Protection of Metals, Vol. 37, No. 4, 2001, pp. 323326. Translated from Zashchita Metallov, Vol. 37, No.

4, 2001, pp. 366369. Original Russian Text Copyright 2001 by Tyrina, Rudnev, Abozina, Yarovaya, Boguta, Panin, Gordienko.

Formation of Anodic Layers with Mn, Mg and P on Titanium and Aluminum

L. M. Tyrina, V. S. Rudnev, E. A. Abozina, T. P. Yarovaya, D. L. Boguta, E. S. Panin, and P. S. Gordienko
Institute of Chemistry, Far East Division, Russian Academy of Sciences, pr. Stoletiya Vladivostoka 159, Vladivostok, 690022 Russia
Received January 14, 2000

AbstractIt is shown that by varying the molar ratio n = [polyphosphate]/[Me(II)] in aqueous electrolytes it is possible to control the contents of Mg, Mn, P, Al and Ti in the anodic layers that are formed at potentials of sparking and microarc discharges on aluminum and titanium. The effects of the nature of a treated metal on the parameters of the formation, thickness, and elemental composition of coatings are compared.

INTRODUCTION Anodic layers formed in aqueous electrolytes at sparking and breakdown potentials on the surface of aluminum and titanium articles protect the metals against corrosion and mechanical wear, enhance biological compatibility of implants, provide decorative nish of the articles, etc. [16]. Aqueous electrolytes with the addition of complex ions enable one to diversify the preassigned chemical composition of such coatings [713]. In more detail, this question was studied for aluminum alloys in solutions with the addition of polyphosphate complexes of Me(II) and Me(III) [7, 9, 10, 12, 13]. The lms produced contain considerable amounts of P and the Me. In addition to phases Al2O3 and AlPO4 , the lms presumably contain oxides or phosphates of Me(II) or Me(III). Depending on the proportions of P and Me(II), or Me(III), as well as the nature of the metals, the layers on aluminum exhibit biocidic properties and decorative colors and are promising for use in catalysis, as adsorbents, and luminophors [7, 10, 12, 13]. It is of interest to clarify whether the regularities characteristic of aluminum alloys can be applied to other rectifying metals. This work is devoted to comparing the processes of the formation of anodic-spark layers on titanium and aluminum in aqueous electrolytes containing hexametaphosphate complexes of Mn(II) and Mg(II). The obtained coatings may be of interest in the sphere of developing new materials with corrosion resistance, catalytic, ion-exchange, and decorative properties. METHODS AND MATERIALS Anodic lms were formed under galvanostatic conditions (i = 5 A/dm2) in one to two hours after the preparation of an electrolyte. Specimens made of a 1-00 titanium alloy and measuring 25 5 0.5 mm and an aluminum alloy measuring 40 10 0.5 mm

were oxidized during 6 and 10 min, respectively. The electrodes were prepared according to [14]. The design of the electrochemical cell, ways of stirring and cooling the electrolyte, and the current source are described in study [7]. In all the cases, the onset of sparking on the anode surface was observed during the rst minute of the process. During anodizing, the electrolyte temperature did not exceed 30C. Upon anodizing, the specimens were rinsed with distilled water and dried in air. The elemental composition of the surface layer of coatings was determined on a JXA-5A electron x-ray spectrum microanalyser, and the phase composition was on a DRON-2.0 x-ray diffractometer in CuK radiation. The thickness of lms was estimated with a MBI-15 optical microscope in reected light on coatings' cleavages with an accuracy of 2 m. Electrolytes were prepared of commercial reagents, such as chemically pure sodium hexametaphosphate Na6P6O18 (further designated as HMP), chemically pure Mn(CH3COO)2 4H2O and Mg(CH3COO)2 4H2O. Polyphosphate was dissolved in distilled water with subsequently adding preassigned amounts of manganese or magnesium acetate to the solution so as to obtain a needed molar ratio n = [HMP]/[Me]. EXPERIMENTAL RESULTS The state of the prepared solutions depends on the molar ratio of components n = [HMP]/[Me(II)]. The electrolytes containing HMP and Mn(II) at n 2, and HMP and Mg(II) at n 1, are transparent and true. At lower values of n, the solutions evolve colloidal and suspended particles. Figs. 1a, 1b presents the elemental composition (EC) of coatings formed in electrolytes with different n values. In solutions with n < 3, we observed increased contents of P and Mn in the composition of coatings on both aluminum and titanium, though the content of P in

