WEAR

ELSEVIER
Wear 181-183 (1995) 258-262

Wear of UHMWPE sliding against untreated, titanium nitridecoated and Hardcor -treated stainless steel counterfaces
B. Derbyshire a, J. Fisher a, D. Dowson a, C.S. Hardaker b, K. Brummitt b
aDepartment of Mechanical Engineering, University of Leeds, Leeds, UK
b DePuy International Ltd, Leeds, UK

Received 3 May 1994; accepted 22 September

1994

Abstract A pin-on-plate reciprocating machine has been used to assess the wear performance of ultrahigh molecular weight polyethylene when sliding against untreated, titanium nitride-coated, and Hardcor -treated stainless steel counterfaces. The initial surface roughness of the stainless steel counterfaces was smooth (R,- 0.01-0.02 pm). Following the surface treatments the surfaces were significantly roughened. In the first set of wear tests run in water the wear rates of the UHMWPE on the roughened treated surfaces were significantly greater than on the smooth untreated stainless steel surface. Both sets of treated surfaces were then polished to the same smoothness as the initial untreated surface. In the second set of tests, run with bovine serum as a lubricant, there was no significant difference in the wear rates between the three counterfaces.
Keywords:

Polyethylene; TiN; Hardcor; Steel

1. Introduction

The long-term success of total joint prostheses has been frustrated by an unacceptable rate of aseptic loosening. The build-up of particulate wear debris in the surrounding tissue is a major contributor to the process of loosening. The debris elicits a phagocytic reaction which may subsequently stimulate bone resorption around the implant [l-3]. The severity of this reaction is considered to be dependent upon the number and, some believe, the size of the wear particles. A reduction in the amount of wear debris is predicted to reduce the incidence of loosening. Since the 1960s ultrahigh molecular weight polyethylene (UHMWPE) has been the material of choice for the concave components of prosthetic joints because of its good biocompatibility and wear performance. However, if the convex component is made of metal, excessive UHMWPE wear may be generated as the metal component becomes scratched by hard particles of cement, bone [4] or metal [5]. The wear process of UHMWPE is extremely sensitive to the roughness of the counterface; slight changes in roughness or a small amount of damage can produce a large increase in the UHMWPE wear rate [6,7]. In an attempt to limit these effects, manufacturers have introduced harder and more

scratch-resistant materials, such as ceramics, to replace metal femoral heads [8,9]. However, knee joints cannot be readily fabricated from ceramic, and there is some concern about using small sized, alumina ceramic, femoral heads because of their susceptibility to fracture. As an alternative approach, various surface hardening processes have been considered for the metal components. These include ion implantation of titanium alloy [lo], and the surface coating technique of physical vapour deposition (PVD) of titanium nitride (TiN). The PVD process creates a hard coat H, = 2000), 3-5 pm thick, and has been used to protect titanium alloy implants from wear and third-body abrasion [11,12]. The susceptibility of stainless steel implants to thirdbody abrasion has prompted the consideration of similar surface hardening processes. A recently developed surface treatment for austenitic stainless steels is the Hardcor process [13]. This is an undisclosed, proprietary case hardening process (Hv = 1000-1200) which is said to improve the wear and corrosion resistance of stainless steel. A case thickness of up to 30 pm can be created by this process. In this study, a pin-on-plate reciprocator was used to compare the wear performance of UHMWPE on stainless steel plates which were either untreated or had been subjected to TiN PVD or Hardcor treatments.

