Russian Journal of Applied Chemistry, Vol. 74, No. 11, 2001, pp. 1838!1841.

Translated from Zhurnal Prikladnoi Khimii, Vol. 74, No. 11, 2001, pp. 1784 !1787. Original Russian Text Copyright + 2001 by Falicheva, Spiridonov.

APPLIED ELECTROCHEMISTRY AND CORROSION PROTECTION OF METALS

Electrodeposition of the Cr!Co Alloy from Acid Sulfate Electrolytes

A. I. Falicheva and B. A. Spiridonov
Voronezh State Technical University, Voronezh, Russia
Received July 4, 2001

Abstract The kinetics of electrodeposition of Cr3Co alloys from sulfate electrolytes with monoethanolamine was studied. The influence of the dc and pulsed current modes on the composition and physicochemical properties of the Cr3Co coatings with cobalt content of 5310% was examined.

Chromium coatings electrodeposited from electrolytes containing triple-charged chromium ions and iron-group metals have appreciably improved physicochemical properties: increased heat and oxidation resistance [1], lower fracturing [2, 3], and enhanced corrosion resistance. Sulfate [23 4] and chloride [135] electrolytes have been recommended for preparing electrolytic Cr3Co alloy. The previous studies have shown that Cr3Co coatings can be prepared from sulfate electrolytes with monoethanolamine (MEA) or hexamethylenetetramine in both static [3, 4] and pulsed [6] current modes. In this work, we continued the study of the electrodeposition of Cr3Co alloy from sulfate electrolytes. EXPERIMENTAL The electrolyte contained (M) 0.5 [modified] green chromium(III) sulfate (spectral characteristics: l1 = 4153 416 nm and l2 = 5823583 nm; e1 ; e2 = 37) [7, 8], 0.5 sodium sulfate, and 0.032 MEA. To the electrolyte, from 1 to 5 g l31 of cobalt sulfate was added. For comparative studies on cobalt deposition we prepared electrolyte containing 2 g l31 CoSO4 and MEA. The pulsed electrolysis was performed using a transistor generator of rectangular pulses. The pulse repetition frequency was varied from 0.1 to 10 Hz and the pulse length, from 0.1 to 50 s. Copper cathodes and platinum anodes were used. The current efficiency (CE) by the alloy was determined gravimetrically using a copper coulometer with account taken of the alloy composition. The cobalt content of the alloy was determined spectrophotometrically with nitroso-R salt and the chromium content,

by the persulfate3silver method. The cathodic polarization was studied galvanodynamically (6 mA min31) on a P-5827 M potentiostat with a KSP recording potentiometer. All the potentials are given vs. silver chloride reference electrode which served as reference; platinum was used as an auxiliary electrode. The partial polarization curves were obtained by resolution of the overall curves on the basis of data on the current efficiencies by hydrogen, chromium, and cobalt. The quality of the deposits was judged from outward appearance of the coatings; their reflectivity was studied with an FM-58 M photometer and the morphology, with an MIM-7 microscope. The phase analysis was done on the alloy films 500 31000 A thick (separated from copper substrate) at a 100 kV voltage. The lattice period was determined according to [9]. The hydrogen content in the cathode deposits was determined by vacuum extraction [10]. Analysis of the partial polarization curves derived from the overall curve of Cr3Co deposition from sulfate electrolyte with MEA (Fig. 1) shows that chromium(III) is reduced to chromium(II) (E0 3+/Cr2+ = Cr 3 0.41 V) simultaneously with the formation of hydrogen (E0 +/H0 = 0 V), cobalt (E0 2+/Co0 = 30.277 V), H Co and chromium (E0 3+/Cr0 = 30.71 V). The previous Cr data show that, apart from hydrogen evolution, the formation of cobalt is the most probable from the thermodynamical standpoint. However, owing to the increase in the chromium(II) ion concentration and the shift of the ECr3+/Cr2+ potential toward negative region, chromium (curve 1c) is deposited simultaneously with cobalt (curve 1d), as revealed by analysis of the cathode deposits and partial curves. Reduction of chromium(III) ions during the alloy deposition occurs with lower polarization than deposition of pure

1070-4272/01/7411-1838$25.00 C 2001 MAIK [Nauka/Interperiodica]

