An innovative technique to simply fabricate ZrO2-HA-TiO2 nanostructured layers.

For the first time, ZrO2-HA-TiO2 layers were synthesized through EPD-Enhanced MAO (EEMAO) technique in only one step where no supplementary treatment was required. SEM, XRD, EDX, and XPS techniques were employed to propose a correlation between the growth parameters and the physical and chemical properties of the layers. The layers revealed a porous structure where applying higher voltages and/or utilizing higher concentrated electrolytes resulted in formation of wider pores and increasing the zirconium concentration in the layers; meanwhile, prolonging the growth time had the same effects. The layers mainly consisted of anatase, hydroxyapatite, monoclinic ZrO2, and tetragonal ZrO2 phases. Increasing the voltage, electrolyte concentration, and time, hydroxyapatite as well as tetragonal ZrO2 was decomposed to α-TCP, monoclinic ZrO2, and ZrO. The nanosized zirconia particles (d = 20-60 nm) were further accumulated on the vicinity of the layers when thicker electrolytes were utilized or higher voltages were applied. Emphasizing on the chemical and electrochemical foundations, a probable formation mechanism was finally put forward.

Aging effect on the phase evolution of water-based sol-gel hydroxyapatite.

In a number of recent reports on the synthesis of sol-gel hydroxyapatite, aging of the precursor solution has been found to be critical in developing an apatitic phase. Critical aging time is required to complete reaction between Ca and P molecular precursors to form a desired intermediate complex that permits a further transformation to apatite phase under appropriate thermal treatment. In this investigation, we employed a water-based sol-gel process recently developed to fabricate hydroxyapatite at relatively low temperatures. The aging effect on apatite formation was systematically studied in terms of aging time and temperature. Experimental results show that the aging time is considerably reduced as aging temperature rises. Long-term thermal aging was unfavorable for apatite formation. The optimal aging parameters for apatite formation were experimentally determined, which was further consolidated into a phase evolution map. Aging kinetic was investigated by monitoring the variation of solution pH, following the determination of an apparent activation energy, which has a value as high as 10.35 kcal/mol, for the chemical reaction occurring upon aging. Optimal solution chemistry was elucidated based on the corresponding phase evolution map.

In-vitro forming of calcium phosphate layer on sol-gel hydroxyapatite-coated metal substrates.

In-vitro deposition of calcium phosphate layer (CPL) on metallic substrate requires special surface preparation in order to provide an interfacial bond. In this work 316 stainless steel surface is modified through deposition of a thin film ( approximately 0.5 microm) of sol-gel hydroxyapatite (SG-HA). This well-bonded film acts as an intermediary and nucleation surface of the CPL film. The SG-HA films were annealed at 375 degrees C (samples coded 375-ACS) and 400 degrees C (400-ACS) to achieve different crystallinity of the films, and thus to affect and study the CPL nucleation process. The CPL growth was investigated in terms of deposition kinetics and microstructural development. A deposition rate of dense CPL of about 0.43 microm/day was achieved on the crystallized film of 400-ACS, and 0.22 microm/day of porous CPL on amorphous 375-ACS. A compositional variation of Ca/P ratio across the CPL film thickness (400-ACS) was observed. Lower Ca/P ratio of 1.2 was detected near the substrate-CPL interface and about 1.5 near the solution-CPL interface. Infrared analysis showed the CPL to be of apatitic calcium-deficient structure. Kinetic model explaining the advancement of the CPL upon the in-vitro immersion is proposed.

Effect of hydrolysis on the phase evolution of water-based sol-gel hydroxyapatite and its application to bioactive coatings.

In a previous report, we demonstrated a successful synthesis of crystalline hydroxyapatite (HA) through the use of a water-based sol-gel process. It was shown that the apatite can be obtained at temperatures generally below 400 degrees C, providing a great advantage for practical bioactive coating purposes. The influence of hydrolysis of phosphorus sol solution on the phase evolution of the resulting HA is the focus of this investigation. Experimental results show that, in the absence of acid catalyst, a long-term hydrolysis, i.e. >4 h, is required for better evolution of apatitic phase. Such a phase evolution is mainly attributed to an increased concentration of apatitic phase, rather than improved crystallinity in the calcined gels. With the aid of acid catalyst, we found that a well-crystalline HA can be synthesized over a time period shorter by 2-3 orders of magnitude than those without catalyst, i.e. a few minutes. In almost all cases, a small amount of tricalcium phosphate (TCP) was detected, which may be explainable by the formation of oligomeric derivatives of the phosphorus sol during synthesis, where calcium phosphate derivatives with lower Ca/P ratio than stoichiometry can be developed. By selecting an optimal sol as a dipping source, highly-porous dental root specimens were coated and a thin, dense, adhesive (upon finger-nail scratching test) coating was achieved after calcinations at 375 degrees C. An in vitro test also shows a bioactive character of the coating.

