ICAMB 2012, Jan 9-11, 2012

Comparison of dry sliding wear of Ti-6Al-4V and Ti-6Al-7Nb implant alloys when subjected to heat treatment
B.K.C.Ganesh, N.Ramanaih P.V.Chandrasekhar Rao and S .V.N.Pammi

Abstract Titanium and its alloys are having very attractive properties enabling them to be used in the fields of aero space, biomedical, marine and many other corrosive environments. The application of these alloys is more attractive today in the field of biomedical implant materials due to their superior biocompatibility and strength. These alloys have high coefficient of friction and poor abrasive wear resistance which results in wear of the implant during its fixation in the body. Implant wear is a common phenomenon which is resulted due to high friction between artificial materials which is much higher than healthy and natural joints. The corresponding wear of the implant results in the accumulation of wear debris in the body tissues which results in inflammation, pain and loosening of implant resulting in shorter life period of the implant. Solution treatment of the alloy is one of the important techniques to improve the sliding wear properties of the alloy. These properties can be obtained by changing the microstructure of the alloy where the formation martensitic structure (acicular or retained ) is resulted. The formation of martensitic structure in titanium alloy results in improved hardness value with a subsequent improvement in its sliding wear behavior. In this work the both the Ti-6al-4V and Ti6Al-4V implant alloy materials are subjected to heat treatment above their transformation temperature followed by slow cooling in furnace, air and water. These specimens were further aged and tested for dry sliding wear properties against hardened steel disc using a pin- on-disc apparatus. Weight loss method with a optimal load of 50N and a sliding distance of 500metres is considered for conducting the wear test.An improvement in wear rate is observed under different heat treatment condition and also high wear resistance of Ti6Al-7Nb is reported. The conditions which favor the above results are properly discussed with the help of Energy dispersive X-ray spectroscopy (EDS) and an analysis of the wear tracks of the same is done using Scanning Electron Micrograph (SEM) is reported. KeywordsBiomaterials, Transformation temperature, Wear resistance, Vickers micro hardness Value.

I. INTRODUCTION i-6Al-4V and Ti-6Al-7Nb are binary alloys of titanium which have gained wide popularity as Implant materials.Ti-6Al-4V which has been used extensively for aerospace and marine applications is also being used as biomaterial due to its excellent biocompatibility and corrosion resistance. Though these metals have excellent strength to weight ratio and low density, these alloys have a high coefficient of friction which results in implant wear. This factor is very important while considering the friction between the artificial implant material coming in contact with the healthy and natural bone joint. Two main properties have been suggested with respect to the poor tribological properties of titanium alloys. [1]. 1. Low resistance to plastic shearing and low work hardening 2. Low protection exerted by the surface oxide which may form as a consequence of frictional heating The impact of the above factors such as low sliding wear resistance and protection exerted by the surface oxides has promoted many surface modification techniques which are under continuous development to improve the wear resistance of these alloys while working in a specific tribological environment. Titanium exists in various allotropic forms. At low temperatures, it has a closed packed hexagonal crystal structure known as , whereas above 883oC, it has a body centered cubic structure known as . The to transformation temperature of pure titanium either increases or decreases based on nature of the alloying elements. The alloying element such as aluminium, oxygen, nitrogen, etc that tend to stabilize are called alpha stabilizers and the addition of these elements increase beta transus temperature, while elements that stabilize phase are known as stabilizers such as vanadium, molybdenum, niobium, iron ,etc and addition of these elements depress the transus temperature. Some of the elements such as zirconium and stantium which do not have marked effect on the stability of either of the phase but form solid solutions with titanium are termed as neutral elements. [2].Ti-6Al-4V is now replaced by Ti-6Al-7Nb due to its excellent wear resistance and identical mechanical properties consisting of + microstructure. It is also replaced due to possibility of pain, inflammation and toxicity being developed by elemental vanadium which is formed as a result of abrasive wear of the implant when in contact with the 30

F. B.K.C.Ganesh is working asa research scholar in Mechanical Engineering Department, College of Engineering (A), Andhra University, Visakhapatnam. Email: bkcganesh @ yahoo.com. Mobile +91 98854 25863 S. N.Ramanaih .Ph.D is working as Associate Professor in the department of Mechanical Engineering ,College of Engineering, Andhra university, Visakhapatnam. T. P.V.Chandrasekhar Rao,Ph.D is working as a Associate professor in Mechanical Engineering Department, Lakireddy Balireddy college of Engineering, Mylavaram , Vijayawada.. T.S.V.N.Pammi Ph.D is working as Co-ordinator ,Advaced Analytical Laboratory,DST-PURSE programme, Andhra University, Visakhapatnam.