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chromium (curve 2c). From an electrolyte containing no cobalt(II) ions, chromium is electrodeposited at Dc = 25 A dm32 (pH 0.75). At simultaneous deposition with cobalt, the necessary current density decreases to 15 A dm32, because the free energy decreases owing to formtion of the crystal lattice of the cathodic chromium3cobalt solid solution. Electron-microscopic study of the chromium3cobalt deposits containing 10% cobalt showed that the simultaneous deposition of chromium and cobalt results in the formation of a solid solution with a lattice period of 2.87 A. According to the phase diagram, the b-phase with a centered cubic lattice, which is a solid solution of cobalt in chromium [11], is formed in the chromium3cobalt system at cobalt content of up to 10%. The lattice period of chromium deposited from chromium-plating sulfate electrolyte with MEA under the similar conditions is a = 2.89 A. Apparently, a slight decrease in the lattice period of Cr3Co alloy compared to chromium is explained by the decreased hydrogenation. For example, with the cobalt content of the alloy increased from 2.3 to 8.6%, the hydrogen content is decreased approximately 2.7-fold (Fig. 2). The decrease in the alloy hydrogenation with increasing cobalt content of the alloy can be explained by the decrease in the current efficiency by hydrogen in chromium-plating sulfate electrolyte with added CoSO4. For example, with cobalt sulfate concentration increased from 1.0 to 5 g l31, the cobalt content of the alloy is increased from 1.8 to 12% and the CE by the alloy, from 6.2 to 10.3% (Dc = 20 A dm32, pH 0.75). Under these conditions the rate of hydrogen formation decreases simultaneously (see table), whereas that of cobalt formation increases approximately 4-fold. The self-discharge of cobalt(II) ions occurs at a considerably higher rate (Fig. 1, curve 3) than at simultaneous electroplating with chromium (curve 1d). One of the reasons responsible for overpolarization of Co2+ discharge is the adsorption of colloidal surfaceactive Cr(OH)3 on active sites of the cathode. As a result, the cobalt formation is hindered. This phenomenon is characteristic of codeposition of chromium with iron-group metals, for example, nickel [8] from sulfate electrolytes. The alloy deposits containing up to 10 312% cobalt are lustrous and acquire a shadow typical of cobalt coatings at higher cobalt concentrations. With cobalt sulfate concentration increased from to 5 g l31, the Dc interval corresponding to deposition of lustrous coatings is broadened essentially (to 80 A dm32, pH 0.5).
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Dc, A dm!2

1b 2b 2a

1c

2c1d
3E, V

Fig. 1. Cathodic polarization curves of deposition of (1) Cr3Co alloy, (2) chromium, and (3) cobalt from sulfate electrolytes with MEA. (Dc) Current density and (E) potential. Partial curves of formation of (1a, 2a) H2, (1b, 2b) Cr2+, (1c, 2c) Cr0, and (1d) Co0.

VH , cm3/100 g
2

CCo, %
Fig. 2. Hydrogenation VH of Cr3Co cathode deposits vs. 2 cobalt content CCo of the alloy. Dc = 30 A dm!2, thickness 5 mm, pH 0.75, and T = 25oC.

With increasing electrolyte pH the rate of the alloy deposition increases. For example, with pH varied from 0.5 to 1.0, the hydrogen discharge current is decreased nearly twofold (from 19 to 10 A dm32) and the partial rate of the alloy deposition is increased approximately 9.50-fold (E = 31.4 V). Such a change in the electrolyte pH increases the current efficiency by the alloy (from 5 to 26% at Dc = 30 A dm32). Comparison of the partial current densities of the chromium(III) and cobalt(II) ion formation shows that with pH increasing in the given range the partial current density of the cobalt separation decreases from 6.2 to 1.8% (at Dc = 30 A dm32), and the alloy is
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FALICHEVA, SPIRIDONOV

Partial current densities of hydrogen, chromium(II), cobalt, and chromium formation at 25oC

iH iCr2+ iCo0 iCr0 2 A dm!2, at indicated concentration of CoSO4 in electrolyte, g l!1 Dc, A dm!2 2 5 2 5 2 5 2 5 20 14.00 13.44 5.24 5.33 0.15 0.39 0.61 0.84 30 18.46 16.38 10.43 12.00 0.10 0.26 1.01 1.36 40 21.83 18.65 16.62 18.87 0.09 0.20 1.46 2.28
60 A dm32. This suggests that at high Dc the formation of chromium hydroxide film is hindered with increasing Q, thus creating the more favorable conditions for the Co2+ discharge compared to steady-state regime. At low Dc, the pHs increase is slower, the chromium(III) ion concentration in the near-cathode space increases relative to cobalt(II) concentration, and the alloy is enriched with chromium. For example, at Dc = 10 A dm32 the cobalt content in the alloy decreases from 4.6% (curve 2) to 2% (curve 5). The effect of the pulse repetition frequency on the alloy component ratio is less marked than that of the pulse to dead time ratio. For example, if f = 0.3 Hz, then at Dc = 10 A dm32 the cobalt content in the alloy is lower by 0.8% (curve 5) than at Dc = 60 A dm32. With f increasing to 0.35 Hz the cobalt content in the alloy decreases by 0.5% (curve 5`). At f > 0.35 Hz and Q > 2 the current efficiency by the alloy is considerably lower (by ~ 12%), which can be explained by the cathode passivation at higher pulse repetition frequences typical of electrodeposition from sulfate electrolytes [12]. CONCLUSIONS (1) Chromium and cobalt can be codeposited from electrolytes containing cobalt and chromium sulfates [the latter in the form of modified green chromium(III) sulfate] and luster-producing monoethanolamine. (2) The method of partial curves has revealed that the electrodeposition of Cr3Co alloys occurs with depolarization, and that of cobalt, with enhanced polarization.
Dc, A dm!2

