Materials Letters 59 (2005) 2159 2162 www.elsevier.

com/locate/matlet

Improvement of wear resistance of Ti6Al4V alloy by means of thermal oxidation

F. BorgioliT, E. Galvanetto, F. Iozzelli, G. Pradelli
Dipartimento di Ingegneria Civile, Universita di Firenze, via S. Marta 3, 50139 Firenze, Italy ` Received 16 July 2004; accepted 19 February 2005 Available online 13 March 2005

Abstract Thermal oxidising treatment is an easy and environmental friendly technique that can be used to harden the surface of titanium alloys, and hence improve the poor tribological properties of these materials. The aim of the present research was to evaluate the tribological behaviour of thermally oxidised titanium alloy samples as both counterparts. With this purpose, Ti6Al4V alloy disks were treated in an air circulating furnace at 1173 K for 2 h at 105 Pa, and then quenched using compressed air, in order to remove the poorly adherent part of the oxide scale. The modified surface layer shows decreasing hardness values, from ~970 HK0.025 to matrix values; the case depth of the hardened layer is ~35 Am. Wear tests, carried out on both untreated and oxidised samples in block-on-ring configuration, in dry sliding conditions, with sliding velocity in the range 0.41.6 m s1, 50 N coupling load and 3000 m sliding distance, show that the thermal oxidation treatment is able to substantially improve the wear resistance of Ti6Al4V samples, reducing the wear volumes from about 4 to 6 times in respect of the untreated alloy. Moreover, further wear tests (sliding velocity: 0.8 m s1; coupling load: 50 N; sliding distance: 1700 m), performed on untreated, glow-discharge nitrided and thermally oxidised samples, point out that, with the used test conditions, a marked improvement of the wear resistance is obtained for the oxidised samples in respect of both untreated and nitrided ones. D 2005 Elsevier B.V. All rights reserved.
Keywords: Titanium alloy; Ti6Al4V; Thermal oxidation; Wear

1. Introduction The poor tribological properties of titanium alloys are still a limit for their widespread use in many industrial fields. The wear resistance of these materials can be improved by using surface treatments, which are able to increase the surface hardness of titanium alloy components decreasing the wear rate [1]. In particular, by taking advantage of the high reactivity of titanium with respect of carbon, nitrogen or oxygen it is possible to modify the surface characteristics of titanium alloys by means of diffusion-based treatments. Among them, glow-discharge nitriding treatment is widely used to improve the wear resistance of titanium alloy components; nevertheless, this

T Corresponding author. Tel.: +39 055 4796 403; fax: +39 055 4796 504. E-mail address: fborg@dicea.unifi.it (F. Borgioli). 0167-577X/$ - see front matter D 2005 Elsevier B.V. All rights reserved. doi:10.1016/j.matlet.2005.02.054

treatment is not completely satisfactory when high specific loads or high sliding velocities of the components are used, since in these severe working conditions a microfragmentation of the nitride surface layer may occur and severe wear is observed due to a third body abrasion mechanism [2,3]. The wear resistance of titanium alloys may also be improved by using oxidation techniques. When titanium is exposed to air at high temperatures, it rapidly oxidises and a thick, usually poorly adherent, surface oxide scale on an inner hard diffusion layer is produced [4,5]. The hardening effect of this process was shown to be suitable to improve the wear resistance of titanium alloy components [6]. However, in spite of the easiness of the technique, in recent years only a fairly low number of papers has been devoted to the thermal oxidation process as an effective way for improving the wear resistance of titanium alloys [712]. In our previous papers we showed that the thermal oxidation of titanium alloys is able to produce a hardened surface layer

2160

F. Borgioli et al. / Materials Letters 59 (2005) 21592162

XRD intensity (a.u.)

-Ti Ti3Al

TiNxOy TiO2

each test were carried out. The wear volume of the disks was evaluated by measuring their weight loss by means of a precision balance (104 g), according to the ASTM norm [16]. The morphology and constitution of the worn samples and the debris were examined by light and scanning electron microscopies, EDS analysis and X-ray diffraction analysis.

