UHMWPE-based composites obtained by mechanical activation and hot pressing and filled with ceramic particles can be used as a biocompatible material for the replacement of cartilage defects. Modern biocompatible materials, used for joint implantates, must have high impact strength, wear-resistance and corrosion resistance.
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Original Title
Biocompatible Polymer Composites Based on Ultrahigh Molecular Weight
UHMWPE-based composites obtained by mechanical activation and hot pressing and filled with ceramic particles can be used as a biocompatible material for the replacement of cartilage defects. Modern biocompatible materials, used for joint implantates, must have high impact strength, wear-resistance and corrosion resistance.
UHMWPE-based composites obtained by mechanical activation and hot pressing and filled with ceramic particles can be used as a biocompatible material for the replacement of cartilage defects. Modern biocompatible materials, used for joint implantates, must have high impact strength, wear-resistance and corrosion resistance.
Biocompatible polymer composites based on ultrahigh molecular weight
polyethylene perspective for cartilage defects replacement
F.S. Senatov a , M.V. Gorshenkov a, , S.D. Kaloshkin a , V.V. Tcherdyntsev a , N.Yu. Anisimova b , A.N. Kopylov b , M.V. Kiselevsky b a National University of Science and Technology MISIS, Moscow, Russian Federation b N.N. Blokhin Russian Cancer Research Center of RAMS, Moscow, Russian Federation a r t i c l e i n f o Article history: Available online 22 October 2012 Keywords: UHMWPE Composite Biomaterial Wear Mechanical activation a b s t r a c t The purpose of this study was to evaluate mechanical properties, microstructure and biocompatibility of nano-compounds obtained by mechanical activation of UHMWPE powder and several types of particulate llers in a planetary ball mill. The effect of particle shape and concentration of Al 2 O 3 on properties of the composite was investigated. The effectiveness of reinforcing a polyethylene matrix by mechanoactivated alumina in the form of nanopowder or microspheres was shown. Reinforcing of the polymer by nanopar- ticles signicantly improves wear-resistance. No signs of blood serum brin deposition on the surface of the samples were observed. Also no signs of pathological changes in physiology or anatomy were noticed on the animals with implanted samples. UHMWPE-based composites obtained by mechanical activation and hot pressing and lled with ceramic particles can be used as a biocompatible material for the replace- ment of cartilage. 2012 Elsevier B.V. All rights reserved. 1. Introduction The development of synthetic implantates to replace cartilage defects, for example, the replacement of joints, is an actual prob- lem of modern medicine. Modern biocompatible materials, used for joint implantates, must have high impact strength, wear-resis- tance and corrosion resistance. Ultrahigh molecular weight poly- ethylene (UHMWPE) is used in joint replacement prostheses because of its excellent properties of bio-compatibility, chemical stability, and low friction coefcient. To improve the functional characteristics, such as strength, polymers may be reinforced with hard inorganic llers [1]. Ultrane llers, including nanosized par- ticles, are of particular interest. It was shown [2] that the use of nanosized powders as llers for polymer matrices can signicantly enhance the mechanical, tribological and other functional charac- teristics of polymer composites. Currently, for obtaining composite polymeric materials mechanical activation of polymer and ller is widely used for pre-processing of raw materials. Mechanical activation increases the adhesion of the ller to the matrix [3,4]. Mechanical activation also helps to reduce the particle size of polymers and in some cases, may be accompanied by rupture of polymer chains, the transformation of the crystalline and amorphous structures, the appearance of oriented amorphous regions [59]. As noted in [10], brous form of UHMWPE particles increases the contact area of the particles during compaction and gets a denser structure than in the case of spherical particles. Therefore in this paper, we pro- pose to make a preliminary mechanical treatment of UHMWPE powder and several types of particulate llers in a planetary ball mill and evaluate microstructure and biocompatibility of obtained nano-compounds. 