Medical Engineering & Physics 32 (2010) 908913

Contents lists available at ScienceDirect

Medical Engineering & Physics

journal homepage: www.elsevier.com/locate/medengphy

A new material for hip prosthesis without considerable debris release

Adelina Borruto
University of Rome La Sapienza, Department of Chemical Engineering and Materials, Via Eudossiana, 18, 00184 Rome, Italy

a r t i c l e

i n f o

a b s t r a c t
This work presents an alternative bearing surface in the eld of total hip replacements. It is composed of a polymer composite polyether-ether-ketone (Peek) as the matrix and a carbon bre as reinforcement. The authors carried out experimental research in order to investigate the formation of debris caused by tribological coupling of three types of Peek and cobalt chrome alloy. The wear tests (ASTM 99G) have been performed with a pin on disc tribometer in an air environment, under the following conditions: dry, water lubrication using demineralised water as a lubricant and human serum. A method of ltering under vacuum is used to extract the debris from the lubricants used in the tribological test, and the analysis at Scanning Electron Microscopy (SEM) is used to characterize the debris. 2010 IPEM. Published by Elsevier Ltd. All rights reserved.

Article history: Received 9 July 2009 Received in revised form 24 June 2010 Accepted 24 June 2010 Keywords: Hip Debris Wear Carbon bre Peek

1. Introduction Total hip joint replacements have been used for over 30 years with considerable success but it has been shown through clinical studies [1,2] that no fewer than 10% of implants require revision in the rst 10 years of use. Today the most common type of hip joint implanted comprises a highly polished metallic or ceramic femoral head articulating against an ultra-high-molecular weight polyethylene (UHMWPE) acetabular cup. Polyethylene wear particles are released into the surrounding tissue and this can cause aseptic loosening of the femoral or acetabular components. The wear particles activate macrophages, which release cytokines or inammatory mediators, stimulating osteoclasts, which result in bone absorption. The volume and the size (in the size range 0.210 m) of the particles [36] produced an important bearing on their biological activity [79]. The release of UHMWPE wear particles from the articulating surfaces of metal on UHMWPE hip prostheses, and the subsequent biological reactions to these wear particles have been identied as one of the major causes of osteolysis and failure of total hip replacements [1014]. Metal on metal articulations have been used in total hip joint replacements, but the clinical results have not always been positive [1518]. Although the wear volumes produced by metal on metal articulations have been estimated to be 40100 times lower than metal on polyethylene bearings [19,20], the effects of the

metal particles, that have a range of 0.11 m [21], are difcult to determine. Indeed it is not known how the biologic environment is affected by the presence of high levels of foreign ionic species: cobalt, chromium, and titanium may bind to proteins and circulate in the blood [22]. The presence of metallic wear particles in periprosthetic tissues is well documented from retrieval studies of metal on UHMWPE prostheses [2328]. With regard to the tribological coupling of ceramic-onceramic hip prostheses, the SEM analysis revealed particles in the 0.053.2 m size range, and TEM revealed particles in the 590 nm size range [29]. Therefore, in order to increase the longevity of total hip replacement joint, the rate of wear debris generated by the articulation surface must be reduced. In this study it was decided to examine the debris produced by Peek carbon bre material, chosen for its ability to have a low coefcient of friction and its resistance to attack by a wide range of organic and inorganic chemicals and solvents and its biocompatibility. 2. Materials and methods 2.1. Wear and friction tests Wear-friction tests on three different types of Peek (Table 1) with roughness intervals Ra (m) (0.030.08) have been performed with a pin on disc tribometer (ASTM 99G norm), in air environment: under dry conditions; with lubricants: demineralised water and human serum.

Tel.: +39 0644585637; fax: +39 0644585451. E-mail address: adelina.borruto@uniroma1.it.

1350-4533/$ see front matter 2010 IPEM. Published by Elsevier Ltd. All rights reserved. doi:10.1016/j.medengphy.2010.06.007

A. Borruto / Medical Engineering & Physics 32 (2010) 908913 Table 1 Materials. Material Ketron Peek 450G (Quadrant) Larpeek Peek CA (Lati spa)

909

Description Polyether-ether-ketone, thermoplastic polymer (extrusion or injection) Polyether-ether-ketone, thermoplastic polymer with 30% randomly oriented carbon bres (extrusion or injection). Fibre length = 1 mm Polyether-ether-ketone, thermoplastic polymer with 30% of monodirectional carbon bres (under pressure in a mould at melting point). Fibre length > 1 mm High molecular weight thermoplastic polymer of ethylene Super alloy (30% Cr, 5% Mo)