Water-based sol-gel synthesis of hydroxyapatite: process development.

Hydroxyapatite (HA) ceramics were synthesized using a sol-gel route with triethyl phosphite and calcium nitrate as phosphorus and calcium precursors, respectively. Two solvents, water and anhydrous ethanol, were used as diluting media for HA sol preparation. The sols were stable and no gelling occurred in ambient environment for over 5 days. The sols became a white gel only after removal of the solvents at 60 degrees C. X-ray diffraction showed that apatitic structure first appeared at a temperature as low as 350 degrees C. The crystal size and the HA content in both gels increase with increasing calcination temperature. The type of initial diluting media (i.e., water vs. anhydrous ethanol) did not affect the microstructural evolution and crystallinity of the resulting HA ceramic. The ethanol-based sol dip-coated onto a Ti substrate, followed by calcination at 450 degrees C, was found to be porous with pore size ranging from 0.3 to 1 microm. This morphology is beneficial to the circulation of physiological fluid when the coating is used for biomedical applications. The satisfactory adhesion between the coating and substrate suggests its suitability for load-bearing uses.

Development of plasma-sprayed bioceramic coatings with bond coats based on titania and zirconia.

Bond coats for plasma-sprayed hydroxyapatite (HAp) coatings on Ti-6A1-4V hip endoprotheses are being developed for improved in vivo performance. Bond coat powders consisting of (i) CaO-stabilized zirconia, (ii) a eutectic composition of titania and non-stabilized zirconia, and (iii) titania were applied by atmospheric plasma spraying (APS) to Ti-6A1-4V-coupons and 100 microm-thick Ti-6A1-4V foils. Subsequently, a thick layer of HAp was sprayed onto the thin bond coats. Peel tests on Ti-6A1-4V foil/bond coat/HAp top coat assemblies revealed that titania and titania/ zirconia bond coats increased the peel adhesion strength in a statistically significant way from 22 N m(-1) (HAp without a bond coat) to >42 and 32 N m(-1), respectively. Microstructural investigations by SEM on cross-sections of coatings leached in simulated body fluid for up to 28 days led to the conclusion that the chemically very stable bond coats act as an improved chemical barrier against in vivo release of metal ions from the implant, as well as an improved adhesive bond by development of very thin well-adhering reaction layers, presumbly composed of perovskite, calcium dititanate, and/or calcium zirconate.

Adhesion of thermally sprayed hydroxyapatite-bond-coat systems measured by a novel peel test.

Ti6Al4V foils, 100 microm thick, were coated with thin (10-15 microm) bond coats based on titania and zirconia, and subsequently coated with a thick (100-120 microm) hydroxyapatite layer, using atmospheric plasma spraying. Peel adhesion tests of the coating systems performed on the foils showed that titania, and mixed titania/non-stabilized zirconia bond coats improved the adhesion of the ceramic layers to the metallic substrate in a statistically significant way, while a partially CaO-stabilized zirconia bond coat led to a decrease of the peel adhesion strength when compared to hydroxyapatite coatings without a bond coat.

Novel fracture toughness test using a notchless triangular prism (NTP) specimen.

The aim of this study was to develop and validate a new method for determining the fracture toughness of materials and adhesive interfaces. The new test specimen is a notchless triangular prism (NTP) which, when placed in the testing holder, achieves a configuration similar to that of the standard chevron-notched short rod (CNSR) specimen. It can be cast, ground, or simply machined easily and reproducibly without cutting an initial notch. Finite element analysis of a modeled NTP specimen loaded in tension showed a stress distribution similar to a CNSR specimen. A very good correlation was obtained between the NTP and CNSR fracture toughness values of poly(methyl methacrylate) during a calibration study. Fracture toughness values similar to those reported in the literature were obtained for several dental materials and one adhesive interface using the NTP test. The fracture patterns were indicative of plane strain conditions during testing. All bulk specimens and most of the adhesive specimens showed crack arrest, which suggested a stable, well-controlled testing procedure. These results suggest that the NTP fracture toughness test can be used to determine the fracture mechanics of bulk materials and adhesive interfaces.