Synthesis of hydroxyapatite/poly(vinyl alcohol phosphate) nanocomposite and its characterization

Hydroxyapatite (HAp)/poly(vinyl alcohol phosphate) (PVAP) nanocomposite has been prepared using a solution‐based method varying HAp from 10 to 60% (w/w). X‐ray diffraction, Fourier transform infrared absorption spectra (FTIR), and thermal analysis have indicated the presence of bonding between HAp particles and PVAP matrix. Transmission electron microscope analysis shows the needle‐like crystals of HAp powder having a diameter of 6–10 nm and a length of 26–38 nm. The surface roughness and the homogeneous dispersion of HAp particles in the polymer matrix have been observed by scanning electron microscopy. Particle size distribution analysis shows the narrow distribution of hydrodynamic particles in the polymer matrix. The tensile stress–strain curves show the improvement in mechanical properties of the composites with increase in amount of HAp particles loading. The composites along with polymer are highly hemocompatible. The use of PVAP promotes the homogeneous distribution of particles on the polymer matrix along with strong particle–polymer interfacial bonding, which has supported the improvement in mechanical properties of the composites. The prepared HAp/PVAP composite with uniform microstructure would be effective to act as a potential biomaterial. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

Processing and properties of nano‐ and macro‐hydroxyapatite/poly(ethylene‐co‐acrylic acid) composites

Hydroxyapatite (HAp)/poly(ethylene‐co‐acrylic acid) composites have been synthesized by a solution‐based method, using nanosized (n‐HAp) and coarse hydroxyapatite (c‐HAp) particles, respectively. X‐ray diffraction study has indicated the development of compressive and tensile stresses in composites because of the thermal expansion mismatch between the particles and polymer matrix. Fourier transform infrared absorption spectra and thermal analysis have showed the presence of strong interfacial bonding between the particles and polymer. The surface roughness and the homogeneous dispersion of HAp particles in the polymer matrix have been observed by scanning electron microscopy. A comparison in mechanical properties between composites prepared with n‐HAp and c‐HAp particles, respectively, has been studied. Nanosized particles contribute excellent improvement of mechanical properties of the composites rather than the coarse particles. The uniform dispersion of HAp particles, followed by the improvement in mechanical properties of the composite, provides a means of preparing HAp/polymer composites for low load‐bearing implant applications. POLYM. COMPOS., 27:633–641, 2006. © 2006 Society of Plastics Engineers     

An aqueous synthesis of photocatalyst by selective dissolution of titanium oxide/hydroxyapatite composite

A novel synthesis method of a highly active photocatalyst was proposed. Titanium dioxide (TiO₂) nano-particles were prepared by three-step procedure, precipitation of hydroxyapatite (HAp) on TiO₂ particles, heat treatment of the TiO₂/HAp composites, and acid treatment in hydrochloric acid. The unique point of this procedure is the selective dissolution of HAp to obtain exposed TiO₂ surfaces. The HAp precipitation was achieved by stirring TiO₂ powders in the mixtures of Ca(NO₃)₂ and NH₄H₂PO₄ aqueous solutions at pH 8.5. Then, the heat-treated TiO₂/HAp composites were treated with hydrochloric acid. The precipitated HAp avoided the direct contact of TiO₂ particles and suppressed the phase transformation from anatase-to-rutile >200 °C. The HAp also suppressed a decrease of specific surface area of TiO₂ during the heat treatment. The photocatalytic activities were evaluated from an absorbance decrease of methylene blue (MB) under ultraviolet (UV) irradiation. The MB photodecomposition was approximated to the first-order reaction and the reaction rate constants of the obtained TiO₂ powders heated at various temperatures were higher than those of conventional TiO₂ powders heated at same temperatures. The enhanced photocatalytic activity is attributed to the suppression effects for the phase transformation to rutile phase and the decreasing of specific surface area in the heat treatment.     