2. Materials and experiment UHMWPE powder Polinit-2 (OJSC Kazanorgsintez, Russia) with molecular weight 2 . 10 6 g/mol was used as the polymer matrix, Al 2 O 3 was used as a strength- ening phase in the form of nanopowder with 50 nm particles (JSC Siberian Chem- ical Combine, obtained by plasma method) or microspheres with size 1000 nm (National University of Science and Technology MISIS, obtained by pyrolysis of ultrasonic aerosols). The rst stage of the process of polymer composite obtaining was mechanical activation of UHMWPE powder and alumina with various ratios in a planetary ball mill Fritsch Pulverisette 5 (Germany), equipped with agate grind- ing bowl (500 ml) and alumina grinding balls (10 mm). The grinding bowl lling with grinding bodies was 45 vol.%. Based on changes of morphology of the particles of UHMWPE during mechanical activation the optimal duration was chosen. Hot pressing of the mechanoactivated mixture was performed using a hydraulic thermo press MEGA KSC-10A (Spain) on the following mode: compression load 76 MPa with heating for 1.5 h from 20 C to 160 C, holding at this temperature for 30 min, followed by hot pressing with a load of 80 MPa and subsequent cooling un- der pressure. Study of the shape and size of the powder particles after the mechanical activa- tions was performed with a scanning electron microscope JEOL JSM-6610LV (accel- erating voltage 20 kV). For studying of non-conductive polymeric samples, the surface of polymer composite samples was covered with a layer of platinum (10 20 nm) by Auto Fine Coater JFC-1600 (Jeol, USA). 0925-8388/$ - see front matter 2012 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.jallcom.2012.10.014
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E-mail address: mvg@misis.ru (M.V. Gorshenkov). Journal of Alloys and Compounds 586 (2014) S544S547 Contents lists available at SciVerse ScienceDirect Journal of Alloys and Compounds j our nal homepage: www. el sevi er . com/ l ocat e/ j al com To study the effect of particle shape and concentration of Al 2 O 3 on properties of the composite microindentation, the determination of tensile strength and impact strength were used. Microhardness measurements were performed using microind- enter CSM Micro Indentation (CSM Instruments SA, Switzerland) with a load of 100 mN (the maximum depth of 200 microns, the depth resolution 0.3 nm). Mea- surement of tensile strength, yield strength, elongation and Youngs modulus of the specimen in tension was carried out according to Russian measurement stan- dards (GOST11262-80) on Instron 150LX (USA) with the strain-rate 10 mm/min using a rectangular sample measuring 60 10 2 mm. Toughness was determined on samples of size 80 10 4 mm with a V-notch Charpy method in accordance with Russian measurement standards (GOST 4647-80) on POE Instron 2000 (USA) with a reserve of the pendulum energy 50 J. Tribological tests were carried out in the regime of friction in distilled water by pin-on-disk method on CETR-UMT-3 (Bruker AXS, Switzerland). Form of the test sample: pin with a diameter of 6.3 mm and a length of 10 mm; counter-body: steel 45; sliding velocity 200 rpm, normal load 5 MPa, the test time 4 h, the length of fric- tion 4 km, temperature 27 C. These parameters were similar to standard parame- ters of cartilage friction tests in some other works [1113]. Biocompatibility of the samples (Al 2 O 3 /UHMWPE-0.50.5) was researched in vitro and in vivo. Samples were sterilized in the 96% ethanol during 24 h and then were dried in sterile conditions. We made our research on mouse bone-marrow derived MSC (mesenchymal stem cells) and human broblasts. We took C57/BlackB mouse bone marrow as a source of MSC. Cell concentration was 440 10 5 cell/ml. MSC were placed on the surface of a sample, and cultivated in cultural medium (RPMI-1640 (Sigma, USA) containing 10% heat-inactivated (56 C, 30 min) fetal bo- vine serum (Hyclone Laboratories, Logan, UK), 2 mM L-glutamine and antibiotics (100 lg/ml penicillin sodium salt and 100 lg/ml streptomycin sulfate (Sigma, USA)) in 37 C, 5% CO 2 during 30 days xed by May Grunwald giemsa