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ICAMB 2012, Jan 9-11, 2012 natural and healthy joint. Mitsuo [3] reported that the application of stress by rapid quenching results in the formation of martensitic structure in steels which contain residual austenite in their microstructures. This phenomenon is called stress or strain induced martensitic transformation which enhances ductility or fracture toughness of steel. Deformation induced martensitic transformation also occurs in titanium where unstable beta phase is retained at room temperature by rapid cooling such as water quenching from a high temperature near the beta transus temperature. The surface modification and change in microstructure can be obtained by heat treating the various samples at beta transus temperature (transformation temperature) where primary changes from hexagonally closely packed crystallographic structure () to body centered cubic crystallographic structure ().These specimens were Subsequently cooled by rapid quenching ,furnace cooling and air cooling followed by aging of these alloys at 500 0 centigrade .The objective of conducting the heat treatment cycle is to improve the hardness of the alloy which is beneficial in increasing the wear resistance of the alloy by retaining the transformed beta at the room temperature in order to achieve strengthening of the alloy. Wear rate calculation by pin and rotating disc machine using weight loss method is one of the common techniques to evaluate dry sliding wear behaviour of Titanium implant materials. A. Molinari et.al,[4] investigated on dry sliding wear mechanism of Ti-6Al-4V alloy. In their experimental work it has been found that the wear volume of the rotating specimens is reported as a function as sliding distance and the load applied on the pin. An increase in wear volume is resulted with an increase in applied load. O.Alam et.al, in their experimental work of dry sliding wear have reported that under a constant load of 45N applied on pin ,an increase of wear rate is identified up to a sliding distance of 500 meters. There after a steady state is attained which does not show any appreciable change in the wear rate behaviour of the alloy. B.D.Venkatesh.et.al [5] reported an improvement in various mechanical properties when + alloys were heat treated above the beta transus temperature and cooled by water quenching, air cooling and furnace cooling. Sami Abualnoun Ajel .et. al [6] have studied the influences of heat treatment on Ti-6Al-7Nb implant alloy, where the improvement in the strength of the alloy is reported to change with the modification of the alloy microstructure. It is evident that from the above literature that the effect of various types of heat treatment influences the various changes in the respective microstructures which further results in obtaining tailor made mechanical properties and tribological properties of the implant alloy. In this work dry sliding wear tests are conducted on Ti-6Al-4V and Ti-6Al7Nb implant alloys under various heat treating conditions. These tests we conducted on a Ducom wear testing machine considering an optimal load of 45N with sliding distance of 500metres under a constant velocity of 1m/sec. II. MATERIALS AND METHODS Both the materials are imported from Baoji Litai Corporation, Shanxi,China.The chemical composition by weight of the metals are as follows:
TABLE 1 CHEMICAL COMPOSITION OF IMPLANT ALLOYS

% COMPOSITION OF ELEMENT TITANIUM ALUMINIUM VANIDIUM/NIOBIUM IRON CARBON

TI-6AL-4V 89.6 6.29 3.95 0.09 0.029

TI-6AL-7N 87.6 5.80 6.50 0.037 0.017

The implant alloys are heat treated at 950o centigrade for one hour (beta transus temperature) in an Argon controlled atmosphere for a period of one hour. It is then aged at 550o centigrade for a period of three hours in an Air controlled furnace. The pins were cut according to the standard dimensions as shown in the figure 1 for the evaluation of wear track and microstructure. All the cut specimens were mechanically polished via a standard metallographic procedure to a final level of 0.3 m alumina powder and etched with a solution of water, nitric acid and hydrofluoric acid (80:15:5 in volume).Scanning Electron Micrograph (SEM) analysis is also conducted to study the wear track behaviour of various heat treated specimens. Hardness values are measured by Vickers Micro Hardness testing machine with a constant load of 0.5 kg. Average surface roughness (Ra) value of the wear track is measured by surface roughness testing instrument. In this work three samples of each condition were heat treated and subsequently cooled under different cooling environments such as Cooling in a furnace, air and quench in water followed by aging. These specimens were then tested by wear testing machine and the results are reported

