Microwave synthesis of hydroxyapatite and physicochemical study of its properties

Method for microwave liquid-phase synthesis of hydroxyapatite samples was developed. The composition of the synthesis products obtained and natural hydroxyapatite was studied by X-ray phase and X-ray fluorescence microanalysis. IR spectra were measured and the dispersity of hydroxyapatite powders obtained, their solubility in water at 20°C, and structural parameters were determined in comparison with natural hydroxyapatite and that produced by the common (“classical”) liquid-phase technique. The microwave-synthesized hydroxyapatite compares well in its properties with the biological and “classical” hydroxyapatites.     

Effect of temperature on crystallite size of hydroxyapatite powders obtained by wet precipitation process

In this investigation, HAp powders were synthesized using the wet chemical precipitation technique. The temperature of the heat treatment (80 °C, 120 °C, and 160 °C) and the addition of glutamic acid were the considered process parameters. After the reaction between the precursors calcium nitrate [Ca(NO₃)₂] and ammonium phosphate [(NH₄)H₂PO₄], decantation of the residue, drying, and finally, heat treatment of the residue were done sequentially. X-ray diffraction (XRD) analysis, scanning electron microscope (SEM) observations, and X-ray fluorescence (XRF) analysis were carried out to characterize the synthesized HAp powders. It was found that at a high heat treatment temperature plus the addition of glutamic acid are suitable process parameters to acquire uniform HAp powders with plate morphology and fibers with an average particle size of ～100–200 µm. The Ca/P ratio obtained was like the hydroxyapatite present in the bones in the order of 1.72. This situation can be indicated as an essential advantage in the biocompatibility of the synthesized material. The use of glutamic acid suggests crystal growth in a preferential direction as reported in our previous work. The manufacture of hydroxyapatite, especially in powder, is of great interest in developing additive manufacturing systems for the biomedical market.     

Characterization of Fine Hydroxyapatite Powders Synthesized by Wet Process

Abstract

We prepared fine hydroxyapatite powders by dropping ammonium bi-phosphate into a calcium acetate solution and by vigorously stirring at 3O°C. We measured the powders' specific surface area to be 290 m²/g by the BET technique. The powders were mono-dispersed ultrafine particles by transmission electron microscopy investigation. No phase other than hydroxyapatite (JCPDS: 9–432) was revealed by X-ray diffractometry. A quantitative chemical analysis gave a Ca/P ratio very close to the exact hydroxyapatite stoichiometry (Ca/P: 1.67). Shrinkage started up to 800°C according to a dilatometric measurement and the dense products were obtained when heated at 1000°C for 2 h in air. We used a quadrupole mass spectrometer to monitor the gases desorbed from the hydroxyapatite powders at a constant heating rate of 5°C/min in a high vacuum. It is noted here that there were two peaks of H₂O and CO₂, respectively, and that we observed an increase in desorption of H₂. The two peaks were explained clearly with an infrared spectrometry analysis and a thermal analysis we made separately.     

Low-temperature synthesis of porous hydroxyapatite scaffolds using polyaphron templates

A method to synthesize porous hydroxyapatite (HA) structures at a low temperature was investigated in this study. Polyaphrons, a class of high-internal-phase-ratio emulsions were used as the shape-directing template for the sol-gel reactions that facilitated the formation of the structures. Electron micrographs revealed a three dimensional porous structure with pore sizes in the range of 1–5 microns. X-ray diffraction images showed that the hydroxyapatite structure formed after treatment at 400°C matched exactly with commercial HA spectra indicating that the phase transformation was complete. IR spectra of the samples confirm the formation of the structural components characteristic of commercial HA.     