and staining by hematoxylineosin [14]. For evaluation of brin dropping we took citrated healthy donor blood serum and extracted plasma on the surface of the sample. After moistening of the samples, we incubated them in blood serum during ve days, in 37 C and 5% CO 2 . In vivo we researched sample toxicity in six mice C57/Black, they were narco- tized by ether, skin on their back was dissected and 0.6 0.6 samples were im- planted subcutaneously into 1 1 area. After 60 days mice were euthanized and samples were taken out. Also connective tissue surrounding the sample was taken out too. Samples were xed and stained. Biocompatibility features were evaluated with light reecting microscopy, with AxioScop 40 microscope (Zeiss, Germany). 3. Results and discussion It was shown [15] that due to the high melt viscosity UHMWPE particles can retain the shape of the initial particles after thermo pressing. Owing to this fact the microstructure of UHMWPE can be regarded as a polycrystalline structure in metals, where grains are the particles of UHMWPE. An example of the UHMWPE struc- ture is shown at the Fig. 1. Mechanical activation in certain modes can contribute to obtaining a more dense structure of the compos- ite by changing the shape of the original UHMWPE particles. The hard reinforcing particles at a rate much smaller than the size of the original polymer particles are distributed on the surface of UHMWPE only. Therefore, the hard particles reinforce only the grains boundary and do not reinforce the body of the UHMWPE particle as it shown at Figs. 2 and 3. The homogeneous tension composite without necking associ- ated with high molecular weight of UHMWPE, while stretching the compacted samples containing different amounts of micro- spheres and ultrane alumina powder, is observed, and it conrms the results of [16]. Both strength and Youngs modulus increase was determined after addition of a ller in UHMWPE. According to [17], reinforcing of the material by mechanically activated dis- persed llers due to the retention of oxide particles in a polymer matrix by van der Waals forces and hydrogen bonds with the molecular chains of UHMWPE. In accordance with previous study [18], the optimal polymer lling was 3 wt.% of ceramic particles. Increasing of ultimate stress limit by 38% and Youngs modulus in 2.85 times was achieved by lling UHMWPE with alumina particles (Table 1). There is less yield strength in the case of lling the polymer matrix by micro- spheres. This fact can be explained by a smaller surface area (12 m 2 /g) and spherical shape of particles, which can leave the ma- trix under the load. Nanoparticles also have a greater surface area (55 m 2 /g) and irregular shape, which increases the contact area with the polymer matrix and improves the adhesion. Such behav- ior of mechanical properties of polymeric composites is conven- tional, reinforcing of polymer matrix with hard particles (including nanosized powders) results in an increase of elasticity modules and yield stress [19]. Very often this gain in elasticity Fig. 1. SEM micrograph of quasibrittle fracture surface of UHMWPE-based composite. Fig. 2. Grain boundary of UHMWPE-based composite reinforced by Al 2 O 3 microspheres. Fig. 3. Grain boundary of UHMWPE-based composite reinforced by Al 2 O 3 nanoparticles. F.S. Senatov et al. / Journal of Alloys and Compounds 586 (2014) S544S547 S545 modulus and yield stress is desirable, because in most cases these properties dene the stress limit of material under loading and it does not undergo plastic deformation. The destruction of UHMWPE, as other amorphouscrystalline polymers, carried out by spreading of microcracks. Hard ceramic particles inhibit the spreading of cracks that leads to an increase of elongation. As a consequence, there was a signicant increase in the impact strength of the composite. Positive effect on the im- pact strength of the composite states in the case of lling by micro- spheres is higher than in the case of lling by nanopowders, because microspheres behave like closed pores. The ratio of the elastic modulus of the nanocomposite to the elastic modulus of bone tissue is 1:13 and 1:14 versus 1:21 in the case of unlled UHMWPE, which is especially important be- cause a large difference of the elastic modulus can