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ICAMB 2012, Jan 9-11, 2012 (C) Air cooled (d) Furnace cooled

Fig. 1.Dimensions of the (a) Friction pin (b) Rotating disc in millimeters

2 (a) Base Material

(b) Water Quenched

III. RESULTS AND DISCUSSION A. Wear track analysis The following figure 2 shows the wear track micrographs of both the alloys. It is evident from the microstructures that the alloy Ti-6Al-4V hereafter referred as Ti64 has the presence of a protective layer in its water quenched and air cooled specimens. The presence of this layer is only seen when the alloy is cooled at a faster rate which cannot been seen in a slow cooling of the alloy in a furnace. Figue 3 shows the scanning electron micrograph (SEM) of water quenched specimen. It consists of two layers,a protective and a non protective layer. The energy dispersive spectrometry (EDS) of the base and Water quenched specimen is shown in figure 4 (a) ,(b),(c). From the EDS analysis of the base wear specimen it is clear that the oxygen and carbon content are limited to 2.34 and 0.56 % by weight respectively. But when the specimen is heat treated above the beta transus temperature and quenched with water there is a formation of a protective and a non protective layer as can be seen from the figure 3.The EDS analysis of the non protective layer shows huge amount oxidation with its weight % at 12.14 and carbon percentage of 1.11% as shown in figure 4(b).whereas the EDS analysis of protective layer shown in figure 4 (c) indicates an increase in the carbon at 1.71% by weight. This increase in the percentage of carbon clearly suggest that there is a formation of carbide layer which inhibits the amount of wear on this area of the specimen. Further the EDS analysis of the non protective layer also indicates a higher amount of metal to metal contact with increasing percentage of iron content when in contact with the steel disc.

(C) Air cooled

(d) Furnace cooled

Fig. 2. Wear Track of 1. Ti-6Al-4V and 2. Ti-6Al-7Nb subjected to various heat treatment processes at 20 X magnification

It is evident from the literature that when titanium and its alloys are exposed to oxygen containing atmosphere it results in the formation of an oxide layer on its surface with an oxygen diffusion zone beneath it. Hasen Gluryuz (2008).This formation is more pronounced when the alloy is heat treated above transformation temperature and cooled rapidly in air or quenching by water. This formation further plays an important role in developing a protective oxide layer which promotes remarkable advantage of the alloy while working in a friction and wear environment. Further the Scanning electron micrograph of quenched specimen shows the presence of acicular martensitic structure () in white globular primary and matrix. The presence of needle like acicular alpha greatly improves the hardness values of the quenched specimen.. The microstructures have been consistent with respect to the work done on this alloy by A.K.Jha .et.al. (2010) and A.Molinari .et.al.(2010).

1 (a) Base Material

(b) Water Quenched

Fig 3 Scanning Electron Micrograph of Water Quenched wear specimen.

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ICAMB 2012, Jan 9-11, 2012

Element CK OK Al K Ti K VK Fe L

Weight% 0.56 2.34 1.79 90.36 4.41 0.53 Total 100

Atomic% 2.10 6.53 2.96 84.13 3.86 0.83 CK OK Al K Ti K VK 1.71 11.29 0.46 83.26 3.29 Total 100 5.33 26.45 0.63 65.17 2.42 Element Weight% Atomic%

Fig 4 (a) EDS analysis of base wear specimen

Fig 4 (c) EDS analysis of Protective layer

Element CK OK Al K Ti K VK Fe L

Weight% 1.11 12.14 1.60 71.47 4.30 9.38 Total 100

Atomic% 3.49 28.57 2.24 56.19 3.18 6.32 Fig 5. Scanning Electron Micrograph of Quenched Specimen.

