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High-Speed Anodic Dissolution of Heat-Resistant Chrome-Nickel

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High-Speed Anodic Dissolution of Heat-Resistant Chrome-Nickel ISSN 1068-3755, Surface Engineering and Applied Electrochemistry, 2007, Vol. 43, No. 3, pp. 155–162. © Allerton Press, Inc., 2007. Original Russian Text © A.I. Dikusar, I.A. Ivanenkov, B.P. Saushkin, S.A. Silkin, S.P. Yushchenko, 2007, published in Elektronnaya Obrabotka Materialov, 2007, No. 3, pp. 4–12. ELECTRIC DIMENSIONAL TREATMENT OF MATERIALS High-Speed Anodic Dissolution of Heat-Resistant Chrome–Nickel Alloys Containing Tungsten and Rhenium: II. Nitrate Solutions A. I. Dikusara, b, I. A. Ivanenkovc, B. P. Saushkinc, S. A. Silkinb, and S. P. Yushchenkoa, b a Institute of Applied Physics, Academy of Sciences of Moldova, ul. Akademiei 5, Chisinau, MD-2028 Republic of Moldova b Shevchenko Dniester State University, ul. 25 Oktyabrya 128, Tiraspol, 3300 Republic of Moldova c MATI-Russian State Technological University, Berezhkovskaya nab. 14, Moscow, 109240 Russia Received October 26, 2006 Abstract—Anodic dissolution of two heat-resistant chrome–nickel alloys containing 12% (weight) tungsten and 8% tungsten with 6% rhenium in a 2 M NaNO3 solution was investigated using the rotating disk electrode method at current densities up to 30 A/cm2. It is shown that anodic dissolution of these alloys occurs in the trans- passive region of potentials with transition of the components in solution to forms with the highest oxidation level. Various mechanisms of alloy dissolution determining the processing speed (together with electrochemical dissolution) are proposed, including disintegration of the hardening phase, chemical oxidation of low-valence intermediates by solution components, and electrochemical formation of surface oxide layers. The results of change in the chemical composition of surfaces depending on the processing regimes are presented. Some vari- ants of control by regimes of electrochemical dimensional processing (ECDP) of details from these alloys to achieve the optimal parameters of ECDP are proposed. DOI: 10.3103/S1068375507030015 INTRODUCTION solutions is the destruction of surface oxides at high current densities and, as a result, transition from the In [1], the results of high-speed anodic dissolution reaction of oxygen release to the reaction of anodic dis- of heat-resistant chrome–nickel alloys containing tung- solution on an increase in current density [2, 3]. A con- sten and rhenium in chloride solutions are described. sequence of this effect is the increasing dependence of For processing of the above materials, electrochemical current yield on current density, which provides the dimensional processing (ECDP) is widely used and conditions for increasing localization of the process of nitrate solutions or their mixtures with chlorides are ECDP of these metals [2–4]. used as electrolytes [2–4]. Use of nitrate solutions may be expedient for a num- ber of reasons. First, the cathode process in the condi- ϕ, V tions of ECDP in nitrates may proceed without gas 4 release or with its considerable decrease since, in 3 nitrates, the cathode reaction of gaseous hydrogen 3 release may be replaced by the reaction of reconstruc- 2 tion of nitrate ions up to products that do not produce a 2 gas phase, which is fundamentally important in the case 1 of use of small interelectrode gaps and, therefore, for increasing the process localization [2–4]. Second, for a 1 number of metals and alloys in nitrate solutions, an increasing dependence of current yield on current den- sity is typical, which is also important for increasing process localization in the conditions of ECDP [2–4]. 0 2 4 6 8 10 12 14 16 Moreover, on dissolution of heat-resistant chrome– τ nickel alloys containing the hardening γ phase in nitrate , s and chloride electrolytes, its decomposition is possible, which decreases the power intensity of an electrochem- ical treatment process [5]. Fig. 1. Typical dependences of the dissolution potential on time for alloys I (1–3) and ZhS-6U (4) in 2 M NaNO3 at cur- A distinguishing feature of anodic dissolution of rent densities (A/cm2) 1.0 (1), 3.0 (2), 5.0 (3), and 10.0 (4) metals of the iron subgroup (including nickel) in nitrate and RDE speeds (rpm) of 260 (1, 3) and 1260 (2, 4). 