lead to micro- strain on the border of the prosthesis-bone and lead to degradation of the implantate. The friction coefcient has decreased in 2.5 times after 4 h of friction in case of composite with microspheres in comparison with pure UHMWPE, but increased in 1.4 times in the case of com- posite with nanoparticles as it is shown in Fig. 4. But wear-resis- tance has decreased in case of lling polymer matrix with microspheres (Fig. 5). This can be attributed to the larger size of microparticles compared with the nanoparticles and, most impor- tantly, their spherical shape. Consequently, the ceramic particles more active crumble from the polymer matrix during the loading, leading to intensive wear of the composite body and counter-body. Based on the tribological properties composites with nanoparticles are preferred, because of higher wear-resistance. This fact is very important for using this material in joint replacement operations. We did not observed signs of blood serum brin deposition on the surface of the samples. That is a good feature of material for cartilage defects replacement, because brin dropping with follow- ing calcication can cause decreasing of the smoothness of the joint surface, pain and loss of function. Studying the surface of samples showed absence of MSC monolayer on the surface, we no- ticed only single adhered cells (04 cells/sm 2 ) on the surface of the tested samples after cocultivation with human broblasts (Fig. 6). No signs of pathological changes in physiology or anatomy were noticed on the animals with implanted samples. Studying the microstructure showed absence of signs of colonization by recipi- ent cells on the surface. The implantate for replacement cartilage defects must not adhere cells of recipient tissues on its surface be- cause this will result in decreasing its quality and characteristics. So that characterizes Al 2 O 3 /UHMWPE composite as a very perspec- tive for using as a implantate. 4. Conclusions As a result of the investigation it was shown that UHMWPE- based composites lled by ceramic particles with better physicalmechanical properties can be obtained by mechanical activation and hot pressing, and can be used as a biocompatible material for the replacement of cartilage. Table 1 Comparison of the values of various parameters for the pure UHMWPE and the composite material with 3 wt.% Al 2 O 3 of different types. Ultimate strength (MPa) Youngs modulus (MPa) E material /E bone Yield strength (MPa) Elongation (%) Hardness (MPa) Impact elasticity (kJ/m 2 ) UHMWPE 31.9 0.97 1:21 22.0 120 50 50 Composite with nanoparticles 40.0 1.53 1:13 26.5 160 109 63 Composite with microspheres 36.0 1.4 1:14 24.5 150 100 73 Fig. 4. Friction coefcients of UHMWPE and UHMWPE-based composites. Fig. 6. UHMWPE-based composite surface with single adhered cells (04 cells/sm 2 ) after cocultivation with human broblasts. Fig. 5. Wear of UHMWPE and UHMWPE-based composites. S546 F.S. Senatov et al. / Journal of Alloys and Compounds 586 (2014) S544S547 According to the study of the complex mechanical properties of composite materials based on UHMWPE, the effectiveness of rein- forcing a polyethylene matrix by mechanoactivated alumina in the form of nanopowder or microspheres was shown. Effect of micro- spheres on the mechanical properties of the composite is compara- ble to the effect of nanopowder, but the reinforcing of the polymer matrix occurs to a much lesser extent, due to the smaller surface area because of the spherical shape and smaller surface area. Be- cause of this fact wear of samples with microspheres is much more intensive. Therefore, the composites with nanoparticles are prefer- able to use as implantates for replacement cartilage defects. References [1] N.N. Mallikarjuna, A. Venkataraman, T.M. Aminabhavi, J. Appl. Polym. Sci. 94 (6) (2004) 25512554. [2] Mahfuz Hassan, S. Islam Muhammad, K. Rangari Vijaya, et al., Composites 35 (68) (2004) 543550. [3] G. Wang, Y. Chen, Q. Wang, J. Polym. Sci. B 46 (8) (2008) 807817. [4] H. Huang, J. Appl. Polym. Sci. 74 (6) (1999) 14591464. [5] H. Huang, J. Appl. Polym. Sci. 78 (11) (2000) 20162024. [6] M. Stranz, U. Koster, F. Katzenberg, J. Metastab. Nanocryst. Mater. 2425 (2005) 463466. [7] J. Fonta, J. 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