0033-1732/01/3704-0323$25.00 2001 MAIK Nauka /Interperiodica

324 wt % 40 (a)

TYRINA et al. wt % 40 Al P Mn (b)

20

Ti P Mn

20

0 h, m 40

(c) Ti Al

0 Uc, V 400

(d)

20

200

Al Ti

10 n

10 n

Fig. 1. The effect of the molar ratio n = [polyphosphate]/[Me(II)] on the (a, b) elemental composition, (c) thickness h, and (d) the nal voltage of the formation Uf of anodic layers on 1-00 titanium and aluminum alloys. The bath contains: 30 g/l Na6P6O18 and Mn(CH3COO)2 4H2O.

the coatings on titanium less strongly depends on n than in those on aluminum. The color of the coatings, both on titanium and aluminum, changes, with a decrease in n, from the light gray to rose-tinted gray with a gradual increase in the color deepness. The thickness (h) and the nal formation voltage of coatings (U) depend on the n value (see Figs. 1b, 1e). Changes in all the parameters are the largest when the electrolyte evolves a precipitate or approaches this state (n < 3). The graphs in Fig. 2 illustrate the effect of the concentration of polyphosphate in an electrolyte with a constant molar ratio n = 1 on the characteristics of anodic layers. An HMP concentration range from 10 to 20 g/l is the boundary one. Above this boundary, an increase in the thickness of coatings at relatively constant contents of P and Me (II) and a decrease in the Na content in the coating are observed on both the titanium and aluminum electrodes. Below this range, the contents of P and Me (II) in coatings decrease. On titanium, all the layers formed are amorphous according to an x-ray diffraction analysis, whereas those on aluminum contain traces of crystalline phases, such as -, -, -, -Al2O3 and AlPO4 . DISCUSSION OF THE RESULTS An analysis of the experimental data shows that, by and large, the molar ratio n in electrolytes similarly affects both the composition and thickness of coatings on titanium and aluminum. Both on Ti and Al, the main changes in the composition of the coating (EC/n), its

thickness (h/n), and the nal formation voltage (U/n) take place when the electrolyte becomes colloidal (n < 12), or when it approaches this state (n < 3, the transient or metastable range). In accordance with studies [15, 16], in such solutions, which have undergone no electrolysis, the colloidal particles consist of medium or double hydrous polyphosphates Me (II) (in our case, for instance, Mn3P6O18 nH2O, Na2Mn2P6O18 nH2O, etc.). Calcinating the filtered deposit leads to the formation of high-temperature phosphates of a general formula Me(PO3)2 , which are characteristic of manganese or magnesium [1517]. In studies [10, 13], it was already supposed that at a molar ratio less than 35, the embedding of P and Me (II) into the coating is also a result of thermal transformations of a deposit of aqueous polyphosphates Me (II) or Me (III) under the effect of electric breakdowns. Thermolysis possibly proceeds according to the mechanisms described in [1517]. At n > 35, the manganese polyphosphates that have been deposited at the anode on the site of a breakdown are soluble and transfer into electrolyte as the site cools. These conceptions are consistent with the following experimental data obtained in the work. (1) The embedding of the electrolyte elements and an increase in the coating thickness were observed either at a colloidal state of the solution or in a preceding metastable range (see Figs. 1a, 1b). The increase in the coating thickness with a decrease in n value (Fig. 1c) is associated with an increase in the mass of the insoluble deposit that forms during breakdown, including colloidal particles embedded into the coating.
PROTECTION OF METALS Vol. 37 No. 4 2001