Peek CF (made in laboratory)

UHMWPE CoCr alloy

maximum load of 500 kg, therefore the weight for cm2 will be: 500/7.4 = 67.6 kg/cm2 = 0.67 kg/mm2 . Assuming in the rst instance a contact area value of nearly 1 mm2 in the tribological coupling at pin on disc, the load results 0.67 1 = 0.67 kg. Choosing a safety factor equal to three, the load to be applied to the tribometer will be 0.67 3 = 2 kg = 20 N. Then, with a load of 20 N, the effective contact area was calculated by Hertz formulas for various couplings, then the nominal contact pressure also was calculated (Table 2). During the tests environmental temperature and the relative humidity were measured. The friction coefcient and wear were recorded in real time. The pin and the disc were weighed at the beginning and at the end of the tests. For every coupling typology the tests were performed at least three times (each plotted curve is the average of three curves) and moreover, inverse couplings were tried. All the specimens were observed under the electronic microscope (SEM). 2.2. Debris analysis 2.2.1. Extract of the debris The tribometer pin on disc, used for this test, has a container for lubricating uids. The machine was washed thoroughly before the start of each test. At the end of each test the machine was again washed using the lubricating uid to recuperate any particles that had been lost/missed. The collected lubricant was then ltered.

Fig. 1. Samples shape, size are in mm.

2.3. Filter of the debris The dry wear tests were realized to know the behavior of prosthetic material in the event of accident, i.e. due to a change in the prosthesis position, other words when the prosthesis is in the absence of lubrication. For comparison, wear-friction tests on UHMWPE were also performed in the same way. The tribological coupling used was: Pin CoCrDisc Peek or UHMWPE. Specimens were cut in shape and size shown in Fig. 1, then they were lapped to obtain the request roughness. The working conditions are shown in Table 2. In order to choose the load to apply to the pin on disc tribometer, we operated in the following way. Whereas the radius (r) of femoral head of CoCr alloy is equal to 1.4 cm, the spherical surface will be 4 r2 = 24.63 cm2 . The real surface that bears the load is nearly 30%: 24.63 0.3 = 7.4 cm2 . Supposing that the average body weight of a person is 70 kg and calculating it in some particular movements (running, getting up, going up and down the stairs) the load will be seven times higher than the body weight, we can consider a total
Table 2 Operative condition. Angular velocity Linear velocity Normal load applied Average nominal contact pressure Surface nishing Cleansing solvent Lubrication Lubricant Test duration Quantities measured during the test 100 cycles/min 0.18 m/min, mean radius of track 1.7 cm 20 N 0.12 GPa (Peek) Ra (m) = 0.030.08; Ra (m) = 0.083 Acetone CO(CH3 )2 Continuous drop addition Demineralised water, human serum 10,000 cycles = 1 km Tangential force (measured every 1000 cycles) Wear (mm) (measured every 1000 cycles)

The collected lubricant was ltered under vacuum. In particular: - For the liquid from the water test it was enough to repeat the ltering once (23 times) only using a laboratory system of vacuum ltering (Millipore). Cellulose acetate lters were used, rstly with a cut-off of 0.47 m and then with a cut-off of 0.22 m (Schleicer and Schuell). It was necessary to use lters of 0.22 m because no debris was apparent when using lters with larger pores. The debris deposited on the upper part of the membrane was then removed using a sticky tampon/stab and SEM and EDS tested. - For the tribological tests in which the ultra-ltered human serum lubrication was used (SigmaAldrich), the procedure was modied. The agglomeration of a proteolytic and lipoid nature formed after ltering (a polarising effect of the membrane itself), was removed from the membrane: after ltering the serum, the membrane was rst thoroughly rinsed with an abundance of distilled water (about 1.5 L previously ltered), to remove any deposits of a proteolytic nature and then with ethylene (about 0.5 L previously ltered) to remove any traces of lipoid aggregates. It was then possible to remove the debris of the wear test from the treated membrane using the previously described procedures. 3. Results 3.1. Results of the wear tests Figs. 25 show the trend of the friction coefcient and the wear versus the number of cycles, both with and without lubrication, of the following tribological couplings: (1) Pin CoCrDisc Peek 450G (Fig. 2) The friction coefcient at 10,000 cycles under dry conditions took on a value equal to 0.2 with a wear value of 0.013 mm. In water condition the friction coefcient at 10,000 cycles took on a value equal to 0.09 with a wear value of 0.010 mm. The trend

