Russia, Novosibirsk, Academician Lavrent ev ave, 11

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1 Advanced Materials Research Online: ISSN: , Vols , pp doi: / Trans Tech Publications, Switzerland Cladding of Tantalum and Niobium on Titanium by Electron Beam, Injected in Atmosphere M.G. Golkovsky 1, f T.V. Zhuravina 2, b, I.A. Bataev 2, c, A.A. Bataev 2, d, S.V. Veselov 2, e, V.A. Bataev 2, f, E.A. Prikhodko 2, g Russia, Novosibirsk, Academician Lavrent ev ave, Russia, Novosibirsk, Karl Marks ave., 20 a golkovsky@inp.nsk.su, b zhuravina@ngs.ru, c ivanbataev@ngs.ru, d bataev@adm.nstu.ru, e veselov_s@inbox.ru, f vabataev@yandex.ru, g helens_case@ngs.ru Keywords: cladding, tantalum, niobium, titanium, electron beam. Abstract. The aim of the work was to clad Ti-Ta-Nb coating on a substrate of pure titanium. Cladding was carried out by non-vacuum electron-beam treatment. As a result a good quality coating thickness of about 2 mm was obtained. Microstructural and microhardness tests were conducted. Dendritic structure and the borders of the former grains of β-phase were revealed. At the microlevel, the coating has a martensitic structure. The average hardness of coating is about 4000 MPa. Introduction At the present time titanium and its alloys are the most popular materials destined for use in aggressive environments. The wide use of titanium in many areas of industry is explained by high set of its physical and mechanical properties, particularly by high specific strength and phenomenal corrosion resistance. Nevertheless, even more stringent requirements to materials properties are required in some fields of industry. Tantalum has even higher corrosion resistance compared to titanium. This material is resistant to almost all kinds of acids, as well as to many liquid metals (Na, K, Li). However the widespread use of tantalum is limited by several factors, mainly its high cost and low production volumes. In recent years, new alloys of Ta-Ti-Nb system are of particular interest due to their high corrosion resistance and lower price compared to pure tantalum. In papers [1,2] it was noted that alloy containing 40 % of tantalum provides the same corrosion resistance as that of pure tantalum. Authors of [3] note that alloys of titanium and tantalum are the most promising for nuclear waste processing plants, when it is important to take into account corrosion resistance, mechanical properties, availability and cost of material. Possible application of Ta-Ti-Nb alloys in biomedicine was noted in [4]. Ta-Ti-Nb coatings on a substrate of pure titanium are promising from the position of the cost reduction of the corrosion resistant composition. This work studies the structure of Ta-Ti-Nb coatings, obtained on a pure titanium substrate by high-power electron beam injected in the atmosphere. The advantages of this method are that the coating is produced in an air atmosphere and the process is short [5]. Experimental procedure and research methods Commercially pure titanium plates were used as substrates. Dimensions of the substrates were as follows: 100x50x10 mm. Powders of pure titanium, tantalum and niobium were used for cladding. Some characteristics of cladding powder are presented in table 1. It should be noted that commercially available powders of tantalum, niobium and titanium contain sufficiently large amount of oxygen on the surface. СаF 2 and LiF mixture was used as flux. Non-vacuum electron beam cladding was performed on the facility ELV-6, produced by the Budker Institute of Nuclear Physics SB RAS. All rights reserved. No part of contents of this paper may be reproduced or transmitted in any form or by any means without the written permission of Trans Tech Publications, (ID: , Pennsylvania State University, University Park, USA-19/02/16,23:09:25)

2 24 Advanced Manufacturing Technology, ADME 2011 Table 1. Features of cladding powders. Powder type Ta Nb Ti Oxygen content according to EDXanalysis, wt. % 5,7 3,5 - The average particle size, µm * *- Porous titanium with the size of the porous conglomerates of about 200 microns, composed of particles about 5 microns was used. a) Б b) Fig. 1. Photos of the powders used for deposition a) titanium b) tantalum c) niobium Before the cladding mixtures of Ta, Ti and Nb powders with addition of the flux were deposited on the substrate surface. The composition of the mixture is presented in table 2. During the cladding the substrate with a layer of powder progressively moved relative to the electron beam at a speed of 10 mm/sec. In order to increase processing efficiency beam scanned the surface of the sample in the transverse direction. Scanning amplitude was equal to the width of the sample (50 mm). Scanning frequency (50 Hz) was sufficient to ensure the homogeneity of the beam exposure over the sample area. Electrons energy was 1,4 MeV, beam power was 33,5 kw. Table 2. Parameters of treatment and composition of the alloy Powders filling density [g/cm 2 ] Velocity of the samples movement [mm/s] Beam current [ma] В) c) Mass fraction of the component before cladding [%] Ta Nb Ti CaF 2 LiF 0, ,3 8 The cladding structure was studied by metallographic analysis using a microscope AxioObserver A1m. Mechanically polished cross-sections were etched by a five percent aqueous solution of hydrofluoric acid. To study local chemical composition of the cladding scanning electron microscope Carl Zeiss EVO50 with INCA XACT EDX-analyzer was used. Diffraction patterns were recorded by θ-θ diffractometer using a copper X-ray tube as a source of X-rays. Pictures were recorded with increments 2θ = 0,02 and 0.05 and dwell time 3-9 sec. Microhardness studies were performed using the device WolpertGroup 402MVD. Four-sided diamond pyramid was used as indenter. The load on the indenter was 0.98 N. Results and discussion Fig. 2 shows appearance of the coating formed during the cladding. The cladding thickness is about 2 mm. At least three clearly separated zones can be marked out in the cladding structure: a zone of a melted metal (1), a heat affected zone (2) and an unaffected zone (3). Average chemical composition of the cladding determined by EDX microanalyses is presented in table 3.