3. Results and discussion

30 40 50

3.1. Microstructure and microhardness The treated samples show a modified surface layer, consisting of an outer compound layer and an inner diffusion layer. X-ray diffraction pattern of the surface layers of a thermally oxidised sample is shown in Fig. 1. The X-ray diffraction analysis shows that, after the removal of the poorly adherent part of the oxide scale, the compound layer consists essentially of TiO2 (rutile type; tetragonal); small amount of TiNx Oy (f.c.c.) was also detected. The diffusion layer consists of a-Ti (h.c.p.) grains, rich in interstitial atoms (oxygen, nitrogen), which form a nearly continuos layer and extend into the matrix, as shown in Fig. 2. X-ray diffraction analysis shows that the intermetallic phase Ti3Al (hexagonal), stabilised by the high oxygen content, is present near the compound layerdiffusion layer interface; this phase forms, with the a-Ti solid solution, a peculiar microstructure at the interface, as observed previously [13]. Roughness measurements were performed on the samples before and after the treatments. While the untreated samples have a mean surface roughness (R a) of 0.5 Am, after the treatment and the removal of the poorly adherent part of the oxide scale a roughness increase up to 1 Am is observed. The rougher surface of the treated samples can be ascribed to the growth mechanism of the oxide layer: with the used treatment conditions, as time increases this layer becomes porous and develops a stratified structure, increasing the surface roughness [8,17].

2 (deg)
Fig. 1. X-ray diffraction pattern of a Ti6Al4V sample thermally oxidised at 1173 K for 2 h.

on Ti6Al4V samples [13] and to reduce their wear in dry sliding conditions in respect of both untreated and nitrided alloy, when hardened and stress relieved AISI O2 steel is used as counterpart [14]. The aim of the present research was to evaluate the sliding wear behaviour of thermally oxidised Ti6Al4V alloy as both counterparts. As reference, wear tests were carried out also on untreated Ti6Al4V alloy samples as both counterparts.

2. Experimental procedure Ti6Al4V alloy disks (diameter: 50 mm; thickness: 8 mm) were obtained from an annealed Ti6Al4V bar (diameter: 60 mm) by cutting and grinding. The disks were treated by means of thermal oxidation performed in an air circulating furnace. The treatments were performed in plain air, at 1173 K, for 2 h, at 105 Pa. After the treatments the samples were quenched using compressed air, in order to remove the poorly adherent part of the oxide scale. The microstructure of the treated samples was examined by light and scanning electron microscopies. X-ray diffraction analysis (Cu Ka radiation) was performed to identify the phases present in the surface layers of the samples; the diffraction patterns were analysed by means of a fitting program using the Rietveld method [15]. Microhardness measurements (Knoop indenter, 25 gf) were carried out on the modified layers and on the matrix. Roughness measurements were performed on the surface of the samples before and after the treatments by using a stylus surface tester (measuring range: 0.0110 Am). Wear resistance was tested by means of a tribometer in block-on-ring configuration (ASTM G77-98 [16]), in sliding conditions, without lubricants and in air. The blocks for wear tests were obtained by cutting the disks. Tests were performed by using a coupling load of 50 N, at sliding velocities in the range 0.41.6 m s1 and with sliding distances of 1700 and 3000 m. At least three repetitions of

Fig. 2. Micrograph of the diffusion layer of a Ti6Al4V sample thermally oxidised at 1173 K for 2 h.

F. Borgioli et al. / Materials Letters 59 (2005) 21592162

2161

1000

Microhardness (HK0.025 )

800

600

400 0 50 100 150 200

Depth (m)
Fig. 3. Microhardness profile of a Ti6Al4V sample thermally oxidised at 1173 K for 2 h.

