Russian Journal of Applied Chemistry, Vol. 78, No. 1, 2005, pp. 82!84.

Translated from Zhurnal Prikladnoi Khimii, Vol. 78, No. 1, 2005, pp. 83!85. Original Russian Text Copyright + 2005 by Makarov, Prusov, Lebedeva.

APPLIED ELECTROCHEMISTRY AND CORROSION PROTECTION OF METALS

Electroless Deposition of Nickel Coatings with High Phosphorus Content

V. F. Makarov, Yu. V. Prusov, and I. O. Lebedeva
Nizhni Novgorod State Technical University, Nizhni Novgorod, Russia
Received March 22, 2004

Abstract Acid hypophosphite solution for electroless deposition of a Ni3P alloy containing up to 12 wt % phosphorus was developed and recommended for practical use. The possibility of repeated use of the solution developed was examined.

Nickel3phosphorus coatings formed by electroless deposition exhibit important functional and high protective properties. Among them, coatings deposited from acid solutions have the highest corrosion resistance [1], owing to increased phosphorus content and considerably lower porosity [2]. The melting point of the alloy containing 7.9 wt % P is 890oC and that of pure Ni, 1455oC, i.e., it decreases with increasing phosphorus content in the alloy [3]. This result is important for welding, soldering, and other operations with nickel3phosphorus coatings, which are widely used in electronic engineering [3]. The freshly deposited nickel3phosphorus alloys containing more than 8 wt % P are virtually resistant to magnetization [4]. The single use of a nickel-plating solution, with discharge of a large amount of hazardous and often rather valuable substances, is inadmissible from both the environmental and economical standpoints. Therefore, the subject of this study is rather urgent. The coatings were deposited onto Cr18Ni10Ti steel plates in a temperature-controlled cell with a load of 1 dm2 l!1 at 90oC for 1 h. Prior to coating deposition, the samples were subjected to the standard pretreatment. The deposition rate was calculated from the gain in the sample mass. The P content in the coatings was determined analytically [5]. The solutions were analyzed for the content of phosphite and hypophosphite ions and for the nickel content by the methods described in [6]. The pH value of nickel-plating solutions was measured with a pH-121 ionometer. All solutions were prepared from chemically pure and analytically pure grade chemicals. The automated correction was performed in a lab model of an AkNAR automated electroless nickel-plating installation [7]. The hypophosphite nickel-plating solutions used today contain organic ligands and buffer additives in

relatively high concentrations [8], which increases the cost of these solutions and makes them more environmentally hazardous. Therefore, in development of a hypophosphite solution, attempts were made to avoid, as far as possible, the use of various organic compounds. The starting solution contained (g l!1) NiSO4 20 330, (NH4)2SO4 20 330, NaH2PO2 20 330, and NaNO2 (stabilizer) 0.023 0.03. The temperature was 80 385oC. The required pH of the solution was adjusted with 30% ammonia. The P content in the coatings deposited from such solution varied from 18.4 to 14.5 wt %, depending on solution pH (Fig. 1). However, the deposition rate of the coatings was inadmissibly low (2.333.4 mm h!1 depending on solution pH). This is probably due to the fact that the buffer effect exerted by the above solution lies at pH ~ 3.4, which can be judged from the solution pH after coating deposition (Fig. 1). As known [9], at such pH values the coating deposition
v, mm h!1 P, wt %

Fig. 1. Influence of pH of the initial electroless nickelplating solution on the (1) coating deposition rate v, (2) P content in the coating, and (3) solution pH after the coating deposition.

1070-4272/05/7801-0082 + 2005 Pleiades Publishing, Inc.

ELECTROLESS DEPOSITION OF NICKEL COATINGS

83 P, wt %

virtually does not occur. Furthermore, in the course of the deposition, sparingly soluble nickel phosphite precipitated from the solution, making it turbid. To avoid the above drawbacks, a part of the solution was modified. For example, to shift the region where the solution exerts the buffer effect toward necessary pH values and to increase the buffer capacity of the solution, the (NH4)2SO4 concentration was increased to 50 g l!1 and acetic acid (20 ml l!1) was added into the solution. Moreover, this prevents the nickel phosphite precipitation owing to its binding into the ammonia complex. The pH of the given solution was adjusted by varying NH4OH concentration. In the pH range studied here (4.835.6), quality lustrous coatings containing 12.538.5 wt % P were deposited from the solution at a rate of 12323 mm h!1 (Fig. 2). Both before and after the coating deposition, the solution was always stable and transparent. Thus, the phosphorus content in the coating, and, consequently, its functional properties can be controlled using the dependences shown in Fig. 2. It was established that the pH range 5.0 35.2 (12315 ml l!1 NH4OH) is optimal. In this case, the rate of the coating deposition and the P content are fairly high, 153 18 mm h!1 and 12311 wt %, respectively. The suggested nickel-plating solution was used repeatedly under laboratory conditions. The solution was corrected nine times (ten deposition runs). The content of the main solution components (nickel salt and sodium hypophosphite) was adjusted according to the results of the analysis. The solution pH was adjusted to the initial value with 25% NH4OH. The results are given in Table 1. The results obtained made it possible to calculate the average consumption of the main components of a nickel-plating solution in one deposition run. In calculations, allowance was made for the consumption of components for coating deposition, their entrainment by parts, and evaporation. The component consumption in one deposition run was the following (g l!1): NiSO4 . 7H2O 5.5, (NH4)2SO4 0.05, NaH2PO2 . H2O 7.0, and NaNO2 0.015; CH3COOH 1.0 and NH4OH 4.0 ml l!1. These values served as basis for the development of correcting solutions. In an AKhNAR installation, the pH of the coating solution was adjusted automatically by adding equal portions of correcting solutions. Therefore, the ratio of the component concentrations in the correcting solutions must correspond to the given condition and their values must be reasonably large to prevent dilution of the coating solution. Moreover, the composition of
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 78