Sorption of uranium on lead hydroxyapatite

The uranium sorption from diluted aqueous solution onto lead hydroxyapatite was studied by using a batch-mode technique and the fluorimetric determination of uranium mass concentration. Partially crystallised lead hydroxyapatite [Pb₁₀(PO₄)₆(OH)₂] was obtained by direct precipitation and mild heating. This material presents very high specific surface, which is the key factor in the sorption of uranium from diluted solution. This material has a high ability to remove uranium (K _d,max from 5,661 to 18,833 ml/g, at 4 and 60 °C, respectively) in the chosen setup conditions (initial concentration of uranium 5 × 10^?6 M and pH 5.65).     

Sol–gel synthesis of calcium hydroxyapatite thin films on quartz substrate using dip-coating and spin-coating techniques

Sol–gel synthesis route was suggested to prepare calcium hydroxyapatite (Ca₁₀(PO₄)₆(OH)₂, CHA) thin films on quartz substrates. CHA thin films were obtained using dip-coating and spin-coating techniques by coating the substrates 1, 5, 15 and 30 times. In the sol–gel process, the ethylenediaminetetraacetic acid and 1,2-ethandiol as complexing agents were used. Moreover, triethanolamine and polyvinyl alcohol were used as gel network forming materials. After each coating procedure the films were annealed at 1,000 °C. The results obtained from dip-coating and spin-coating techniques were compared in this study. It was demonstrated, that the formation of calcium hydroxyapatite depends on dipping (or spinning) time and annealing duration.     

Self-organization processes and phase transitions in nanocrystalline hydroxyapatite according to exoemission data

Low-temperature (20–360°C) exoemission of negative charges from nanocrystalline hydroxyapatite Ca₁₀(PO₄)₆(OH)₂ was studied. Thermal cycling and storage at 20°C were found to induce self-organization processes with charge separation and the formation of a negatively charged layer on the surface. The negative charge formed was long retained at elevated temperatures and only decreased during cooling in the temperature region of the structural transition, as is characteristic of thermoelectrets. No stable electrets formed in hydroxyapatite samples calcined at a high temperature (>800°C).     

Photoelectron spectroscopic studies of the formation of hydroxyapatite films on 316L stainless steel pretreated with etidronic acid

The valence band and core‐level X‐ray photoelectron spectroscopy was used to probe hydroxyapatite films formed on the surface of stainless steel. These films formed on steel may find application in medical implants. The key to the successful adhesion of the hydroxyapatite films is shown to be the initial formation of a thin, oxide‐free etidronate film on the metal. It was not found possible to prepare the hydroxyapatite films directly on the metal surfaces. Since hydroxyapatite is a key component of bone and teeth, it is likely that the coated metals will have desirable biocompatible properties. The hydroxyapatite film was exposed to air, water, and 1M sodium chloride solution as representative components of the environment of the film in the human body, and these exposures led to no detectable decomposition of the film. The thin hydroxyapatite and etidronate film on the metal show differential charging effects that caused a doubling of the peaks in some core level spectra. The valence band spectra proved especially valuable in the identification of the surface chemistry of the films, and these spectra were interpreted by comparing the experimental spectra with spectra calculated using band structure calculations which showed good agreement with experiment. The calculated spectrum of etidronic acid was found to be significantly different to that of etidronate. Copyright © 2012 John Wiley & Sons, Ltd.     

Increased thermostability of non-polar wall-coated open tubular columns

A method of deactivating the inner surface of glass capillary columns is described, which can be used at 350°C without detoriation. A non-polar liquid phase was prepared from a commercially available liquid phase which, when coated on a glass surface, can withstand temperatures of 325°C for isothermal analysis and 350°C for temperature-programmed analysis. After deactivation, the column was coated using the static coating method. Then it was conditioned, tested and kept for 48 hours at 35O°C before being used for the analysis of a mixture of chlorinated pesticides.     