910

A. Borruto / Medical Engineering & Physics 32 (2010) 908913

Fig. 2. Tribological coupling: Pin CoCrDisc Peek 450G at 20 N in air, dry condition and water lubrication. (a) Friction and (b) wear. Fig. 4. Tribological coupling: Pin CoCrDisc Peek CF at 20 N in air, dry condition, water and human serum lubrication. (a) Friction and (b) wear.

of the curve is shown to rise slightly with the increase in the number of cycles. (2) Pin CoCrDisc Peek CA (Fig. 3) The friction coefcient at 10,000 cycles under dry conditions took on a value equal to 0.15 with a wear value of 0.05 mm. In water condition the friction coefcient at 10,000 cycles took on a value equal to 0.05 with a wear value of 0.010 mm. The trend of the wear curve is to atten out with the increase in the number of cycles. The friction both under water lubrication and dry conditions tends to level out too with the difference that under dry conditions the values were slightly higher. (3) Pin CoCrDisc Peek CF (Fig. 4) This tribological coupling was also tested using human serum. The friction coefcient at 10,000 cycles under dry conditions took on a value equal to 0.1 with a wear value of 0.001 mm. In water condition the friction coefcient at 10,000 cycles took on a value equal to 0.05 with a wear value of 0 mm.

With human serum, wear values of 0 mm and a friction coefcient of 0.04 were found. The trend of the wear curve and of friction was parallel with the x-axis. (4) Pin CoCrDisc UHMWPE (Fig. 5) The friction coefcient at 10,000 cycles under dry conditions took on a value equal to 0.2 with a wear value of 0.003 mm. In water condition the friction coefcient at 10,000 cycles took on a value equal to 0.06 with a wear value of 0.035 mm. In this case we see that there was an actual inversion of the values, the wear under water lubrication being greater than under dry condition. 3.2. Results of the SEM tests All the tests were examined using and electronic microscope (SEM) and EDS analysis. For the sake of brevity we are reporting only signicant cases.

Fig. 3. Tribological coupling: Pin CoCrDisc Peek CA at 20 N in air, dry condition and water lubrication. (a) Friction and (b) wear.

Fig. 5. Tribological coupling: Pin CoCrDisc UHMWPE at 20 N in air, dry condition and watery lubrication. (a) Friction and (b) wear.

A. Borruto / Medical Engineering & Physics 32 (2010) 908913

911

Fig. 6. SEM pictures of Pin and Disc worn surfaces (20 N, 10,000 cycles) under water lubrication. (a and b) Pin CoCrDisc Peek CF coupling, efcient lubrication with the absence of debris; (c and d) Pin CoCrDisc UHMWPE coupling, formation of notable quantity of debris.

Fig. 6 shows two tribological couplings: Pin CoCrDisc UHMWPE and Pin CoCrDisc Peek CF after 10,000 cycles under water lubrication. It is noted that, in the case of the Peek CF there is an absence of debris whereas with the tribological coupling with UHMWPE the Pin and the track on the Disc appear to be covered by debris. Fig. 7 shows the tracks on the three Discs of Peek CA after 10,000 cycles under dry conditions, water and serum lubrication. There is no sign of wear either on the Pin or on the track on which it is noted that there has been no alteration of the bres. 3.3. Result of the analysis of the debris An examination of the wear, of the friction coefcient and of the results of the SEM tests demonstrates clearly that the amount of debris produced from Peek with carbon bre is rather scarse.

Therefore it has been necessary to have an accurate control of the extract of the dust and to SEM end EDS test the particles taken to not incur errors due to a later pollution of the samples after extraction. Fig. 8(a) shows the stab with the debris extracted from the dry test. This particles have dimensions varying from 0.1 to 3 m. Fig. 8(b) shows the rare isolated particles that, at a high magnication, these also are shown to be accumulations of the much smaller particles (Fig. 8(c) and (d)). Fig. 9(a) shows the accumulation of the particles taken from the tests with lubrication. Fig. 9(b) and (c) shows the particles magnied. Again, in this case we see that the larger particles are composed of an accumulation of smaller particles. It is necessary to consider that the accumulation of the smaller particles is caused by the ltering process.

Fig. 7. SEM pictures of tracks on the three Disc of Peek CA (20 N, 10,000 cycles). (a) Dry conditions; (b) water lubrication; (c) human serum lubrication.

912

A. Borruto / Medical Engineering & Physics 32 (2010) 908913

Fig. 8. Debris extracted from the dry test. (a) Total particles on the stub; (b) accumulation of particles; (c and d) magnication of a single particle.

