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Corrosion Resistance of Multilayer Ti-Ta Coatings Obtained by Electron Beam

Cladding in the Atmosphere

Article  in  Advanced Materials Research · September 2014

DOI: 10.4028/www.scientific.net/AMR.1040.759

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Advanced Materials Research Vol 1040 (2014) pp 759-763 Online: 2014-09-24
© (2014) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.1040.759

Corrosion Resistance of Multilayer Ti-Ta Coatings Obtained by Electron

Beam Cladding in the Atmosphere
Ruktuev Alexey1,a *, Golkovski Mikhail2,b, Samoylenko Vitaly1,c,
Komarov Pavel1,d, Bataev Ivan1,e, Bataev Anatoly1,f
1
Novosibirsk State Technical University, 630073 Novosibirsk, Karl Marks 20, Russia
2
Budker Institute of Nuclear Physics, Siberian Branch, Russian Academy of Sciences, 630090
Novosibirsk, Akademika Lavrentieva prospect 11, Russia
a
alex47@211.ru, b golkovski@mail.ru, c samoylenko.vitaliy@mail.ru, d pasha-molotov@mail.ru , e
ivanbataev@ngs.ru, f bataev@adm.nstu.ru

Keywords: non-vacuum electron beam treatment, corrosion resistance, titanium, tantalum

Abstract. A method of surface alloying of titanium substrates with tantalum in order to obtain
corrosion-resistant layers is described. An electron beam injected into the atmosphere is used as a
power source. A powder layer containing a composition of alloying components and a fluxing agent
was placed on the surface of a Ti plate. The plate exposed to a scanning beam was moved at a speed
of 1cm/sec. The scanning range was 5cm, the scanning frequency was 50 Hz and the beam power
was 33.5 kW. To enhance the degree of alloying the coating procedure was repeated up to 4 times.
Alloyed layers 2-3 mm thick containing up to 40 wt % Ta were obtained. The rate of corrosion in
HNO3 depends on the Ta concentration in the deposited material. It is tens and hundreds times
lower than the rate of corrosion of unalloyed titanium for all coatings. Surface deposition by the
proposed method can be used to protect internal surfaces of chemical reactors operating in media
containing aggressive acids at increased temperatures up to the boiling temperature.
Introduction
An increased interest in Ti-Ta alloys has been displayed in recent decades because of their
extremely high corrosion resistance in a number of aggressive media. Currently a feasibility to use
the proposed system as a material for reactor vessels designed to recycle nuclear fuel from atomic
power plants is considered [1]. The advantage of the Ti-Ta system is an unlimited mutual solubility
at a temperature higher than the temperature of the titanium α-β transition of 1155 K. However,
obtaining Ti-Ta alloys having various melting temperature values entails great difficulties. In
addition, these metals interact actively with oxygen at temperatures higher than 873 K. The
proposed method of deposition makes it possible to overcome these challenges. The present paper is
a continuation of research [2, 3] into the deposition of powder compositions containing Ta and Nb
on the surface of Ti work pieces. A high-voltage electron beam of 1.4 MeV is used as a power
source. A high energy of electrons makes it possible to inject a focused electron beam into the
atmosphere. A distinctive peculiarity of this beam is its high ability to permeate materials including
powders. The beam is generated by the industrial accelerator ELV-6 that is series-produced by the
Budker Institute of Nuclear Physics, Novosibirsk, Russia. The beam is released into the atmosphere
by a special device separating a vacuum part of the accelerating beam path from the atmosphere. An
electron beam is focused, then it passes through a special adapting vacuum system and is released
through a hole of 1mm in diameter in this device. Some expansion of the beam occurs in the
atmosphere mainly due to elastic scattering on the nuclei of air atoms. To protect the components of
obtained coatings against atmospheric impacts, specially selected flux agents are used.
The aim of the research was to study corrosion resistance and a number of other characteristics
of coatings formed by multiple cladding using the proposed method.
Experimental
Work pieces for electron-beam cladding were made of commercially pure titanium. The cladded
material consisted of a composition of a Ta powder (an average particle size was 50µm), a Ti
powder (an average particle size was 20µm) and a flux agent. The initial powder composition