155 156 DIKUSAR et al. 2 Table 1. Composition of surface layer after anodic dissolution of alloys at i = 2 A/cm in 2 M NaNO3 (wt %) Ni Cr W Re Co Ti Al C Si O Place Alloy ZhS-6U in Fig. 3 Initial com- 56.5 ± 0.8 9.1 ± 0.7 12.1 ± 2.0 – 9.5 ± 0.4 2.6 ± 0.5 5.5 ± 0.1 4.5 ± 0.6 – – position (e) Basic 53.1 8.7 14.2 – 9.1 1.8 4.4 4.5 – 3.5 phase (d) Boundary 49.2 6.6 6.7 – 6.1 2.8 3.2 21.0 – 4.3 phase (f) Phase 66.0 3.3 5.5 – 6.9 4.8 6.4 4.4 – 2.8 enriched with Ni (γ') Alloy I Initial com- 62.1 ± 0.1 4.8 ± 0.1 7.8 ± 0.5 5.6 ± 0.7 10.1 ± 0.4 – 5.0 ± 0.3 3.7 ± 0.2 0.9 ± 0.1 – position (a) Basic 59.4 4.5 9.3 5.2 9.0 – 5.8 3.5 1.0 2.2 phase (c) Boundary 62.9 2.4 9.7 – 7.3 – 7.8 5.9 – 4.0 phase (b) Oxidized 42.6 3.2 22.4 2.7 4.8 – 4.2 4.4 1.6 14.3 phase 2 Table 2. Composition of surface layer after anodic dissolution of alloy I at i = 5 A/cm in 2 M NaNO3 (wt %) Ni Cr W Re Co Al C Si O Place Initial in Fig. 5 62.1 ± 0.1 4.8 ± 0.1 7.8 ± 0.5 5.6 ± 0.7 10.1 ± 0.4 5.0 ± 0.3 3.7 ± 0.2 0.9 ± 0.1 – composition (b) Basic phase 68.8 ± 1.5 4.4 ± 0.5 9.8 ± 1 – 10.1 ± 0.6 7.0 ± 0.6 – – – (a) Oxidized phase 59.2 ± 5.7 2.4 ± 0.3 10.4 ± 2.0 – 7.2 ± 0.7 7.0 ± 1.3 6.2 1.7 6.3 ± 3.0 Average 64 3.4 10.1 – 8.7 7.0 3.1 0.9 3.2 Table 3. Composition of surface layer after anodic dissolution of alloys I (i = 29 A/cm2) and ZhS-6U (i = 24 A/cm2) in 2 M NaNO3 (wt %) Place Ni Cr W Re Co Al Ti O Others in Fig. 6 Alloy I (c) Basic phase 33.5 ± 8.0 7.9 ± 0.8 26.9 ± 7.0 4.6 ± 0.7 6.6 ± 1.3 2.1 ± 0.9 – 16.3 ± 1.1 ~2.8 (d) Oxidized 4.0 ± 0.4 5.3 ± 0.4 50.4 ± 3.8 ~2.0 – – – 30.3 ± 1.9 ~7.0 phase ZhS-6U (a) Basic phase 55.1 ± 5.0 5.1 ± 0.9 11.7 ± 4.5 – 6.9 ± 0.5 5.6 ± 0.4 4.7 ± 1.7 9.2 ± 0.2 – (b) Oxidized 39.0 3.2 27.7 – 3.8 3.1 6.1 17.2 – phase In the case of high-speed anodic dissolution of at a high concentration (i.e., with the formation of a chrome–nickel alloys in nitrates, a similar effect is not solid solution of tungsten in nickel, ~(20–30)% W), the observed [2–5]. Electrochemical dissolution of alloys alloy behaves similarly to chrome–nickel alloys, i.e., it of nickel with tungsten in nitrates depends to a greater is dissolved with high speed, while, at low concentra- extent on the concentration of tungsten in an alloy, and, tions of tungsten, its electrochemical characteristics are SURFACE ENGINEERING AND APPLIED ELECTROCHEMISTRY Vol. 43 No. 3 2007 HIGH-SPEED ANODIC DISSOLUTION OF HEAT-RESISTANT CHROME–NICKEL ALLOYS 157 close to the electrochemical properties of pure nickel i, A/cm2 [6]. High-speed dissolution of chrome–nickel alloys with rhenium, as well as with tungsten in which tung- sten is partly replaced by rhenium, in nitrate electro- lytes was not investigated earlier. It is known, however, 10 that, in contrast to tungsten, rhenium at high current 5 densities is dissolved in nitrates with high speed, while for tungsten a deep passivity is typical due to the forma- 4 tion of insoluble oxide WO3 [2, 3, 7]. Anodic dissolu- tion of rhenium in nitrates at high current densities takes place with the formation of the ion ReO4 [7]. The main task of the present work (as in [1] with ref- erence to the dissolution of these alloys in chlorides) was the investigation of the mechanism of formation of 1 surface covering layers on anodic dissolution of the above-mentioned alloys in nitrate electrolytes in a wide 3 area of current densities and their role in the achieve- 1 ment of specific values of material removal speeds dur- ing ECDP, as well as the influence of macroscopic 2 inhomogeneity of alloys in the formation of composi- tion and surface properties. EXPERIMENTAL 0.1 Anodic dissolution of two chrome–nickel alloys is investigated, the composition of which is presented in Table 1. The method of investigation completely corre- 012 3 4 5 6 sponded to the method described in [1], with the only ϕ, V difference that the maximum current densities achieved in the present paper were less than those described in Fig. 2. Galvanostatic polarization curves in 2 M NaNO3 for [1] (~30 A/cm2) and the dissolution occurred in 2 M alloys I (1, 3) and ZhS-6U (2) at RDE speeds (rpm) of 260 NaNO .
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