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2. Materials and method Twelve surgical grade (316) stainless steel plates were ground and lapped to a mirror finish (0.01 pm <R, < 0.02 pm). Two plates were coated with TiN and two were subjected to the Hardcor treatment (by Hardcor BV, Beekbergen, Netherlands) to a depth of 22 pm. The treated plates were supplied through Depuy International Ltd, Leeds. The average surface roughness (R,) of each plate was measured, prior to and following surface treatment and during the course of the wear tests, using a Rank-Taylor-Hobson Talysurf 5 instrument with a cut-off of 0.8 mm. (Tables 1 and 2). The surfaces of the Hardcor -treated plates were found to be very rough after treatment (Table 2) and were therefore polished to a smoother finish, which was still rougher than the stainless steel. The TiN surfaces were also roughened in Table 1. Cylindrical pins were machined from compressionmoulded UHMWPE block (GUR412, Chirulen P, Hoechst, Germany). They were not y irradiated. Each pin was 12 mm in diameter and 20 mm long with one end having the shape of a truncated cone with a 30 taper and a wear-face diameter of 3 mm. The wearface of each pin was microtomed to remove machining marks. The pins were initially cleaned in an ultrasonic cleaning bath but subsequent cleaning was carried out using tissue-paper with isopropanol as a solvent. The pins were left to stand in de-ionized water for two weeks in order to pre-soak them. They were then left
Table 1 Surface roughness R. (pm) for the stainless steel and TiN surfaces in Test 1 Station 1 2 3 5 6 ss ss ss TiN TIN 0 km 0.012 0.009 0.013 0.011 a, 0.045 0.013 n, 0.034 63.25 km 0.012 0.009 0.012 0.027 0.037 124.96 km 0.013 0.009 0.013 0.021 0.033 259.16 km 0.014 0.010 0.014 0.027 0.035

Stainless steel surface roughness before TIN treatment.

Table 2 Surface roughness R. (pm) of Hardcor and stainless steel surfaces in Test 2 Station 1 2 3 5 6 ss ss ss HC HC 0 km 0.010 0.010 0.010 0.013 0.160 b, 0.017 = , 0.010 e, 0.165 b, 0.018 = 162.92 km 0.012 0.012 0.011 0.017 0.025 381.17 km 0.012 0.011 0.014 0.018 0.025

to acclimatize in a temperature controlled (20 C) metrology room for a standard period (2.5 days), after which all pins were weighed using a Mettler microbalance (sensitivity of 1 pg). Three tests were carried out using a six-station pinon-plate reciprocating machine [9]. In Test 1, two TiNcoated and three standard, stainless steel plates were installed in the reciprocator baths. In Test 2, two Hardcor -treated and three standard stainless steel plates were installed. For these two tests, the reciprocator baths contained de-ionized water, the levels of which were maintained (because of evaporation) by a continuous drip feed. In Test 3, two TiN-coated, two Hardcor -treated, and two standard, stainless steel plates were installed in the baths containing bovine new-born calf serum (Sera-lab, Sussex) supplemented by 0.1% sodium azide to retard bacterial growth. The levels were maintained by a six cylinder syringe driver containing a 1% solution of sodium azide. The same TiN-coated and Hardcor -treated plates used in Tests 1 and 2 were used in Test 3. However, the counterfaces which had been roughened by both surface treatments and polymer transfer film were lapped prior to the test. This reduced the surface roughnesses of all the plates (Table 3) to the range 0.01 to 0.02 pm. Each test pin was loaded to 80 N by a weight and lever arrangement, producing a nominal contact stress of 12 MPa. An unloaded soak-control pin accompanied each test pin during the test so that changes in test pin weight due to random fluctuations in liquid absorption could be compensated. At weekly intervals, the pins were removed and cleaned; any adhering ribbons of debris at the edges of the wear faces being wiped away. After acclimatizing for the standard period, the pins were weighed and then re-installed in the cleaned and replenished reciprocator baths. After two weeks of Test 1 (125 km), optical micrographs were taken of the wear surfaces of the pins and plates. Tests were run for between 260 and 400 km and with a stroke length of between 40 and 44 mm corresponding to a peak sliding speed of between 0.31 and 0.35 m s -1 . Wear volume loss was calculated from the weight loss by assuming the density of UHMWPE to be 0.936 mg mmm3. Wear factors between each measurement
Table 3 Surface roughness R. (pm) of the counterfaces Station 1 2 3 4 5 6 ss ss TiN TIN HC HC 0 km 0.012 0.010 0.016 0.023 0.017 0.018 125.04 km 0.010 0.010 0.016 0.022 0.015 0.021

in Test 3 372.38 km 0.010 0.011 0.022 0.020 0.017 0.020

234.81 km 0.011 0.010 0.018 0.017 0.017 0.019

a Stainless steel surface roughness before Hardcor treatment. b Surface roughness following Hardcor treatment. Surface roughness of Hardcor treated surface after lapping.