Knoop microhardness measurements were carried out on the diffusion layer of the treated samples. The microhardness profile of a sample is shown in Fig. 3; depth is measured from the compound layerdiffusion layer interface. The modified layers show decreasing hardness values, from ~970 HK0.025 to matrix values (~380 HK0.025); the case depth of the hardened layer is ~35 Am. 3.2. Wear behaviour The wear volumes of untreated and treated samples measured after 3000 m sliding distance as a function of sliding velocity are shown in Fig. 4. Wear tests show that the wear volumes of both untreated and oxidised disks have a minimum for 0.8 m s1 sliding velocity; however, the volumes of the treated samples are from ~4 to 6 times lower in respect of the untreated alloy. The analysis of the wear debris shows that for both untreated and thermally oxidised samples they consist of titanium plates and small TiO (f.c.c.) oxide particles; as an example, the wear debris of thermally oxidised samples tested at 0.4 and 1.6 m s1 sliding velocities are shown in Fig. 5. For both sample types the
untreated thermally oxidised
Fig. 5. Wear debris of thermally oxidised Ti6Al4V samples tested with 0.4 (a) and 1.6 (b) m s1 sliding velocity, 50 N coupling load and 3000 m sliding distance.

30

Wear volume (mm3 )

20

volume fraction of oxide decreases as sliding velocity increases, but for the treated samples the oxide amount in the debris tends to be greater than that of the untreated samples tested with the same conditions. At 1.6 m s1 sliding velocity only small amount of oxide is detectable for oxidised samples, while for untreated samples no traces of oxide are detected. The observed trend of wear volume as a function of sliding velocity and the analysis of wear debris suggest that the wear is due to oxidation and delamination phenomena and that a transition from oxidation wear to delamination dominated wear occurs as sliding velocity increases [18,19]. The thermal oxidation of Ti6Al4V alloy allows to shift the transition to delamination wear towards slightly higher sliding velocities and to substantially improve the wear

10

Table 1 Characteristics of the modified layers of glow-discharge nitrided Ti6Al 4V samples [3]

0.4

0.8

1.6

Sliding velocity (m s -1 )
Fig. 4. Wear volumes vs. sliding velocity of untreated and thermally oxidised Ti6Al4V samples tested with 50 N coupling load and 3000 m sliding distance.

Nitriding temperature (K) 973 1073 1173

Compound layer thickness (Am) 12 34 57

Compound layer phases TiN, Ti2N TiN, Ti2N TiN, Ti2N

Diffusion layer thickness (Am) 25 4050 7590

2162

F. Borgioli et al. / Materials Letters 59 (2005) 21592162

25 20 15 10 5 0

Fig. 6. Wear volumes of untreated, thermally oxidised and glow-discharge nitrided (treatment temperatures: 973, 1073, 1173 K) Ti6Al4V samples, tested with 0.8 m s1 sliding velocity, 50 N coupling load and 1700 m sliding distance.

resistance, in respect of the untreated samples, in all the tested wear conditions. Further wear tests (sliding velocity: 0.8 m s1; coupling load: 50 N; sliding distance: 1700 m) were performed in order to compare the wear volumes of thermally oxidised samples with those of glow-discharge nitrided Ti6Al4V samples, previously tested in dry sliding conditions using nitrided samples as both counterparts [3]. As reported previously [3], the samples were nitrided at 973, 1073 and 1173 K for 24 h; the characteristics of the modified layers are summarised in Table 1. The wear volumes of untreated, thermally oxidised and nitrided samples are shown in Fig. 6. With the used test conditions the nitrided samples are not able to effectively improve the wear resistance of the Ti 6Al4V alloy; the high wear volumes of these sample types can be ascribed to a microfragmentation of the nitride surface layer, which causes an abrasive wear due to the hard nitride fragments [3]. On the contrary, the wear volume of the oxidised samples is from 6 to about 8 times lower than that of untreated and nitrided samples, so that a substantial improvement of the wear resistance is obtained.