FORMATION OF ANODIC LAYERS wt % 60 40 20 0 wt % 4 2 0 Al Ti 20 10 (a) Ti P Mn wt % 60 40 20 0 h, m 30 (b) Al P Mg

325

(c)

(d)

Al Ti

25

50 Uc, V 600 400 200

75

100 (e)

25

50

75

100 C, g/l

Al Ti

25

50

75

100 C, g/l

Fig. 2. The effect of the concentration of Na6P6O18 on the contents of (a, b) Ti, Al, P, Mn, Mg, and (c) Na in the coatings; (d) thickness h, and (d) the nal voltage of the formation Uf of anodic layers on 1-00 titanium and aluminum alloys. The bath contains 30 g/l Na6P6O18 and Mn(CH3COO)2 4H2O (for titanium), or Mg(CH3COO)2 4H2O (for aluminum) at n = 1.

(2) Nearing each other by U values (Fig. 1d), as well as coating colors, on both types of anodes. (3) Dependence of the elemental composition and the thickness of coatings with an invariable molar ratio upon the concentration of HMP in the solution (Fig. 2). According to [15], at a concentration of HMP < 0.020 mol/l, one does not succeed, at any values of n, in precipitating hexametaphosphates of the Me(II) series, including those of the Mn(II) series. Accordingly, at a concentration of HMP less than 1020 g/l (0.016 0.033 mol/l), the lms are formed predominantly of TiO2 on titanium and of Al2O3 on aluminum, whereas at higher concentrations are mainly from the electrolyte components. The change in the content of Na in the coating with an increase in the concentration of polyphosphate complexes in electrolyte (see Fig. 2c) may be explained by the increase in the mass of a deposit formed at each breakdown, unequal thermolysis through the bulk of the deposit, and embedding (sealing up) of double polyphosphates of Na and Me(II) in the anodic layer. The high phosphorus content in the coating on titanium
PROTECTION OF METALS Vol. 37 No. 4 2001

(Fig. 1a) is apparently associated with the formation of phosphate-titanates as a result of the high-temperature interaction of TiO2 with polyphosphates in the breakdown sites throughout the whole investigated range of n values. On the other hand, it may be caused by dissolving Ti during the oxidation with the formation of its hexametaphosphate complex, followed by its thermolysis at the anode. Earlier [57], some of us observed synthesis of Ti phosphates in the process of the titanium spark oxidation both in phosphate and polyphosphate electrolytes, including Co(II)Co(III)Ti(PO4)3 . MoreAtomic ratios of elements in the coatings on titanium n 10 3 1 0.5 P/Ti 0.7 0.9 1.7 2.2 P/Mn 36.7 7.7 3.1 1.9 O/P 5.2 5.2 4.3 4.6 O/(Ti + Mn) 4.6 4.6 4.8 4.7

Note: The concentration of oxygen was determined on the assumption that the total of all the elements involved is equal to 100 wt %.