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stage were calculated k=

using the formula

m3 N-1 m-

Volume loss Load x Sliding distance

The mean and standard deviation of the UHMWPE wear factors for each type of plate surface were calculated and the means were statistically compared, using Student t-test, for both lubrication conditions. s

3. Results The variation of wear volume with sliding distance for Test 1 is shown in Fig. 1. It is immediately apparent from this graph that the TiN-coated plates resulted in a rapid rate of UHMWPE wear during the first 63 km. This was followed by a reduction in the wear rate as the wear levelled off for the rest of the test. In comparison, UHMWPE wear on the untreated stainless steel plates remained relatively low for the duration of the test. The mean wear factor of UHMWPE on TiN-coated plates was 7.43 X lo- mm3 N- m- and on untreated plates it was 0.42x10- mm3 N-l m-I (Fig. 4). The difference was statistically significant @<0.02). A transfer film of UHMWPE was formed on all the plates in Test 1. Table 1 documents the variation in surface roughnesses of the plates prior to and during Test 1. All of the plates were initially very smooth (Ra =0.01-0.02 pm). After TiN treatment, the surface roughnesses of plates 5 and 6 had increased by up to fourfold. The reason for this increase can be seen in Fig. 5(a) which is a Talysurf record of TiN-coated Plate 6 before the test. The Talysurf record is intermittently punctuated by sharp peaks which probably represent individual,

solidified droplets of TiN. This effect is typical of TiN coatings. In contrast, Fig. 5(b) shows a record of an untreated stainless steel surface which is characterized by smaller, smoother, peaks and valleys. The very shallow transfer film which had developed on the untreated plates had caused only a very slight increase in surface roughness by the end of the test. The TiNTcoated plate 5, however, was relatively rough initially but became smoother as the deep transfer film developed over it. The TiN-coated plate 6 stayed at the same roughness throughout the test. The variation of wear volume with sliding distance for the Test 2 pins is shown in Fig. 2. UHMWPE wear on the untreated stainless steel counterfaces was very low for the first 160 km but increased gradually thereafter. UHMWPE wear on Hardcor -treated surfaces increased at an approximately constant rate from the start of the test. The mean wear factor (Fig. 4) for UHMWPE on Hardcor surfaces was approximately twice that on the untreated surfaces. The difference was statistically significant (p <0.02). All Test 2 plates appeared to develop polymer transfer films. However, the surface roughness of only one of the plates (plate 6) increased appreciably during the test (Table 2). Fig. 3 shows the UHMWPE wear volume losses during Test 3. The slope (wear rate) of each of these graphs was very similar. Pin 5, on the Hardcor plate, wore slightly less than the other pins during the first 55 km, but, thereafter, the wear rate was similar to the other pins. The wear rate of Pin 3 on the TiN-coated plate increased temporarily after 183 km of sliding, and this coincided with a slight increase in surface roughness of the plate (Table 3). The surface roughnesses of the other plates did not change throughout the test. No polymer transfer film was observed on any of the plates.

0.75

0.65

-0.10

I~, ~,~,,,,,~ , /~~ ~/ ,, ~,, ~ ,~

50 Slid,ng 100 O,s!an e 150 km

200

250

100 Sl,dq

Distance

200 km

Fig. 1. Variation of UHMWPE wear volume with sliding distance for untreated and TiN-coated counterfaces in water.

Fig. 2. Variation of UHMWPE wear volume with sliding distance for untreated and Hardcor -treated counterfaces in water.

B. Derbyshire
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261

I
UHMWPE Ptns on StaInless Steel. TIN coated and HARDCOR treated surfaces In serunl / ,, If / STN STN STN STN STN STN 1 2 3 4 5 6 SS SS TIN TIN HC HC , ??