Atomic layer deposition (ALD) as a coating tool for reinforcing fibers

Layers of alumina were deposited on to bundled carbon fibers in an atomic layer deposition (ALD) process via sequential exposure to vapors of aluminium chloride and water, respectively. Scanning electron microscopic (SEM) images of the coated fibers revealed that each individual fiber within a bundle was coated evenly and separately, fibers are not bridged by the coating. SEM and transmission electron microscopic (TEM) images indicate that the coating was uniform and conformal with good adhesion to the fiber surface. Average deposition rate, measured from SEM images, was 0.06 nm per cycle at 500 °C. SEM also revealed that at deposition temperatures of 500 °C few of the fibers were damaged. At temperatures of 300 °C, no damaged fibers were observed, the average deposition rate decreased down to 0.033 nm per cycle. Oxidation resistance of the alumina-coated fibers was characterized by thermogravimetric analysis (TGA). The alumina coating improved oxidation resistance of the carbon fiber significantly. Oxidation onset temperature was 600 °C for fibers coated with a 45 nm thick alumina. Uncoated fibers, on the other hand, started to oxidize at temperatures as low as 250 °C.     

Micro-PIXE analysis of bioconductive hydroxyapatite coatings on titanium alloy

Bioconductive materials and in particular implants using Ti alloy (Ti6–Al4–V) coated with hydroxyapatite (HAp) have proved to be a suitable surgical procedure. However, experience has shown that these implants not always have the required reliability to guarantee their expected life-span of approximate 15 years. In this research, experimental Ti alloy-implants coated with HAp and incubated in a simulated body fluid (r-SBF) under controlled physiological conditions were studied by nuclear microprobe (NMP). Selected HAp coatings, were analysed by micro-PIXE using protons of 1.5 MeV at the iThemba LABS NMP facility. Major elements (Ti, Al, V, Ca and P) as well as trace elements (Si, K, Fe, Zn and Sr) were determined. The effect of longer incubation time was of particular interest. Results confirmed that secondary Ca-deficient defect hydroxyapatite precipitated from the simulated body solution onto the HAp coating surface after prolonged incubation. This newly formed layer is thought to be of vital importance for bonding of implants with living bone tissue.     

Sorption of aqueous palladium onto synthetic hydroxyapatite

The sorption of Pd(II) on hydroxyapatite (Ca₁₀(PO₄)₆(OH)₂) has been studied at 25 °C as a function of pH, in 0.01 M NaClO₄, and 0.01 and 0.025 M Ca(ClO₄)₂ aqueous background electrolytes and Pd(II) concentration (9.3 to 47 ??M), trying to minimize some types of reactions, such as solid dissolution of and metal precipitation. The radiotracer palladium, ¹⁰⁹Pd, obtained by neutron irradiation, has been used to calculate the palladium??s distribution coefficients K _d between aqueous and solid phase. A mathematical treatment of results has been made by ion-exchange theory in order to interpret palladium sorption onto treated solid. For this, we take into account the existence of active sites at the hydroxyapatite surface, and the aqueous solution chemistry of palladium as well as the effect of phosphate anions from solid dissolution. The results can be explained as evidence of sorption of the species PdOH⁺, and of a mixed hydroxo complex of Pd²⁺ like (XCaO^?)?CPdOH⁺·nH₂O fixed onto {??Ca?COH} surface sites of the hydroxyapatite.     

Sol–gel synthesis and characterisation of nanoporous zirconium titanate coated on 316L SS for biomedical applications

In this study, the nanoporous zirconium titanate was prepared using sol–gel process and coated over 316L SS implants via dip-coating technique. XRD patterns of zirconium titanate are crystalline and orthorhombic in structure. FT-IR spectra showed a broad band between 3,500 and 3,300 cm⁻¹, which was assigned to fundamental stretching vibrations of hydroxyl groups. The set of overlapping peaks in the range of 810–520 cm⁻¹ are related to Zr–O and Zr–O–Ti groups. SEM-EDAX and TEM showed the surface morphology of coated zirconium titanate to be porous and uniform. Excellent adhesion of the coating to the substrate has been achieved. The contact angle value was found to be 12°. The coating acts as a barrier layer to the metallic implants and induces the formation of hydroxyapatite layer on the metal surfaces. These results revealed that the nano zirconium titanate coated 316L SS exhibit higher bioactivity compared to that of uncoated 316L SS.     