enriched with chromium. It should be noted that with decreasing electrolyte acidity the reflectivity of the coatings decreases, and at pH > 1.5 they become dull. Increasing cathodic current density decreases cobalt content of the alloy. For example, as Dc is decreased from 10 to 60 A dm32, the cobalt content is decreased from 6 to 0.5%. One of the reasons of the appreciable dependence of alloy composition on Dc is the stronger polarization accompanying cobalt deposition into the alloy (Fig. 1, curve 1d), which is ascribed to the increased pHs and prevention of the Co2+ discharge by facilitated adsorption of Cr(OH) 3 on the cathode. To stabilize electrodeposition and make the dependence of alloy composition on Dc less appreciable, we studied the influence of the transient electrolysis mode using a rectangular pulsed current. It is seen from Fig. 3 that with the pulse to dead time ratio Q (Q = tp + td/tp, where tp is electrolysis time and td is dead time) increased from 1.03 to 1.5, the cobalt content in the alloy is increased from 0.5 to 1.2% at Dc =
CCo, %

Fig. 3. Influence of the cathodic current density dc on the cobalt content of the alloy CCo. Electrolysis: (1) steadystate and (2!5) pulsed. Pulse to dead time ratio Q: (2) 1.03, (3) 1.1, (4) 1.2, and (5, 5`) 1.5. Pulse repetition frequency f (Hz): (2!5) 0.3 and (5`) 0.35.

(3) The sulfate electrolyte with momoethanolamine is developed, allowing preparation of mirrorlustrous Cr3Co coatings (up to 10% Co) at Dc = 10 3 60 A dm32, T = 25oC, and pH 0.531.0. The current efficiency by the alloy is 15325%. (4) For the stabilization of the alloy composition, we recommend to perform electrolysis in the pulsed
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current mode using rectangular pulses with a 0.33 0.35 Hz repetition frequency and the pulse to dead time ratio Q = 1.5. REFERENCES
1. Vyacheslavov, P.M., Elektroliticheskoe osazhdenie splavov (ELectrolytic Deposition of Alloys), Leningrad: Mashinostroenie, 1980. 2. Potapov, I.I., and Kudryavtsev, N.T., Zashch. Met., 1971, vol. 7, no. 1, pp. 55357. 3. Falicheva, A.I., Spiridonov, B.A., Shalimov, Yu.N., and Zhernokleeva, S.V., Zashch. Met., 1975, vol. 11, no. 5, pp. 6223 623. 4. Spiridonov, B.A., Tekh. Mashinostr., 1998, no. 3, pp. 413 42. 5. Harini, D., Clyde, R., and Dwain, C.H., J. Electrochem. Soc., 1994, vol. 141, no. 7, pp. 177331779.

6. RF Patent 2 130 091. 7. Falicheva, A.I., Elektrokhimiya, 1968, vol. 4, no. 7, pp. 856 3858. 8. Spiridonov, B.A. and Falicheva A.I., Zh. Prikl. Khim., 2001, vol. 74, no. 2, pp. 210 3215. 9. Gorelik, S.S., Rastorguev, L.N., and Skakov, Yu.A., Rentgenograficheskii and elektronograficheskii analiz metallov (X-ray and Electron Diffraction Analyses of Metals), Moscow: Metallurgiya, 1963. 10. Gulyaev, A.A., Study on Hydrogenation of Chromium Deposits Prepared from Electrolytes Containing Chromium(III) Compounds, Cand. Sci. Dissertation, Voronezh, 1973. 11. Hansen, M., and Anderko, K., Constitution of Binary Alloys, New York: McGraw-Hill, 1958. 12. Shalimov, Yu.N., Falicheva, A.I, and Spiridonov, B.A., Zashch. Met., 1977, vol. 13, no. 5, pp. 6233 625.

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2001