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760 High Technology: Research and Applications

contained 51% of tantalum, 18% of titanium and 23% of flux. A composition of CaF2 and LiF was
used as a flux agent. The general method of powder composition cladding, in particular Ti alloys, is
described in a number of papers [4-8].
Titanium plates of 12.5 x 50 x 100 mm in size, with a layer of a powder composition containing
an alloying material and a fluxing agent being placed on a big face, were moved in the longitudinal
direction by a scanning beam. The distance between the outlet hole and the plate surface was 90
mm. The Gaussian beam diameter on the plate surface was 12 mm. Beam scanning was used to
increase the process efficiency. Scanning was carried out by an electromagnetic scanning device.
The peak-to-peak value of the scanning electron beam was the same as the sample width and was
equal to 50 mm. A high scanning frequency (50 Hz) provided the uniformity of the beam impact
over the sample area. The beam power was 33.5 kW and the rate of sample motion was 1cm/sec.
The total mass thickness of the powder layer placed on the surface being processed including flux
was equal to 0.45g/cm2. This value depends on the effective penetration depth of the beam through
the material and was chosen based on the ability of the beam to penetrate through the entire powder
layer and to preheat it quickly.
The corrosion resistance was estimated based on the sample mass loss as a result of an action of
an aggressive medium. A concentrated solution (68%) of HNO3 at the boiling temperature was used
as a corrosion medium. Every 12 hours the sample mass was checked on the AND GR-300 balance
to an accuracy of 0.0001. Every 48 hours the nitric acid was replaced. The total duration of the test
was 120 hours. The commercially pure titanium VT1-0 and tantalum were used as comparison
samples.

Results and Discussion

A quantitative evaluation of elements in the surface layer was made by the X-ray fluorescence
analysis. The measurement results are presented in Table 1. It is noted in reference [3] that a
maximum concentration of tantalum in a coating formed by an electron beam cladding during one
passage equal to 22.4%. The cladding of two and more layers results in increasing the Ta
concentration.
Table 1. Chemical composition of the obtained Ti-Ta coatings
Concentration of elements, [%]
Number of
layers Ti Ta Other elements
2 layers 66.01 31.86 2.13
3 layers 62.84 35.71 1.45
4 layers 56.91 36.91 6.18

The X-ray diffraction analysis has shown that three phases are formed in all coatings under
study, namely the hexagonal α΄-phase, the orthorhombic α΄΄-phase and the cubic β-phase. The
structure of such a type is formed on accelerated cooling which results in the suppression of the
diffusion β→ α transformation and the implementation of the martensite-type transformation with
the formation of the α΄- or α΄΄-phase. Figure 1 shows the X-ray pattern taken while studying a
sample with a two-layer coating. The analysis of the profile shape of the X-ray picture reveals the
broadening of peaks probably caused by micro distortions of the crystal lattice and by the formation
of coherent scattering regions of small sizes. The results obtained are in agreement with the data
received by optical and scanning electron microscopy.
 Advanced Materials Research Vol. 1040 761

Fig. 1. XRD pattern of two-layer coating

The process of electron-beam treatment of powder compositions on titanium samples is

implemented at high rates owing to releasing a great amount of energy. In doing so a well-defined
dendritic structure is formed in the deposited coatings. A surface layer is represented by chaotically
oriented dendrites. While etching, equiaxed grains are revealed against their background. Dendrites
of a prolate form can be seen along the layer boundaries (Fig. 2a). Laminar- type crystals can be
observed in the coating structure (Fig. 2b). Features of the dendritic structure disappear when a
coating is formed during several passages in the layer structure.

Fig. 2. SEM micrograph (a) and optical micrograph (b) of coatings

The microhardness of coatings obtained by the tantalum deposition technology is higher than the
microhardness of titanium coatings. A maximum value of microhardness is 6000 MPa. The
distribution of microhardness in the depth of the coating formed by depositing four layers of the
powder composition is shown in Fig. 3.

Fig. 3. Microhardness of the sample with four-layer cladding

762 High Technology: Research and Applications

The destruction of coating occurs over the boundaries of prior grains of the β-phase, with a
peculiar surface geometry being formed (Fig. 4a). Areas of quasi-brittle destruction with some
evidence of plastic deformation (Fig. 4b) can be seen.

Fig. 4. SEM micrographs of the fracture surface

Titanium demonstrates the highest rate of corrosion (0.994 mm/year) in the boiling solution of
HNO3 (Table 2). The corrosion rate of a two-layer sample is 83 times lower than the corrosion rate
of VT1-0 (0.012 mm/year). The rate of destruction of a three-layer coating under exposure to an
aggressive media is 200 times lower as compared to commercially pure titanium. Under exposure to
a boiling acid for 120 hours any changes in masses of pure tantalum and the four-layer Ti-Ta
coating were not observed (Fig. 5). This evidences a high corrosion resistance of deposited layers
comparable to the resistance of pure tantalum.