v, mm h!1

c, ml l!1
Fig. 2. Influence of pH of the modified electroless nickelplating solution and NH4OH concentration c on the (1) deposition rate v and (2) phosphorus content in the coating.

the correcting solutions must ensure their prolonged stability. Taking into account these facts, we tested the correcting solutions containing NiSO4 . 7H2O 550 g l!1, (solution no. 1); NaH2PO2 . H2O 700 g l!1 and NaNO2 1.5 g l!1 (solution no. 2); (NH4)2SO4 5.0 g l!1, NH4OH 400 ml l!1, and CH3COOH 100.0 ml l!1 (solution no. 3). These solutions were tested for the correction of the developed nickel-plating solution in an automated AKhNAR installation. The results are given in Table 2. The solution was stable and transparent over the entire working time (ten deposition runs). The deposited coatings were smooth, lustrous, and strongly adherent to the support. The deposition rate and the P content in the coatings varied within 15318 mm h!1 and 12314 wt %, respectively.
Table 1. Results of repeated use of electroless nickelplating solution. pH of the solution before loading 5.0

Run Solution pH Coating thick- P content, no. after loading ness, mm % 1 4.95 15.5 11.8 2 4.9 16.8 12.7 3 4.95 13.7 12.7 4 4.9 14.7 12.7 5 4.7 13.8 13.7 6 4.85 15.7 13.5 7 4.9 15.2 12.8 8 4.8 16.3 12.8 9 4.9 14.4 12.7 10 4.9 15.6 12.8
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Solution pH Coating P conRun thickness, tent, no. before loadingafter loading mm % 1 5.0 4.9 18.1 3 2 5.0 4.9 14.9 11.9 3 4.95 4.85 14.6 3 4 5.0 4.9 17.1 3 5 5.05 4.95 16.1 3 6 5.05 4.9 14.7 12.7 7 5.1 4.95 14.9 3 8 5.15 5.05 15.3 3 5.1 5.05 14.9 12.3 9 10 5.15 5 15 3

Table 2. Results of repeated use of electroless nickelplating solution in automated mode

NaNO2 0.03; CH3COOH 20 ml l!1; NH4OH 123 15 ml l!1; pH 5.0 35.2. It withstands at least ten deposition runs with intermediate corrections in automated or manual mode. REFERENCES
1. De Minjer, C.H. and Brenner, A., Plating, 1957, vol. 44, no. 12, pp. 129731305. 2. Jhuzlow, K.P., in Conf. on Recent Developments and Use of Electrodeposition Technology and Coatings, London, September 1983, pp. 13 6. 3. Colin, R., Galvanotechnik, 1966, vol. 57, no. 3, pp. 1583167. 4. Saubestre, E., Met. Finish., 1962, vol. 60, no. 9, pp. 593 64. 5. Bogenschutz, A.F., and George, U., Legierungsuber1  zuge und Legierungsbader, Sauglau/Wurtemberg:  1 Leuze, 1975. 6. Nikandrova, L.I., Khimicheskie sposoby osazhdeniya metallicheskikh pokrytii (Electroless Deposition of Metal Coatings), Leningrad: Mashinostroenie, 1971. 7. Makarov, V.F., Prusov, Yu.V., and Flerov, V.N., Zashch. Met., 1980, vol. 16, no. 3, pp. 360 3362. 8. Prusov, Yu.V., Makarov, V.F., and Flerov, V.N., Izv. Vyssh. Uchebn. Zaved., Khim. Khim. Tekhnol., 1992, vol. 35, no. 2, pp. 3319. 9. Gorbunova, K.M., and Ivanov, M.V., Zh. Vses. Khim. O!va. im. D.I. Mendeleeva, 1988, vol. 33, no. 2, pp. 1573164.

Manual correction of the suggested solutions is also possible. This involves addition of solution no. 3 after each deposition run to adjust pH of the coating solution, followed by addition of the same volumes of solution nos. 1 and 2 into the coating solution. CONCLUSION A process for electroless deposition of nickel3phosphorus coatings with a high phopshorus content was developed. The nickel-plating solution containis (g l!1) NiSO4 . 7H2O 20, NaH2PO2 . H2O 25, (NH4)2SO4 50,

RUSSIAN JOURNAL OF APPLIED CHEMISTRY

Vol. 78

No. 1

2005