Effect of head surface roughness and sterilization on wear of UHMWPE acetabular cups.

The impact of femoral head surface roughness on wear of gamma-irradiation sterilized (3 MRad in nitrogen, crosslinked) and nonsterilized (not crosslinked) UHMWPE acetabular cups has been evaluated. Gravimetric wear testing was performed in a hip joint simulator for 2 x 10(6) cycles. CoCrMo heads were used with different surface roughness (R(a) = 15 nm and R(a) = 400 nm). The surface roughness after wear test was unchanged for the roughened heads, whereas the initially smooth heads showed a few scratches. The roughened heads increased the wear of the acetabular cups 2-fold. The gamma-irradiated cups tested against rough heads underwent the highest wear. The absorption of water was highest for the gamma-irradiated cups (0.0204% compared to 0.0031% after 85 days). Raman spectroscopy showed small but significant crystallinity changes in the wear zone, where the gamma-irradiated cups with the most extensive abrasion increased in crystallinity, whereas the nonsterilized cups underwent a crystallinity decrease.

In vitro bioactivity of poly(epsilon-caprolactone)-apatite (PCL-AP) scaffolds for bone tissue engineering: the influence of the PCL/AP ratio.

Porous poly(epsilon-caprolactone) (PCL) is used as long-term bioresorbable scaffold for bone tissue engineering. The bone regeneration process can be enhanced by addition of carbonated apatites (AP). This study was aimed at evaluating the influence of the PCL/AP ratio on the in vitro degradation and bioactivity of PCL-AP composites. To this purpose, PCL-AP samples were synthesised with the following PCL/AP weight/weight ratios: 50/50, 60/40 and 75/25. Vibrational IR and Raman spectroscopies coupled to thermogravimetry (TG) and differential scanning calorimetry (DSC) were used to investigate the in vitro degradation mechanism in different media: 0.01 M NaOH solution (pH=12), saline phosphate buffer at pH 7.5 (SPB), esterase in SPB and simulated body fluid (SBF) at pH 7.5. The latter medium was used to evaluate the bioactivity of the composites. A control PCL sample was analysed before the addition of the AP component. As regards the untreated samples, the method of synthesis utilised for preparing the composite was found to enhance the crystallinity degree. The AP component revealed to be constituted of a B-type carbonated hydroxyapatite with a 3% carbonate content. After 28 days of treatment, the samples showed different degradation patterns and extents depending on the degradation medium, the starting PCL crystallinity and composite composition. Weight measurements, Raman and TG analyses revealed deposition of an apatitic phase on all the composites immersed in SBF. Therefore, all the samples displayed a good bioactivity; the sample which showed the most pronounced apatitic deposition was 50/50, i.e. that containing the highest amount of AP.

Determination of crystallinity and crystal structure of Hylamer polyethylene after in vivo wear.

Hylamer polyethylene is a crystalline form of polyethylene of 70% crystallinity whereas conventional polyethylene (PE) has 50% crystallinity. Crystallinity is the percentage by weight of the crystalline phase present in the whole polymer, which comprises both amorphous and crystalline phases. Clinical experience has shown that Hylamer components used in joint prostheses, if sterilized by gamma rays in the presence of oxygen, are easily affected by wear, which leads to osteolysis. The authors have analyzed the crystallinity of polyethylene liners removed from seven patients who had received Hylamer polyethylene implants sterilized by gamma rays in air and had suffered prosthetic loosening, using Raman spectroscopy coupled with partial least squares (PLS) analysis. The results have been compared to those of two controls who had received Hylamer polyethylene implants sterilized by gamma irradiation in a nitrogen atmosphere. The crystal structure of wear particles released into the tissues from the Hylamer liners sterilized by gamma rays in air is also studied. The materials undergoing two different types of sterilization methods show different crystallinity values (71.50 vs. 69.43), but the crystallinity do not change according to wear (worn and unworn liner region). Both monoclinic and orthorhombic phases are present in the liner, while in wear debris prevalently monoclinic crystals are found in both types of sterilized liners. Different crystallinity rates can explain different wear rates observed in vivo.

Advanced nanocomposite materials for orthopaedic applications. I. A long-term in vitro wear study of zirconia-toughened alumina.