Table 2. Corrosion rate of titanium, tantalum and multi-layer Ti-Ta coatings in the 68% boiling
solution of HNO3
Material Corrosion rate, [mm/year]
Titanium 0.994
Two-layer Ti-Ta coating 0.012
Three-layer Ti-Ta coating 0.005
Four-layer Ti-Ta coating 0
Tantalum 0

Fig. 5. Weight loss versus duration of corrosion resistance test in 68 % solution of boiling nitric
acid
 Advanced Materials Research Vol. 1040 763

Conclusion
Electron-beam deposition of powder compositions containing tantalum in the atmosphere is an
efficient and highly productive method of obtaining corrosion-resistant coatings on the surface of
titanium work pieces. The α΄- , α΄΄- and β-phases are formed in the deposited coatings on exposure
to a high-energy action. When three layers of powder compositions containing tantalum are
deposited, the rate of coating corrosion is almost 200 times lower than the corrosion rate of
unalloyed samples. When exposed to the boiling acid action for 120 hours any changes in the four-
layer Ti-Ta system mass were not observed.

Acknowledgement
This research was supported by the Grant of the President of the Russian Federation for Young
Candidates of Science for 2014-2015 (МK-5280.2014.8)

References
[1] B. Raj, U. K. Mudali. Progress in Nuclear Energy 48 (2006) 283–313
[2] M.G. Golkovsky, T.V. Zhuravina, I.A. Bataev, A.A. Bataev, S.V. Veselov, V.A. Bataev, E.A.
Prikhodko. Cladding of tantalum and niobium on titanium by electron beam injected in
atmosphere. Advanced Materials Research (2011) 314-316, 23-27
[3] M.G. Golkovski, I.A. Bataev, A.A. Bataev, A.A. Ruktuev, T.V. Zhuravina, N.K. Kuksanov,
R.A.Salimov, V.A. Bataev. Atmospheric electron beam surface alloying of titanium with
tantalum. Materials Science and Engineering A578 310–317 (2013)
[4] S.N. Fadeev, M.G.Golkovski, A.I.Korchagin, N.K.Kuksanov, A.V.Lavruhin, S.E. Petrov,
R.A.Salimov, A.F.Vaisman, Radiat. Phys. Chem. 57 (2000) 653–655.
[5] R.A.Salimov, V.G.Cherepkov, J.I.Golubenko, G.S.Krainov, B.M.Korabelnikov,
S.A.Kuznetsov, N.K.Kuksanov, A.B.Malinin, P.I.Nemytov, S.E.Petrov, V.V. Prudnikov,
S.N.Fadeev, M.E.Veis, Radiat. Phys. Chem. 57 (2000) 661–665.
[6] J.C. Oh, K. Euh, S. Lee, Y. Koo, N.J. Kim. Scripta Materialia. Vol. 39. No. 10, pp. 1389-
1394, 1998
[7] J.C. Oh, E.Yun, M.G.Golkovski, S.Lee, Mater. Sci. Eng. A, 351 (2003) 98–108.
[8] M.G. Golkovski. Vacuum-free hardening and surface alloying by relativistic electron beam,
Lambert academic publishing, 2013. (in Russian)
 High Technology: Research and Applications
10.4028/www.scientific.net/AMR.1040

Corrosion Resistance of Multilayer Ti-Ta Coatings Obtained by Electron Beam Cladding in the
Atmosphere
10.4028/www.scientific.net/AMR.1040.759

DOI References
[1] B. Raj, U. K. Mudali. Progress in Nuclear Energy 48 (2006) 283-313.
http://dx.doi.org/10.1016/j.pnucene.2005.07.001
[4] S.N. Fadeev, M.G. Golkovski, A.I. Korchagin, N.K. Kuksanov, A.V. Lavruhin, S.E. Petrov, R.A.
Salimov, A.F. Vaisman, Radiat. Phys. Chem. 57 (2000) 653-655.
http://dx.doi.org/10.1016/S0969-806X(99)00499-5
[5] R.A. Salimov, V.G. Cherepkov, J.I. Golubenko, G.S. Krainov, B.M. Korabelnikov, S.A. Kuznetsov, N.K.
Kuksanov, A.B. Malinin, P.I. Nemytov, S.E. Petrov, V.V. Prudnikov, S.N. Fadeev, M.E. Veis, Radiat. Phys.
Chem. 57 (2000) 661-665.
http://dx.doi.org/10.1016/S0969-806X(99)00486-7

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