Fig4 (b) EDS analysis of Non protective layer

B. Weight loss and Wear rate analysis Maximum amount of weight loss has been reported from as received material as shown in Figure 6, where as less amount wear is reported from both water quenched and air cooled specimens of Ti-6Al-4V alloy. The results commensurate with the hardness values and microstructure behavior of all the heat treated specimens. Various Wear properties including surface roughness values of the heat treated specimens measured perpendicular to the wear track are given in the Table1.The value of as received material is high due low hardness of the specimen. This is due to coarse wear track developed during the testing procedure. The roughness value of water quenched specimen is low due to formation martensitic structure by heat treatment which resulted in an increase in the hardness value. 33

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ICAMB 2012, Jan 9-11, 2012 Presence of high amount of wear is reported from the wear testing of as received material Ti64 alloy . This corresponds to low hardness value which is Vickers hardness number VHN 311 as compared to quenched specimen which is having a hardness value of VHN 380.High amount of hardness values in quenched specimen is due to the presence of acicular (martensitic structure) which has formed due to heat treatment above beta transus temperature followed by water quenching and aging. The wear rate as shown in table 1 is also high as in the case of as received material when compared to air cooling or water quenched specimens. The wear rate of furnace cooling specimen is greater than the water quenched and air cooled specimens due to the formation of lamellar plate like structure where there is no presence acicular or retained beta .This is due to slow cooling of the specimen where complete transformation of body centered cubic crystallographic () structure to hexagonally closely packed () structure has taken place, which indicates more strength due to its high aspect (c/a) ratio of hexagonally packed crystallographic structure. The improvement of wear rate from base specimen to quenched specimen correlates the Archard adhesive wear theory that if all junctions have the same diameter and if the real area of contact is given by the normal load L divided by the hardness H, the total volume of the material removed during sliding through a distance S is given by V=K LS/3H Where K is the wear constant which gives the probability that a wear particle will be formed from an asperity junction. It is understood from the above equation that the amount of the specimen is inversely proportional to the weight loss or volume of the material removed. Therefore Ti64 specimens show a proportional decrease in their wear rate with a significant increase in their hardness values. On the other hand the wear rate for the Ti7nb alloys is almost consistent without any response to heat treatment. There is also no presence of a protective layer as encountered in the quenched specimen of Ti64 alloy. But the base wear rate of Ti7nb is lesser that Ti64 alloy due to abrasive wear resistance of adding niobium which is very much common in manufacturing of resistant steel bolts and nuts as well cutting tool industry for improving wear resistance. Similarly when the wear rate of as received Ti-6Al-7Nb specimen is considered the wear resistance is very high as compared to the as received Ti-6Al-4V specimen though the hardness value of Ti7Nb is lesser than Ti64 specimen .Therefore it is understood that the improvement of the wear resistance contradicts the Archard adhesive wear theory (1953), where there is no correlation between the hardness and wear resistance factors. High wear resistance of Ti 7nb specimens is primarily due to the presence of Nb2O5 in addition to TiO2 oxide. Compared to TiO2 oxide, Nb2O5 oxide is very good lubricating and hard oxide. Due to the presence of dense hard niobium oxide a higher surface roughness value is obtained as can be seen in table 1 and due to its lubricating properties a higher amount of wear resistance is resulted when compared toTi64 implant alloy.
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Fig 6.Weight loss of TI-6al-4V and Ti-6Al-7Nb under heat treating conditions FCA-Furnace cooled and aged. ACA-Air cooled and aged. WQA-Water quenched and aged.

different

The wear resistane of the Ti-6Al-7Nb alloy is also due to delamination wear as shown in the Scanning Electron Micrograph of the alloy in figure 7.The sem image clearly differentiates delaminated region with un delaminated region.
TABLE II. WEAR PROPERTIES OF TI-6AL-4V AND TI-6AL-7NB UNDER VARIOUS HEAT TREATING CONDITIONS

Heat treated condition As Received (Base Metal) Furnace cooled and aged Air cooled and Aged Water Quenched and aged As received (Base Metal) Furnace cooled and Aged Air cooled and aged Water Quenched and Aged

Surface roughness (Ra) Ti-6Al-4V 2.11 1.29 0.858 1.411 Ti-6Al-7Nb 2.23 1.15 1.24 1.55