Fig. 9. (a) Debris extracted from the water and human serum lubrication test; (b and c) magnication of the particles.

4. Discussion and conclusions The Peek carbon bre material was chosen for this study because of its ability to have a low friction coefcient and for its resistance to attack by a wide range of organic and inorganic chemicals and solvents. Tests were carried out using Peek 450G, Peek CA and Peek CF compared with UHMWPE. From the wear test and from the electronic microscope (SEM) observation the following results were obtained: (1) A large quantity of debris from the UHMWPE as a conrmation of all the literature already in existence. (2) The excellent wear results of the Peek carbon bre. The author has already described in a previous work [30] the mechanism of the lubrication, linked to the wettability of the materials and regarding the coupling Pin CoCrDisc Peek carbon bre.

(3) The quantity and the dimension of the debris from the Peek carbon bre being signicantly inferior to those prostheses already in use.

We see, from a large amount of the literature, that the dimensions of the debris from UHMWPE, the material most often used for hip prostheses today, reach dimensions from 0.1 to >1000 m [31]. Furthermore, given the obvious amount of wear of this material with time, noticeable accumulations of debris are consistently found. By the wear tests and SEM tests, Peek reinforced with carbon bres demonstrates a very low wear and therefore an extremely low quantity of debris produced, in water and human serum lubrication and even under dry conditions. It is necessary to remember that the load used for the test (20 N) is a much more drastic load than the real-life conditions.

A. Borruto / Medical Engineering & Physics 32 (2010) 908913

913

The produced debris are composed of particles which have, on average, dimensions of about 0.1 m. Isolated debris particles of 3 m have also been found, but the SEM analysis proved this to be agglomerates of smaller particles. The extremely low quantity of debris produced during the tests using water and human serum as lubricant, as shown by the values of the friction coefcient, by the wear and by the evidence from the SEM tests, have a value less then 0.1 m. The few particles having larger dimensions, taken from the lter of 0.22 m, are again shown to be accumulations of much smaller particles. It can be seen that these casual accumulations are particles that have been ltered several times. To ensure that no errors are caused by an ambient contamination the particles found were subjected to microanalysis (EDS). From this study and from many other tests done, it seems clear that Peek reinforced by carbon bres is an excellent material to use for prosthetic applications in special way in the tribological coupling Peek carbon bre-alloy CoCr. Conict of interest The author declares that there is no conict of interest. References
[1] Wroblewski BM. Charnley low friction arthroplasty: review of the past, present status, and prospect for the future. Clin Orthop 1986;210:37. [2] Marks R, Allegrante JP, Ronald MacKenzie C, Lane JM. Hip fractures among the elderly: causes, consequences and control. Ageing Res Rev 2003;2:5793. [3] Green TR, Fisher J, Matthews JB, Stone MH, Ingham E. Effect of size and dose on bone resorption activity of macrophages by in vitro clinically relevant ultra high molecular weight polyethylene particles. J Biomed Mater Res (Appl Biomater) 2000;53:4907. [4] Matthews JB, Besong AA, Green TR, Stone MH, Wroblewski BM, Fisher J, et al. Evaluation of the responses of primary human peripheral blood mononuclear phagocytes to challenge with in vitro generated clinically relevant UHMWPE particles of known size and dose. J Biomed Mater Res 2000;52:296307. [5] Endo MM, Barbour PSM, Barton DC, Fisher J, Ingham E, Stone M. Comparative wear and wear debris under three different counterface conditions of crosslinked and non-crosslinked ultra high molecular weight polyethylene. Biomed Mater Eng 2001;11:2335. [6] Ingram J, Matthews JB, Tipper J, Stone M, Fisher J, Ingham E. Comparison of the biological activity of grade GUR 1120 and GUR 415HP UHMWPE wear debris. Biomed Mater Eng 2002;12:17788. [7] Green T, Fisher J, Ingham E. Polyethylene particles of a critical size are necessary for the induction of IL-6 by macrophages in vitro. In: Trans. 43rd Orthop. Res. Soc., vol. 22. 1997. p. 733. [8] Athanasou NA, Quinn J, Bulstrode CJK. Resorption of bone by inammatory cells derived from the joint capsule of hip arthroplasties. J Bone Joint Surg 1992;74B:5762.