0.50

0.40

I
0

/f

2
:: s

0.30

-*- x-a - +-+ 0 - -0 _/I--n _o D

E 2 0.20

0.10

0.00 100 Sliding 200 Ofstance km 300 400

Fig. 3. Variation of UHMWPE wear volume with sliding distance for untreated, TiN-coated, and Hardcor -treated counterfaces in serum.

Mean Wear 10

Factor

x lOE-8

mm /Nm

SS TIN Test

SS Test

HC 2

SS

TIN Test 3

HC

* so = 8.96
Fig. 4. Mean and standard deviation of the intermediate UHMWPE wear factors for Tests 1 and 2 (water lubrication) and Test 3 (serum lubrication).

untreated plates, due to the roughening of the counterface by the surface treatment. In tests 1 and 2 lubricated with water, the results were affected by the formation of transfer film on the counterface, as has been found in previous studies [14]. However, in spite of this, introducing additionalvariation to the wear factor, there was still a statistically significant increase in UHMWPE wear rate for the two sets of treated surfaces which were roughened during the surface treatment. It is interesting to consider the different wear processes that may occur for the different surface topographies in the treated and untreated cases. In the case of the smooth untreated stainless steel counterfaces, the microscopic asperities of the counterface (Fig. 5(b)) are likely to produce wear by an adhesive fatigue mechanism [15], while previous studies have indicated that macroscopic polymer asperity wear may also be present on the smooth counterfaces [15]. However, in the case of the roughened surface, the large spikes on the coating (Fig. 5(a)) accelerate the wear caused by the counterface asperities and the mechanism may well change from an adhesive fatigue to a more abrasive action. Under these conditions, one would not expect macroscopic polymer asperity wear to be significant. Recognising that the roughness of the surface treatments caused increased wear, the treated surfaces were lapped prior to test 3 to achieve an equivalent surface roughness to the treated surfaces and serum was used in the test to avoid transfer film formation. The wear rates of the pins remained generally constant throughout the test. The mean wear factor of 1.06 X lo-* mm3 N- m-l for UHMWPE sliding on untreated stainless steel was similar to results found in other pin-on-disc [7] and pin-on-plate [6] studies. Statistical analysis of the UHMWPE wear factors of Test 3 revealed no significant difference between pins sliding on any of the plates.

Statistical analysis of the wear nificant difference in UHMWPE types of plate surface. The mean of the wear factors for Test 3

factors showed no sigpin wear on the three and standard deviation are shown in Fig. 4.
0.2mm -

4. Discussion Although surface hardening treatments for joint prostheses are primarily being introduced to improve the resistance to third-body abrasion, some laboratory studies have suggested that these treatments may also reduce the general wear of the UHMWPE components [ll]. The present study has shown that the wear of lubricated UHMWPE was significantly greater against TiN-coated and Hardcor -treated plates than against

Fig. 5. Talysurf record of the surface profile, prior to testing, for (a) a TiN-coated plate, (b) an untreated plate and (c) a TiN-coated plate after light lapping (Test 3).

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The lapping treatment of the TiN-coated plated removed the individual, solidified vapour droplets of TiN lying above the surface of the plate (Fig. 5(a)) which had contributed to the comparatively high roughness of these plates in Test 1 (Table 1). In addition, the lapping treatment had also removed particles of TiN to create discrete pockets in the surface. The surface profile depicted by the Talysurf record (Fig. 5(c)) then re sembled the sort of topography encountered with ceramic surfaces [6], i.e. a generally smooth surface punctuated by holes in the surface. These TiN surfaces remained relatively smooth for the duration of the test. The dramatically improved wear performance of UHMWPE on the lapped TiN surfaces compared with the unlapped surface suggest that polishing of TiNcoated prostheses, after surface treatment, could be advantageous, but major concerns remain about the damage to the coating by this post treatment polishing. The mean wear factor for the TiN-coated plates was 1.53X lo- mm3 N- m-l which contrasts with the factor of 21.1 X lo- mm3 N-l m-l found by Streicher et al. [12] in a pin-on-disc study of UHMWPE sliding on TiN-coated cobalt-chromium discs. However, Streicher used a different method of wear measurement (change in length), and it has been noted previously that measurement of change in length can produce elevated wear factors as it introduces a measure of creep deformation. In conclusion, this study highlights the importance of counterface topography after surface treatments, and in particular, the harmful effects on UHMWPE wear of positive lumps or spikes on treated counterfaces. Post treatment polishing to produce treated surfaces of equivalent roughness, showed that equivalent wear could be achieved in comparison to untreated surfaces. If hard surface treatments of adequate quality could be produced, then the long-term wear of UHMWPE in the body may well benefit by the improved resistance to damage of a hardened femoral counterface.