Micro Hardness (HV0.5) 311 351 340 380

Wear Rate X 10 -11 m3/m 1.954 0.93 0.186 0.139

278 318 283 326

0.884 0.796 0.766 0.752

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ICAMB 2012, Jan 9-11, 2012 The delamination of the alloy has taken place due to following reseons[ 11]. During wear,dislocations are generated in the material due to the plastic deformation of the surface by the slider.If an oxide layer is present it is broken by the passage of the slider thus exposing a fresh clean surface.This then allows those dislocations nearly parelell to the surface to be eliminated due to the action of stress at the free surface.With continued sliding there will be pile up of dislocations at finite distance from the surface which will lead to the formation of voids.When these voids coalese crack formation takes place. When the crack reaches a critical length the material between the crack and the surface will shear producing a sheet like particle. This eventual presence of delaminated regions play an important role in minimising the loss of material form the pin there by improving the wear resistance.
2. Finer wear tracks were observed when the specimen hardness is increased during rapid quenching and air cooling of the specimen below the transformation temperature 3. Ti-6Al-7Nb resulted in higher wear resistance when compared to Ti-6Al4V alloy due to the presence delamination wear and Niobium oxide which is hard and has lubricating properties. 4. Formation of protective oxide has taken place only in quenched and air cooled specimens of Ti-6Al-4V, which indicates the presence of oxide layer at times of faster rate of cooling the alloy below the transformation temperature 5. Ti-6Al-4V implant alloy resulted in obtaining various dry sliding wear properties when it is heat treated above its transformation temperature. whereas Ti-6Al-7Nb alloy does not show much response to heat treatment. REFERENCES [1]. Md. Ohidul Alam, A.S.M.A.Haseeb. (2002)Response of Ti-6Al-4V and Ti-24Al-11Nb alloys to dry sliding wear against hardened steel, Journal of Tribology International, Vol 35, pp 357-362. [2]. M.Geetha, A.K.Singh, R.Asokamani, A.K.Gogia.(2009) Ti based biomaterials, the ultimate choice for orthopedic implants - A Review .Journal of Progress in Material Science, Vol 54, pp397-425. [3]. Mitsuo Niinomi.(2008) Mechanical biocompatibilities of titanium alloys for biomedical applications. Journal of Mechanical Behavior of Biomedical Materials, Vol 1, pp 30-42. [4]. A.Molinari,G Straffelini,B.Tesi,T.Bacci. (1997) Dry sliding wear mechanisms of the Ti6Al4V alloy, Journal of Wear, Vol 208, pp 105112. [5]. B.D.Venkatesh, D.L.Chen, S.D.Bhole. (2009) Effect of heat treatment on mechanical properties of Ti-6Al-4Valloy, Journal of Material Science & Engineering (A), Vol 506, pp 117-124. [6]. Sami Abualnoun Ajeel, Thair. L. Alzubaydi, Abdulsalam. K. Swadi. (2007) Influence of heat treatment conditions on microstructure of Ti6al-7Nb alloy as used surgical implant materials. Journal of Engineering and Technology, Vol 25, pp 431 442. [7]. A.K.Jha, S.K.Singh, M.S.Kiranmayee.(2010) Failure analysis of titanium alloy (Ti6Al4V) fastener in aerospace application, Journal of Engineering Failure Analysis, Vol 17 ,pp 1457-1465. [8]. Hasen Gluyrez,Huseyin cimanglo (2008)Oxidation of Ti-6Al-4V alloy,Journalof alloy and compounds .doi:10.1016/J.Jallcom.2008.04.024. [9]. J,F.Archard, (1953) ,Journal of Applied Physics, Vol 24 ,pg 981-988. [10]. N.P.Suh, (1973), Journal of Wear, Vol 25,pg 111-124. [11]. N.P.Suh, (1974), The delamination theory of wear, MIT Report submitted to NTIS U.S. Department of Commerce.

Fig 7 Wear track of Ti-6Al-7Nb alloy

IV. CONCLUSIONS 1. The Wear rate of Ti-6Al-4V quenched specimen is very low due to the presence of protective oxide coating layer formed during heat treatment and also due to the presence of acicular martensitic structure (retained beta) in its microstructure.

SMBS, VIT University, Vellore , India

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