[9] Murray DW, Rushton N. Macrophages stimulate bone resorption when they phagocytose particles. Bone Joint Surg 1990;72B:98892. [10] Amstutz HC, Campbell P, Kossovsky N, Clarke IC. Mechanism and clinical signicance of wear debris-induced osteolysis. Clin Orthop 1992;276:718. [11] Maloney WJ, Jasty M, Rosenberg A, Harris WH. Bone lysis in well-xed cemented femoral components. J Bone Joint Surg 1990;72B:96670. [12] Mirra JM, Marder RA, Amstutz HC. The pathology of failed total joint arthroplasty. Clin Orthop Relat Res 1982 Oct;170:17583. [13] Schmalzried TP, Jasty M, Harris WH. Periprosthetic bone loss in total hip arthroplasty: polyethylene wear debris and the concept of the effective joint space. J Bone Joint Surg 1992;74A:849. [14] Schmalzried TP, Kwong LM, Jasty M, Sedlacek RC, Haire TC, Oconnor DO, Bragdon CR, Kabo JM, Malcolm AJ, Harris WH. The mechanism of loosening of cemented acetabular components in total hip arthroplasty: analysis of specimens retrieved at autopsy. Clin Orthop 1992;274:6078. [15] Leinbach S, Barlow FA. 700 total hip replacements. Experience with 6 types. Clin Orthop Relat Res 1973;95(September):17492. [16] Bentley G, Dunthie RB. Comparative review of the McKee-Farrar and Charnley total hip prostheses. Clin Orthop Relat Res 1973;95(September):12742. [17] Okazaki Y, Gotoh E. Comparison of metal release from various metallic biomaterials in vitro. Biomaterials 2005;26:1121. [18] Klapperich C, Graham J, Pruitt L, Ries MD. Failure of a metal-on-metal total hip arthroplasty from progressive osteolysis. J Arthroplasty 1999;14(7). [19] Amstutz HC, Grigoris P. Metal on metal bearings in hip arthroplasty. Clin Orthop Relat Res 1996;329S:S1134. [20] Campbell P, McKellop H, Lu B, et al. Clinical wear performance of modern metalon-metal hip arthroplasties. In: Trans. 24th Ann. Meeting Society Biomat. 1998. p. 210 (Case report). [21] Doorn PF, Campbell PA, Amstutz HC. Metal versus polyethylene wear particles in total hip replacements. A review. Clin Orthop Relat Res 1996;329S:S20616. [22] Hallab NJ, Jacobs JJ, Skipor A, et al. Serum metallo protein carriers of metal in patients with total joint arthroplasty. In: Trans. 24th Ann. Meeting Society Biomat. 1998. p. 211. [23] Agins HJ, Alcock NW, Bansal M, Salvati EA, Wilson PD, Pellicci PM, et al. Metallic wear in failed titanium-alloy total hip replacements. A histological and quantitative analysis. J Bone Joint Surg 1988;70A:34756. [24] Buly RL, Huo MH, Salvati EA, Brien W, Bansai JM. Titanium wear debris in failed cemented total hip arthroplasty. An analysis of 71 cases. J Arthroplasty 1992;7(September (3)):31523. [25] Lombardi AV, Mallory TH, Vaughin And BK, Drouillard P. Aseptic loosening in total hip arthroplasty secondary to osteolysis induced by wear debris from titanium alloy modular femoral heads. J Bone Joint Surg 1989;71A:1337. [26] Salvati EA, Betts F, Doty SB. Particulate metallic debris in cemented total hip arthroplasty. Clin Orthop 1993;293:160. [27] McGee MA, Howie DW, Costi K, Haynes DR, Wildenauer CI, Pearcy MJ, et al. Implant retrieval studies of the wear and loosening of prosthetic joints: a review. Wear 2000;241:15865. [28] Patil N, Jin W, Mow CS. Polyethylene wear particle induced osteolysis in total hip replacement. Malays Orthop J 2008;2(1). [29] Tipper JL, Hatton A, Nevelos JE, Ingham E, Doyle C, Streicher R, et al. Aluminaalumina articial hip joints. Part II. Characterisation of the wear debris from in vitro hip joint simulations. Biomaterials 2002;23:34418. [30] Borruto A, Marrelli L, Palma F. The difference of material wettability as critical factor in the choice of a tribological prosthetic coupling without debris release. Tribol Lett 2005;20(September (1)):110. [31] Tipper JL, Ingham E, Hailey JL, Besong AA, Fisher J, Wroblewski BM, et al. Quantitative analysis of polyethylene wear debris, wear rate and head damage in retrieved Charnley hip prostheses. J Mater Sci: Mater Med 2000;11:11724.