alloy (wt.%) (%)
condition. The values of Rc reduced from 4282, 3508 to 3328
Ni P S Ni P S Ω cm2, as described in Table 5. However, the values of Rc
A 88.50 10.5 micro 85.73 14.1 0.127 0.70 were similar on blacken condition. It indicated that the co-
B 89.31 10.6 micro 85.62 13.9 0.346 0.62 deposited sulfur atoms can greatly decrease corrosion
C 87.55 11.4 0.050 84.83 14.3 0.771 0.55
resistance of deposits on as-plated condition.

Table 5
Fitted results of Nyquist plots for electroless nickel deposits on equivalent circuit described in Fig. 5
Phosphorous 2.87 wt.% 8.39 wt.% 9.13 wt.% 10.1 wt.% 12.9 wt.%
content
As-plated Blacken As-plated Blacken As-plated Blacken As-plated Blacken As-plated Blacken
Rs 14.64 15.99 15.72 15.81 14.2 16.17 14.25 16.03 14.35 15.70
Rc 1356 2122 2954 2139 3648 2095 4200 2674 5772 3012
CPEc
CPEc-T 4.397e − 5 1.165e − 3 7.337e − 5 1.768e − 3 1.077e − 4 2.741e − 3 1.104e − 4 2.749e − 3 1.477e − 4 3.391e − 3
CPEc-P 0.8174 0.9072 0.8463 0.8795 0.8051 0.8533 0.8040 0.9004 0.8244 0.8443
Unit of Rs and Rc is Ω cm2. Unit of CPEc-T is F cm− 2.

Table 6
Fitted results of Nyquist plots for electroless nickel deposits on equivalent circuit described in Fig. 5
Sample A B C
As-plated Blacken As-plated Blacken As-plated Blacken
Rs 16.44 16.36 16.55 16.58 16.48 16.37
Rc 4282 1924 3508 1892 3328 1936
CPEc
CPEc-T 2.124e − 4 1.574e − 3 1.359e − 4 3.299e − 3 5.784e − 4 4.803e − 3
CPEc-P 0.8181 0.8943 0.9084 0.9098 0.9013 0.9058
Unit of Rs and Rc is Ω cm2. Unit of CPEc-T is F cm− 2.
6814 G. Cui et al. / Surface & Coatings Technology 200 (2006) 6808–6814

4. Conclusions References

The purpose of this paper was to report the effect of [1] A. Wurtz, C.R. Hebd, Séances Acad. Sci. 18 (1844) 702.
phosphorus and sulfur content on the physical and electro- [2] A. Brenner, G.E. Riddell, J. Res. Natl. Bur. Stand. (U.S.) 37 (1946) 91.
[3] A. Brenner, G.E. Riddell, J. Res. Natl. Bur. Stand. (U.S.) 39 (1947) 385.
chemical properties of electroless black nickel deposits. The [4] A. Brenner, D.E. Couch, E.K. Williams, J. Res. Natl. Inst. Stand. Technol.
black coatings were prepared in oxidizing acid solution, after 44 (1950) 109.
the electroless plating process. The morphology, chemical [5] S. Kodama, M. Horiuchi, T. Kunii, K. Kuroda, IEEE Trans. Instrum. Meas.
composition and corrosion resistant property of electroless 39 (1990) 230.
plating nickel deposits on as-plated and blacken conditions were [6] C.E. Johnson, Met. Finish. 78 (1980) 21.
[7] J. Hajdu, S. Zabrocky, Met. Finish. 98 (2000) 42.
investigated by AFM, XRF and EIS, respectively. The research [8] E. Wäckelgård, Sol. Energy Mater. Sol. Cells 56 (1998) 35.
results showed that: [9] M.L. Cantú, A.M. Sabio, A. Brustenga, P.G. Romero, Sol. Energy Mater.
Sol. Cells 87 (2005) 685.
(1) The electroless black nickel surfaces with lower [10] S. John, Met. Finish. 95 (1997) 84.
reflectance in the visible region can be prepared by [11] R.J.C. Brown, P.J. Brewer, Martin J.T. Milton, J. Mater. Chem. 12 (2002)
2750.
lower phosphorous content coatings on as-plated [12] S. John, N.V. Shanmugham, B.A. Shenoi, Met. Finish. 80 (1982) 47.
condition. [13] L.M. Abrantes, J.P. Correia, J. Electrochem. Soc. 141 (1994) 2356.
(2) The non-metallic element content greatly improved after [14] K. Parker, Plat. Surf. Finish. 74 (1987) 60.
the black treatment, including phosphorus and sulfur [15] T.S.N. Sankara Narayanan, S.K. Seshadri, J. Alloys Compd. 365 (2004)
elements. It can be attributed to preferential dissolution of 203.
[16] Y.S. Huang, X.T. Zeng, X.F. Hu, F.M. Liu, Electrochim. Acta 49 (2004)
the nickel atoms at the coating surface during the etching 4313.
period. [17] W. Riedel, Electroless Nickel Plating, Finishing Publications Ltd.,
(3) The phosphorous atoms incorporated with nickel atoms Stevenage, UK, 1991.
can effectively increase corrosion resistance of electroless [18] R.C. Agarwala, S. Ray, Z. Met.kd. 79 (1988) 472.
[19] W. Ding, M. Wang, C. Hsiao, Y. Xu, Z. Tian, Scr. Metall. 21 (1987) 1685.
nickel deposits, while sulfur atoms decrease it, on as-
[20] S.W. Court, B.D. Barker, F.C. Walsh, Trans. Inst. Met. Finish. 78 (2000)
plated condition. 157.
(4) The corrosion resistance of high-phosphorus electroless [21] C. Kerr, D. Barker, F.C. Walsh, Trans. Inst. Met. Finish. 74 (1996) 214.
nickel deposits will be significantly reduced after black [22] D. Barker, S. Campbell, F. Walsh, Trans. Inst. Met. Finish. 75 (1997) B110.
treatment. However, that of low-phosphorus deposits will [23] C. Kerr, D. Barker, F.C. Walsh, Trans. Inst. Met. Finish. 75 (1997) 81.
be improved. [24] M. Schlesinger, in: M. Schlesinger, M. Paunovic (Eds.), Modern
Electroplating, 4th ed., John Wiley and Sons, Inc., New York, USA,
2000, Chap. 18.
Acknowledgements [25] I. Petukhov, M. Shcherban, V. Kichigan, Prot. Met. 35 (1999) 85.
[26] H. Xu, J. Brito, O.A. Sadik, J. Electrochem. Soc. 150 (2003) C816.
We greatly thank the Chinese Doctoral Foundation in the [27] W.J. Cheong, B.L. Luan, D.W. Shoesmith, Appl. Surf. Sci. 229 (2004) 282.
form of Grant 20030213007 through the Chinese Education [28] C. Gu, J. Lian, G. Li, L. Niu, Z. Jiang, Surf. Coat. Technol. 197 (2005) 65.
Department for financial support at Harbin Institute of
Technology in PR China.