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TYRINA et al. during Arcing and Breakdown Potentials), Vladivostok: Dalnauka, 1996. Gordienko, P.S. and Gnedenkov, S.V., Mikrodugovoe oksidirovanie titana i ego splavov (Microarc Oxidation of Titanium and Its Alloys), Vladivostok: Dalnauka, 1997. Rudnev, V.S., Gordienko, P.S., Yarovaya, T.P., et al., Elektrokhimiya, 1994, vol. 30, no. 7, p. 914. Timoshenko, A.V., Magurova, Yu.V., and Artemova, S.Yu., Fiz. Khim. Obrab. Mater., 1996, no. 2, p. 57. Rudnev, V.S., Gordienko, P.S., Konshin, V.V., et al., Elektrokhimiya, 1996, vol. 32, no. 10, p. 1242. Rudnev, V.S., Yarovaya, T.P., Konshin, V.V., et al., Elektrokhimiya, 1998, vol. 34, no. 6, p. 575. Shchukin, G.L., Savenko, P.P., Belanovich, A.L., and Sviridov, V.V., Zh. Prikl. Khim. (St. Petersburg), 1998, vol. 71, no. 2, p. 241. Rudnev, V.S., Yarovaya, T.P., Boguta, D.L., et al., Materialy Mezhdunarodnoi konferentsii Korablestroenie i okeanotekhnika. Problemy i perspektivy, SOPP-98 (Proc. Int. Conf. Shipbuilding and Ocean Technique. Problems and Prospects), Vladivostok: DVGTU, 1998, part 2, p. 98. Gordienko, P.S. and Rudnev, V.S. Elektrokhimicheskoe formirovanie pokrytii na alyuminii i ego splavakh pri potentsialakh iskreniya i proboya (Electrochemical Coating Formation on Aluminium and Its Alloys during during Arcing and Breakdown Potentials), Vladivostok: Dalnauka, 1999. Grilikhes, S.Ya., Obezzhirivanie, travlenie i polirovanie metallov (Degreasing, Etching, and Polishing of Metals), Leningrad: Mashinostroenie, 1977. Lazarevski, E.V., Kubasova, L.V., Chudinova, N.N., and Tananaev, I.V., Izv. Akad. Nauk SSSR, Neorg. Mater., 1980, vol. 16, no. 1, p. 120. Lazarevski, E.V., Kubasova, L.V., Chudinova, N.N., and Tananaev, I.V., Izv. Akad. Nauk SSSR, Neorg. Mater., 1982, vol. 18, no. 9, p. 1544. Nariari, H., Motooka, I., and Tsuhako, M., Bull. Chem. Soc. Jpn., 1992, vol. 65, no. 3, p. 777.

over, calculations based on the elemental analysis data (see table) demonstrate that, in the investigated range of n values, the composition of the coatings on Ti corresponds to the formula xTiO2 (2x)MnO zP2O5 , where 2 < x < 0.9, 0.6 < z < 1.5. In the range of the colloidal state of electrolyte, the composition of the coatings formed is close to a MnTi(PO4)2 compound. Thus, titanium electrode follows the same basic relations between the component concentrations of polyphosphate electrolytes and the elemental composition of the anodic layers formed in them under sparking and microarc conditions, that were already described for an aluminum electrode in studies [7, 9, 10, 12, 13]. Using baths with polyphosphate-Me complexes, one can purposefully form, on the surface of titanium and its alloys, coatings containing necessary amounts of needed Me(II) or Me(III) compounds along with phosphorus. Determining the chemical and phase composition and properties of such coatings is the objective of further investigations. REFERENCES
1. Kurze, P., Schreckenbach, J., Schwarz, Th., and Krysmann, W., Metalloberaeche, 1986, vol. 40, no. 12, p. 539. 2. Chernenko, V.I., Snezhko, L.A., and Papanova, I.I., Poluchenie pokrytii anodno-iskrovym elektrolizom (Coating Production by Anodic Spark-Electrolysis), Leningrad: Khimiya, 1991. 3. Markov, G.A., Belevantsev, V.I., Terleeva, O.P., et al., Vestn. Mosk. Univ., Ser. Mashinostr., 1992, no. 1, p. 34. 4. Ishizawa, H. and Ogino, M., J. Biomed. Mater. Res., 1995, vol. 29, no. 1, p. 65. 5. Gordienko, P.S., Obrazovanie pokrytii na anodno-polyarizovannykh elektrodakh v vodnykh elektrolitakh pri potentsialakh iskreniya i proboya (Coating Formation on Anodic Polarized Electrodes in Aqueous Electrolytes

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