The use of ceramic-on-ceramic (alumina- and zirconia-based) couplings in hip joint prostheses has been reported to produce lower wear rates than other combinations (i.e., metal-on-polyethylene and ceramic-on-polyethylene). The addition of zirconia into an alumina matrix (zirconia-toughened alumina, ZTA) has been reported to result in an enhancement of flexural strength, fracture toughness, and fatigue resistance. The development of new processing routes in nonaqueous media has allowed to obtain high-density ZTA nanocomposites with a very homogeneous microstructure and a significantly smaller and narrower particle-size distribution of zirconia than conventional powder mixing methods. The aim of the present study was to set up and validate a new ZTA nanocomposite by testing its biocompatibility and wear behavior in a hip-joint simulator in comparison with commercial alumina and experimental alumina specimens. The primary osteoblast proliferation onto ZTA nanocomposite samples was found to be not significantly different from that onto commercial alumina samples. After 7 million cycles, no significant differences were observed between the wear behaviors of the three sets of cups. In this light, it can be affirmed that ZTA nanocomposite materials can offer the option of improving the lifetime and reliability of ceramic joint prostheses.

Isolation and characterization of wear debris generated in patients wearing polyethylene Hylamer inserts, gamma irradiated in air.

Hylamer polyethylene was used in the early 1990s to make hip-joint components. Clinical experience has shown that these components, if sterilized by gamma rays in the presence of oxygen, are easily affected by wear, which then leads to osteolysis. The authors analyzed polyethylene wear particles in seven patients who had received Hylamer polyethylene implants sterilized by gamma rays in air and had suffered prosthetic loosening. The results were compared to those of six controls, who had received traditional polyethylene implants, sterilized by the same method. The frequency distribution of globular and fibrillar particles was similar in both groups (38.5% in Hylamer, 45.2% in controls). The globular particles in the Hylamer samples had a mean area of 0.12 microm2, which was significantly lesser than that of the controls (0.30 microm2). The width of fibrillar particles in the Hylamer samples was significantly lesser than that of the controls. Therefore, the two materials, despite undergoing the same type of sterilization, produced different types of wear, due to their different properties. In conclusion, the difference in the morphology of Hylamer polyethylene wear particles in comparison with PCA might have caused a more intensive biological response, early and massive osteolysis, and therefore, early loosening.

Comparison between the in vitro surface transformations of AP40 and RKKP bioactive glasses.

Two bioactive silica-phosphate glasses, AP40 and RKKP, were compared in their behaviour in simulated biological environment. Their chemical composition is practically identical, except that RKKP contains small amounts of amphoteric network-former oxides Ta2O5 and La2O3 (composition in wt% for AP40: beta-Ca3(PO4)2 24.50, SiO2 44.30, CaO 18.60, Na2O 4.60, K2O 0.19, MgO 2.82, CaF2 4.99; RKKP: beta-Ca3(PO4)2 24.23, SiO2 43.82, CaO 18.40, Na2O 4.55, K2O 0.19, MgO 2.79, CaF2 4.94, Ta2O5 0.99, La2O3 0.09). Previous investigations showed a better performance in osteopenic bone for RKKP. To gain more insight into these differences in biological behaviour, the in vitro bioactivity of the glasses was studied by treatment with a continuously replenished Hanks' Balanced Salt Solution (HBSS). The glasses were examined before and after HBSS treatment for 20 and 40 days by X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM), X-ray Energy Dispersion (EDX), Raman and IR vibrational spectroscopies. Some slight but notable differences between the two glasses were observed after HBSS treatment. IR and EDX analyses showed that deposits formed on both glasses were composed of a calcium deficient carbonate-apatite; however, the layer formed on RKKP glass was found to be slightly more calcium deficient and thinner. EDX analysis evidenced the presence of a small percentage of F- ions only in the layers formed on the RKKP samples. The differences disclosed, although slight, can contribute to the understanding of the different biological behaviour previously observed.

Effects of the sterilisation method on the wear of UHMWPE acetabular cups tested in a hip joint simulator.