The authors would like to thank Mr.D.H. Darby and Mr. A. Heald for their technical assistance.

References
H.G. Willert, H. Bertram and G.H. Buchhom, Osteolysis in alloarthroplasty of the hip, C&z. Orthop., 258 (1990) 95-107. 121 D.W. Murray and N. Rushton, Macrophages stimulate bone resorption when they phagocytose particles, J. Bone Jt. Surg., 72B (1990) 988-92. [31 M. Jasty and E. Smith, Wear particles of total joint replacements and their role in periprosthetic osteolysis, Current Opin. in Rheumarol., 4 (1992) 204-209. 141 L. Caravia, D. Dowson, J. Fisher and B. Jobbins, The influence of bone and bone cement on counterface roughness in sliding wear tests of ultra-high molecular weight polyethylene on stainless steel, .I. Eng. Med., 204H (1990) 65-70. [51 M. Jasty, C.R. Bragdon, K. Lee, A. Hanson and W.H. Harris, Surface damage to cobalt chrome femoral heads, J. Bone Jt. Srug., 76B (1994) 73-77. 161 B. Weightman and D. Light, The effect of surface finish of alumina and stainless steel on the wear rate of UHMW polyethylene, Biomaterials, 7 (1986) 20-24. [71 J.R. Cooper, D. Dowson and J. Fisher The effect of transfer film and surface roughness on the wear of lubricated ultrahigh molecular weight polyethylene, Clin. Mater., 14 (1993) 295-302. PI H. Okumura, T. Yamamuro, T. Kumar, T. Nakamura and M. Oka, Socket wear in total hip prostheses with alumina ceramic heads, in H. Oonishi (ed.), Bioceramics, Ishiyaku Euro America, Tokyo, 1989, pp. 284-289. [91 B. Derbyshire, J. Fisher, D. Dowson, C.S. Hardaker and K. Brummitt, Comparative study of the wear of UHMWPE with zirconia ceramic and stainless steel femoral heads in artificial hip joints, Med. Eng. Phys., 16 (1994) 229-23. PO1 R.A. Buchhom, E.D. Rigney and J.M. Williams, Ion implantation of surgical Ti 6Al 4V for improved resistance to wear accelerated corrosion, J. Biomed. Mat. Res., 21 (1987) 35566. C.D. Peterson, B.H. Hillberry and D.A. Heck, Component wear WI of total knee prostheses using TXAl_4V, TiN coated Ti-6Al-4V, and Co-Cr-Mo femoral components, L Biomed. Mat. Res., 22 (1988) 887-903. P21 R.M. Streicher, H. Weber, R. Schoen and M.F. Semlitsch, Wear resistant couplings for longer lasting articulating total joint replacements, Adv. Biomaler., 101 (1992) 179-187. iI31 R.H. Van der Jagt, B.H. Kolster and M.W.H. Gillham, Antiwear/corrosion treatment of finished austenitic stainless steel components: the Hardcor process, Mater. Des., 12 (1991) 41-46. [I41 H.A. McKellop, I.C. Clarke and K.L. Markolf, Wear characteristics of UHMW polyethylene: a method for accurately measuring extremely low wear rates, J. Biomed. Mat. Res., 12 (1978) 895-927. 1151 J.R. Cooper, D. Dowson and J. Fisher, Macroscopic and microscopic wear mechanism in UHMWPE, Wear, 162 (1993) 373-384.

VI

Acknowledgements

This project was supported by the Science and Engineering Research Council and by DePuy International.