Improvement of thermal decomposition properties of ammonium perchlorate particles using some polymer coating agents

This research aimed to investigate the optimum conditions for modification of thermal decomposition properties of ammonium perchlorate (AP) particles through microencapsulation techniques. A solvent/non-solvent method has been used to perform microencapsulation of AP particles with some polymer-coating agents such as viton A and nitrocellulose (NC). Differential scanning calorimetry, thermogravimetry, and scanning electron microscopy have been exploited to investigate the thermal properties, heat of decomposition, and coating morphology of pure and coated samples. The preliminary results revealed that AP microparticle could be effectively coated with both NC and viton, but the latter significantly and unfavorably attenuated heat of decomposition of AP so NC was chosen as an appropriate coating agent for modification of thermal properties of AP. The thermal analysis of NC-coated samples, prepared at optimized coating conditions, showed that its first stage decomposition temperature increases about 12 °C with respect to uncoated sample and reaches to 305 °C. Also, the apparent activation energy (E), ΔG ^≠, ΔH ^≠, and ΔS ^≠ of the decomposition processes of the pure and coated AP particles at the optimum conditions were obtained by non-isothermal methods that proposed by ASTM and Ozawa. Finally, the results of this investigation showed that microencapsulation of AP particles with fibrous NC enhance its heat of decomposition (~120 J g^?1) with no obvious effect on kinetic parameters and thermal decomposition temperature.     

Effect of sintering temperature on mechanical and microstructural properties of bovine hydroxyapatite (BHA)

The influence of sintering temperature on densification, microstructure and the mechanical properties of bovine hydroxyapatite (BHA), produced by a calcination method, was investigated. Densification and mechanical properties improved with increasing sintering temperature in the range between 1000°C and 1300°C, with optimum properties being obtained at a sintering temperature of 1200°C. The measured mechanical properties indicate that sintered BHA bodies are interesting biomaterials for further investigation in biomedical applications.     

Preparation of a Carbon-Coated SPME Fiber and Application to the Analysis of BTEX and Halocarbons in Water

A carbon-coated fiber for solid-phase microextraction (SPME) has been prepared from powdered activated carbon (PAC) and a fused-silica fiber. Scanning electron microscopy of the coating revealed the carbon particles were uniformly distributed on the surface of the fiber substrate. Efficient extraction of BTEX (benzene, toluene, ethylbenzene, p-xylene, and o-xylene) and halocarbons (chloroform, trichloroethylene, and carbon tetrachloride), with short extraction and desorption times, was achieved by use of the coated fiber. The maximum working temperature of the coated fiber was 300 °C and the lifetime was over 140 desorption operations at 260 °C. Limits of quantification (LOQ) of the SPME method for the eight analytes ranged from 0.01 to 0.94 μg L⁻¹, and relative standard deviations (RSD) were below 7.2% (n=6). Recoveries were 87.9–113.4% when the method was applied to the analysis of BTEX and the halocarbons in real aqueous samples. An erratum to this article is available at .     

Electrophoretic Deposition of Hydroxyapatite Coatings on Metal Substrates: A Nanoparticulate Dual-Coating Approach