Ultra-high molecular-weight-polyethylene is the most commonly used bearing material in total joint replacement. Wear of polyethylene is a Serious Clinical problem that limits the longevity of orthopaedic implants. Information on degradative changes in the material properties and on the methods used for the sterilisation of polyethylene may help in the selection process of orthopaedic implants with the best wear resistance. This study was performed to investigate the effects of the sterilisation method (gamma irradiation and ethylene oxide treatment) on the wear and on the changes in physical properties of polyethylene acetabular cups. At this purpose, gamma-sterilised and ethylene oxide (EtO)-sterilised acetabular cups were tested against CoCr femoral heads in a hip joint simulator run for 5 million cycles in bovine calf serum. The crystallinity of the cups was evaluated by micro-Raman spectroscopy as a function of the inner surface position. The partial least square calibration was used to correlate the Raman spectra with the crystallinity of the polymer measured by differential scanning calorimetry. The analysis performed on soak control acetabular cups demonstrated that the gamma-sterilised cups are significantly more crystalline than the EtO-sterilised ones. The mean crystallinity values obtained for the gamma-sterilised and EtO-sterilised soak control cups were 65.0% and 63.4%, respectively. Weight loss measurements revealed that the gamma-sterilised acetabular cups exhibited a lower wear rate than that by EtO-sterilised. Thc Raman results obtained on gamma-sterilised and EtO-sterilised acetabular cups showed that the changes in surface crystallinity were mainly caused by irradiation rather than by the mechanical friction during the in vitro tests.

Study of the vibrational spectrum of cuprorivaite.

In this research, after tracing a history of the pigment, the preparation and analysis of samples of Egyptian blue have been reported. The main reactions taking place during its preparation are indicated. X-ray diffractions show that, starting from mixtures of precursors with stoichiometric composition, the product is practically only cuprorivaite. The kind of flux and cristallinity of silica does not seem determining factors for the pigment formation. Infrared and Raman spectra and an assignment of the bands are reported. Impurities ascertained are discussed on the basis on the data available.

Raman spectroscopy in the study of biocompatibility.

This review deals with the application of Raman spectroscopy to the study of the biocompatibility of orthopaedic and ophthalmological materials and includes an introduction, a brief theory on the fundamental concepts of the technique, a description of the method and of the traditional and non-traditional instrumentation and a brief treatment of the surface properties of the different classes of materials. In the orthopaedic field, Raman studies on the structures of glasses, ceramic materials, carbon fibres and polymers before and after implantation are reviewed, particularly as far as structural modifications at the biomaterial-tissues interface are concerned. In the ophthalmological field, the chemical biocompatibility of hydrophobic and hydrophilic polymers for intraocular and intrastromal implants and for soft contact lenses is considered with respect to the presence of monomeric reactive centres in hydrophobic materials and the water amount in hydrophilic ones. The progress of the multichannel Raman technique for 'in-vivo' measurements is also described.

Raman spectroscopy for the study of porous composite alumina coating.

A new acetabular cup prosthesis made of alumina and bioactive glass was studied and evaluated using nondestructive and noninvasive Raman laser spectroscopy. The prosthesis consists of an alumina socket coated with a double layer of alumina beads bonded to the prosthesis with a layer of glass. Raman spectroscopy showed that both the socket and the beads are composed of alpha-Al2O3 (corundum), while the bioactive glass (alkaline and alkaline earth alumosilicate with a small quantity of zirconium oxide) showed this to have an intermediate structure between that of vitreous silica and that of the alkaline and alkaline earth disilicate glasses. The Raman spectra of the contact surfaces between the bioactive glass and the alumina of the assembled prosthesis and of an alumina disk coated with the same glass showed the presence of new bands which may be correlated with a chemical interaction between the components of the prosthesis.

Molecular interactions between nucleic acids and antitumor substances by Raman and NMR spectroscopy.

1-Methyladenosine (1-MeAdo) and protonated 1-Methyladenosine (1-MeAdo.H+) were chosen as a model to study the molecular interactions between the carcinogen dimethylsulphate (DMS) and the base adenine, and the interactions between the antitumoral electrophilic cis-diamminedichlorophatinum (II) (cis-Pt) and the methylation product of the base, respectively. Raman and multinuclear NMR studies show the molecular perturbations caused by the carcinogen on the base and those of the antitumoral substance on the reaction product base-carcinogen.