Wear volume (mm3 )

untreated thermally oxidised nitrided 973 K nitrided 1073 K nitrided 1173 K

sample types have a minimum for 0.8 m s1 sliding velocity. The analysis of the wear debris shows that for both sample types they consist of titanium plates and small TiO particles, and the amount of oxide decreases as sliding velocity increases. The observed trend of the wear volume and the analysis of the wear debris suggest that the wear is due to oxidation and delamination phenomena and that a transition form oxidation wear to delamination dominated wear occurs as sliding velocity increases. As a matter of fact, the wear volumes of the treated samples are from ~4 to 6 times lower than those of untreated samples. Thus, the thermal oxidation treatment, by producing hardened surface layers, is able to improve the wear resistance of Ti6Al4V components. A comparison among the wear volumes of untreated, glow-discharge nitrided and thermally oxidised samples, tested with 0.8 m s1 sliding velocity, 50 N coupling load and 1700 m sliding distance, points out that, with these test conditions, the thermal oxidation substantially improves the wear resistance, in respect of both untreated and nitrided samples. The poor performance of nitrided samples can be ascribed to a third body abrasion mechanism due to the hard nitride fragments produced as a consequence of the failure of the nitride surface layer.

References
[1] A. Bloyce, P.H. Morton, T. Bell, in: ASM Handbook, vol. 5, ASM International, Materials Park, OH, USA, 1994, p. 835. [2] E. Rolinski, Surf. Eng. 2 (1986) 35. [3] A. Molinari, G. Straffelini, B. Tesi, T. Bacci, G. Pradelli, Wear 203204 (1997) 447. [4] A.M. Chaze, C. Coddet, J. Less-Common Met. 124 (1986) 73. [5] S. Frangini, A. Mignone, F. De Riccardis, J. Mater. Sci. 29 (1994) 714. [6] M. Mushiake, K. Asano, N. Miyamura, S. Nagano, SAE Transact. 100 (1991) 475. [7] C. Allen, A. Bloyce, T. Bell, Tribol. Int. 29 (1996) 527. [8] H. Dong, A. Bloyce, P.H. Morton, T. Bell, Surf. Eng. 13 (1997) 402. [9] A. Bloyce, P.-Y. Qi, H. Dong, T. Bell, Surf. Coat. Technol. 107 (1998) 125. [10] H. Dong, T. Bell, Wear 238 (2000) 131. [11] P.A. Dearnley, K.L. Dahm, H. Cimenoglu, Wear 256 (2004) 469. [12] H. Gqleryqz, H. Cimenoglu, Biomaterials 25 (2004) 3325. [13] F. Borgioli, E. Galvanetto, A. Fossati, G. Pradelli, Surf. Coat. Technol. 184 (2004) 255. [14] T. Bacci, F. Borgioli, E. Galvanetto, F. Galliano, Wear 240 (2000) 199. [15] L. Lutterotti, R. Ceccato, R. Dal Maschio, E. Pagani, Mater. Sci. Forum 278281 (1998) 87. [16] Standard Test Method for Ranking Resistance of Materials to Sliding Wear Using Block-on-Ring Wear Test, ASTM G77-98, Annual Book of ASTM Standards, vol. 03.02, American Society for Testing and Materials, West Conshohocken, PA, 1999. [17] G. Bertrand, K. Jarraya, J.M. Chaix, Oxid. Met. 21 (1983) 1. [18] S.C. Lim, M.F. Ashby, Acta Metall. 35 (1987) 1. [19] A. Molinari, G. Straffelini, B. Tesi, T. Bacci, Wear 208 (1997) 105.

4. Conclusions On the basis of the experimental results the following main conclusions can be drawn: The thermal oxidising treatment, performed on Ti6Al 4V samples at 1173 K for 2 h at 105 Pa, allows to produce hardened surface layers, having a ~970 HK0.025 maximum hardness value and a ~35 Am case depth. The wear tests, carried out on both untreated and oxidised samples in dry sliding conditions (sliding velocity: 0.41.6 m s1; coupling load: 50 N; sliding distance: 3000 m), show that the wear volumes of both