Hydroxyapatite coatings can be readily deposited on metal substrates by electrophoretic deposition. However, subsequent sintering is highly problematic owing to the fact that temperatures in excess of 1100°C are required for commercial hydroxyapatite powders to achieve high density. Such temperatures damage the metal and induce metal-catalysed decomposition of the hydroxyapatite. Furthermore, the firing shrinkage of the hydroxyapatite coating on a constraining metal substrate leads to severe cracking. The present study has overcome these problems using a novel approach: the use of aged nanoparticulate hydroxyapatite sols (lower sintering temperature) and a dual coating strategy that overcomes the cracking problem. Dual layers of uncalcined hydroxyapatite (HAp) powder were electrophoretically coated on Ti, Ti6Al4V and 316L stainless steel metal substrates, sintered at 875–1000°C, and characterised by SEM and XRD, and interfacial shear strength measurement. Dual coatings on stainless steel had an average high bond strength (about 23 MPa), and dual coatings on titanium and titanium alloy had moderate strengths (about 14 and 11 MPa, respectively), in comparison with the measured shear strength of bone (35 MPa). SEM and XRD demonstrated that the second layer blended seamlessly with the first and filled the cracks in the first. The superior result on stainless steel is attributed to a more appropriate thermal expansion match with hydroxyapatite, the thinner oxide layer, or a combination of these factors.     

Synthesis of nanosized carbonated apatite by a modified Pechini method: hydroxyapatite nucleation from a polymeric matrix

Pechini method is a materials synthesis method based on the preparation of a polymeric matrix. The advantage of this method is the ability to obtain materials with different particle sizes depending on the synthesis condition with a homogeneous distribution. In this work, carbonated hydroxyapatite (c-OHAp) nanoparticles were obtained by a modified Pechini method. To obtain the polymeric precursor of the c-OHAp, the polymeric matrix was prepared through a polyesterification reaction between citric acid and ethylene-glycol. Adding calcium hydroxide and ortophosphoric acid in aqueous solutions, raising the temperature up to 140 °C/2 h and keeping constant the pH at 8. The polymeric matrix was calcinated at different ranges of temperature from 200 to 600 °C in order to obtain the c-OHAp powder. The results show the presence of c-OHAp a as unique phase. The thermal analysis indicates that the c-OHAp phase was obtained at 600 °C. The particle size of the obtained material was <50 nm.     

Arsenate hydroxyapatite: A physico-chemical and thermodynamic investigation

Arsenate hydroxyapatite, Ca₁₀(AsO₄)₆(OH)₂ (AsHA), was synthesized by precipitation at 100°C, and characterized by X-ray studies, IR spectra, electron microscopy, and thermography (TGA, DTA and DTG). The solubility of AsHA was investigated between temperatures of 308 and 323 K, and in the pH range 4.0–8.0. It exhibited a retrograde solubility. The solubility behaviour can be explained on the basis of the chemical potential and free energy in solution. Standard thermodynamic parameters, ΔH^θ, ΔS^θ and ΔC_p^θ, are reported. The solubility products of AsHA were found to be 4.0 x 10⁻⁹¹, 2.7 x 10⁻⁹¹, 2.1 x 10⁻⁹¹ and 1.2 x 10⁻⁹¹ at temperatures of 3.08, 313, 318 and 323 K, respectively.     

Effect of TiO2–Ti and TiO2–TiN composite coatings on corrosion behavior of NiTi alloy

Two kinds of biocompatible coatings were produced in order to improve the corrosion resistance of nickel titanium (NiTi) alloy. A titanium oxide–titanium (TiO₂–Ti) composite was coated on NiTi alloy using electrophoretic method. After the coating process, the samples were heat‐treated at 1000 °C in two tube furnaces, the first one in argon atmosphere and the second one in nitrogen atmosphere at 1000 °C. The morphology and phase analysis of coatings were investigated using scanning electron microscopy and X‐ray diffraction analysis, respectively. The electrochemical behavior of the NiTi and coated samples was examined using polarization and electrochemical impedance spectroscopy tests. Electrochemical tests in simulated body fluid demonstrated a considerable increase in corrosion resistance of composite‐coated NiTi specimens compared to the non‐coated one. The heat‐treated composite coating sample in nitrogen atmosphere had a higher level of corrosion resistance compared to the heat‐treated sample in argon atmosphere, which is mainly due to having nitride phases. Copyright © 2014 John Wiley & Sons, Ltd.