3 Advanced Materials Research Vols Fig. 2. The cladding appearance Contours of dendritic structure formed during primary crystallization is seen in the molten metal (zone 1). The most clearly dendritic morphology of coatings was observed by the SEM using back scatter electron detector (Fig. 3a). In this case, the dendrites appear as bright and interdendritic spaces in the form of dark areas. Large dendritic crystals are drawn towards the direction of heatsink. High contrast between the branches of dendrites and interdendritic spacing is indirect evidence of a difference in chemical composition and structure of these areas. Results of EDXanalysis, obtained at points 1 and 2 (Fig. 3a) are presented in Table 4. It should be noted that the precise quantification of the oxygen content in titanium by EDX-analysis is a difficult task. This is because the Kα-line of oxygen and L-line of titanium are sufficiently close to each other. Nevertheless, the analysis of the spectral profile presented in Fig. 4a indicates of the presence of a certain amount of oxygen in the material. Its presence may be caused by the oxygen adsorbed in the starting powders and coatings interaction with the atmosphere during the cladding. Preferential concentration of oxygen in the interdendritic spacing is also observed in the maps of oxygen distribution (Fig. 3b). Table 3. Average chemical composition of the coating (results of EDX - Analysis) Element Ta Nb O Ti Content (wt%) 19,2 18,8 6 the rest a) b) Fig. 3. The structure of the coating (in backscattered electrons) (а) and the map of oxygen distribution (b). Table 4. The results of EDX-microanalysis of the points 1 and 2 (see Fig.3a) Ta Nb O Ti Point 1 21,6 20,2 3,8 the rest Point 2 18,3 14,3 12,2 the rest

4 26 Advanced Manufacturing Technology, ADME 2011 a) b) Fig. 4. Sections of the spectra in the low energies, obtained from the point 1 (a) and point 2 (b) (see Fig. 3a) It should be noted that boundaries of large grains can be clearly seen against the dendritic background (Fig. 3a). Analysis of many regions revealed that dendrites are often crossed by grain boundaries. This fact indicates that the formation of grains occurred after the formation of dendritic structure. Data provided by the authors of [6], suggest that the boundaries observed in the photographs are probably the boundaries of the former β-phase. To carry out X-ray analysis the coating material was prepared in form of randomly oriented particles of size nm. This complication of the sample preparation technology was done in order to obtain non-textured objects. Obtained X-Ray pattern is shown in Fig. 5. Analysis of the diffraction patterns of powder material led to the assumption of the presence of cubic modification of titanium (β-ti). This assumption was based on analysis of the diffraction peaks intensities distribution. The ratio of the integrated intensities of most of α-titanium peaks correspond to the distribution of randomly oriented powder. At the same time, the intensity of the (002) peak substantially exceeds the average value, typical for the samples without texture. One can suppose that the strongest line of β-titanium (110) planes also contributes to this peak. Absence of the remaining β-titanium peaks reflects the small volume fraction of this phase in the sample. This phenomenon was also observed by the authors of [6]. The fine structure of the coating was analyzed by SEM and TEM. Analysis of the photographs presented in Fig. 6, indicates that during the cooling process diffusionless transformations β α' occurred and elongated crystals of α'-phase in the martensitic morphology were formed. The method of electron diffraction confirmed the presence of a small amount of residual β-phase. Microhardness distribution profile is shown on Fig. 7. The average level of the coatings microhardness was 4000 MPa, while the microhardness of the initial titanium was at the level of 2000 MPa. Fig. 5. X-ray pattern of the cladding material ground to the state powder.

5 Advanced Materials Research Vols a) b) Fig. 6. Martensitic microstructure of the coating: a TEM, b SEM. Conclusion Fig. 7. Microhardness distribution profile Ti-Ta-Nb coating with a thickness of about 2 mm was formed on a substrate of pure titanium by non-vacuum electron beam cladding. This methods provides high quality of coatings, without pores and cracks. The average microhardness of the coating is about 4000 MPa. The coating structure retained the contours of dendritic structure, and perhaps, the boundaries of the former β-phase grains. At the micro level, the coating has a structure of martensite. Elevated content of oxygen was found in interdendritic spacing. In order to reduce the oxygen content more pure starting powders should be used. References [1]. Andrei Ionut Mardare, Alan Savan, Alfred Ludwig, Andreas Dirk Wieck, Achim Walter Hasse: Corrosion Science 51 (2009) рp [2]. Karen Alves de Souza, Alain Robin: Materials Chemistry and Physics 103 (2007) pр [3]. Baldev Raj, U. Kamachi Mudali: Progress in Nuclear Energy 48 (2006) pp [4]. Ying-Long Zhou, Mitsuo Niinomi: Materials Science and Engineering C 29 (2009) pp [5]. J.C. Oh, E. Yun, S. Lee, M.G. Golkovski: Materials Science and Engineering: A (2003) V pp [6]. R. Mythili, V. Thomas Paul, S. Saroja, M. Vijayalakshmi, V.S. Raghunathan: Materials Science in Engineering A 390 (2005) pp

6 Advanced Manufacturing Technology, ADME / Cladding of Tantalum and Niobium on Titanium by Electron Beam, Injected in Atmosphere /