AIMTo investigate osteoconductive and antimicrobial properties of a titanium-copper-nitride (TiCuN) film and an additional BONIT® coating on titanium substrates.METHODSFor micro-structuring, the surface of titanium test samples was modified by titanium plasma spray (TPS). On the TPS-coated samples, the TiCuN layer was deposited by physical vapor deposition. The BONIT® layer was coated electrochemically. The concentration of copper ions released from TiCuN films was measured by atomic absorption spectrometry. MG-63 osteoblasts on TiCuN and BONIT® were analyzed for cell adhesion, viability and spreading. In parallel, Staphylococcus epidermidis (S. epidermidis) were cultivated on the samples and planktonic and biofilm-bound bacteria were quantified by counting of the colony-forming units.RESULTSField emission scanning electron microscopy (FESEM) revealed rough surfaces for TPS and TiCuN and a special crystalline surface structure on TiCuN + BONIT®. TiCuN released high amounts of copper quickly within 24 h. These release dynamics were accompanied by complete growth inhibition of bacteria and after 2 d, no planktonic or adherent S. epidermidis were found on these samples. On the other hand viability of MG-63 cells was impaired during direct cultivation on the samples within 24 h. However, high cell colonization could be found after a 24 h pre-incubation step in cell culture medium simulating the in vivo dynamics closer. On pre-incubated TiCuN, the osteoblasts span the ridges and demonstrate a flattened, well-spread phenotype. The additional BONIT®coating reduced the copper release of the TiCuN layer significantly and showed a positive effect on the initial cell adhesion.CONCLUSIONThe TiCuNcoating inhibits the formation of bacterial biofilms on orthopedic implants by influencing the “race for the surface” to the advantage of osteoblasts.
The formation of nanosized crystallites of magnetite, Fe 3 O 4 , by heat treatment of a glass containing iron oxide was investigated. The magnetic properties of the glass ceramic manufactured strongly depend on the heat treatment conditions. The evolution of size distribution and volume fraction of the nanocrystallites formed was studied by small-angle x-ray scattering ͑SAXS͒. The size distribution of the nanocrystalline phase turned out to show bimodal shape. The possibility of magnetic contrast variation offered by small-angle neutron scattering ͑SANS͒ was utilized in order to distinguish the small-angle scattering of magnetite from the scattering contributions of nonmagnetic iron containing crystallites that can additionally be formed during the heat treatment. The results obtained reveal that both size grades of particles observed in the size distribution are superparamagnetic consisting of magnetite. The evolution of the volume fraction of magnetite in dependence on the heat treatment was found to be correlated with the magnitude of the specific saturation magnetization of the glass ceramic. The volume size distributions derived from magnetic SANS revealed peaks at smaller radii in relation to those from nuclear SANS and SAXS data. Therefore, the existence of a nonmagnetic surface layer is suggested that surrounds the magnetically active core of the magnetite nanocrystals.
By solving a set of differential rate equations the precipitation of AgCl clusters in the glass system 30Na2O–70B2O3/AgCl has been modeled. Using a parallel algorithm on a CRAY T3E it was possible to investigate the process of homogeneous nucleation and growth, which starts after an initial quench of the glass melt into the miscibility gap of the phase diagram, even including the onset of the Ostwald ripening stage. The method has been applied to the examination of the intermediate stage between independent growth and Ostwald ripening. In particular, the influence of the interfacial tension and the temperature of heat treatment on the evolution of the silver halide clusters has been investigated. The results are in qualitative agreement with those of in situ measurements of small-angle x-ray scattering. Furthermore, general consequences for the interpretation of experimental data on nucleation and growth have been derived.
The kinetics of the primary phase formation in a glass ceramic base glass near the cordierite composition in the MgO–Al2O3–SiO2 system, with additions of ZrO2 and TiO2 as nucleating agents, have been investigated by combining different small‐angle scattering techniques. Phase formation in the base glass heated isothermally at 1093 K has been studied in order to elucidate the structural processes that take place during controlled nucleation before volume crystallization begins. Complementary results of X‐ray diffraction, transmission electron microscopy and electron microprobe analysis reveal that in the final stages of annealing, different crystalline phases, which are dispersed in the residual glassy phase, are developed. The largest particles have sizes of the order of several hundreds of nanometers and consist of magnesium petalite as well as a high‐quartz solid solution. Besides these crystals, two populations of smaller particles, the sizes of which can be resolved by small‐angle scattering, were detected and found to be enriched with TiO2 and/or ZrO2. The growth of particles of intermediate size was studied in situ. The radius, R, of each of these particles increases with increasing treatment time, t, according to the power law R∝t1/2, indicating diffusion‐limited independent growth. The scattering patterns are modified by diffusion zones surrounding the growing particles. The characteristics of the diffusion zones are evaluated by fitting appropriate model scattering curves to the experimental scattering data. The structural arrangement of the Ti and Zr ions was studied by contrast variation with the help of anomalous small‐angle X‐ray scattering and small‐angle neutron scattering. As revealed by the contrast variation experiments, Ti ions are concentrated in the interface between the intermediate‐sized particles and the glass matrix, whereas Zr is homogeneously distributed in these particles. Additionally, the Zr ions participate in the formation of the smallest particles, which are crystallites enriched with ZrO2. Finally, the catalyzing effect of TiO2 and ZrO2 on the nucleation and volume crystallization of the glass ceramic is discussed.
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