Cosmetic properties of TiO2/mica-BN composite powder prepared by spray drying

In the present study, the spray drying process was used to prepare spherical composite powders from TiO₂/mica and h-BN powders. The starting and the as-prepared powders were examined by X-ray diffraction, scanning electron microscopy, particle size analyzer, spectrophotometer, and oil absorption analysis. Particle size distribution, crystalline phases, whiteness, and oil absorption ability were analyzed in order to determine powder morphology. These powders were then mixed into linseed oil to prepare an emulsion for sunscreen protection application. The resultant emulsions were examined using UV–visible–near infra-red (NIR) spectroscopy, sun protection factor tester, and thermal conductivity tester. The experimental results show that spherical composite powder prepared by spray drying not only possess good oil and NIR absorption ability, but also thermal conductivity. The emulsion prepared by spray dried powder exhibits superior sunscreen protection performance compared to its starting counterparts.     

Preparation and morphological investigation on bioactive ion-modified carbonated hydroxyapatite-biopolymer composite ceramics as coatings for orthopaedic implants

Bioactive ions (Mg, Sr, Zn) doped carbonated hydroxyapatite powders (dHAp) and pure carbonated hydroxyapatite (HAp) powders were prepared by wet chemical precipitation method. The bioactive ions were incorporated into the HAp matrix by co-precipitation from solution containing the appropriate amount of chloride salt of different ions. The morphology of pure HAp was mainly needle-like in nanometre size and the particles were disordered showing quasi-amorphous structure. The ion doping changed the morphology of particles, the dHAp particles had distorted spheroid shapes. Owing to the ion addition, the crystallinity of particles decreased. Particle aggregations can also be observed in both types of samples. HAp and dHAp loaded biopolymer polyvinylpyrrolidone (PVP) composite materials have also been developed by novel electrospinning technique. It has been shown that both the HAp and dHAp particles can be successfully incorporated into the PVP fibre web matrix and simultaneously the bioceramic powders were attached to the surface of polymer fibres. The surface of fibres was not fully covered with the particles. The ceramic powder addition to the polymer solution caused the polymer fibres to become more entangled and the diameters of fibres varied over a wider range compared to the base polymer fibres without bioceramic powder addition.     

A Facile Route to the Synthesis of Hydroxyapatite/ Wollastonite Composite Powders by a Two-Step Coprecipitation Method

A facile and fast method has been developed to synthesize pure hydroxyapatite/wollastonite (HAp/WT) composite powders of different weight ratio. HAp/WT composites could be easily prepared by a two-step coprecipitation route and subsequent heating of the precipitant for 2 h, using Ca(OH) ₂ and H ₃PO₄ as starting materials in the first step then adding Ca(NO ₃) ₂.4H ₂O and Na ₂SiO ₃.9H ₂O in the second step. XRD, FT-IR and XRF analyses confirmed the synthesis of pure HAp/WT composite powders. SEM data showed that the synthetic composites have agglomerated particles consisting of small particles with size less than 1 μm. The results indicates that this route for synthesis of HAp/WT composites is promising for medical applications such as bone repair substitutes and drug carriers.     

Synthesis of Nanosized Aluminum Nitride Powders by Pulsed Laser Ablation

The influence of the target material, fluence, laser wavelength, and nitrogen pressure on the synthesis of AlN nanosized powders via reactive laser ablation has been investigated. Using infrared laser radiation and fluences of ≥11 J/cm², pure AlN nanosized powders were produced at nitrogen pressures of ≥1.3 kPa via ablation of an AlN target and ≥13.3 kPa via ablation of an aluminum target. With ultraviolet laser radiation, AlN powders could be synthesized at a lower fluence (9 J/cm² at a pressure of 8 kPa). The mean powder size was 7.5−15 nm.     

Formation of hydroxyapatite on CaSiO3 powders in simulated body fluid

CaSiO₃ powders were prepared from ethanol solutions of Ca(NO₃)₂·4H₂O and Si(OC₂H₅)₄ using NaOH as a precipitant. The resultant powders were heated at three different temperature regimes, (1) 500°C, (2) 500 and 1000^oC and (3) 500 and 1400°C, to obtain the amorphous phase (amorphous-CS), low temperature phase (β-CS), and high temperature phase (α-CS) of CaSiO₃, respectively. The different amorphous and crystalline phases exhibited different microtextures and specific surface areas of the powders. The rough, porous particles of amorphous-CS and β-CS have higher specific surface areas than the smooth, dense particles of α-CS. These CaSiO₃ powders were soaked in a simulated body fluid (SBF) at 36.5°C for 2 h to 30 days. Formation of hydroxyapatite (HAp) was observed on the surfaces of all samples, but the formation behavior and microstructures were different, resulting the differences in microstructure and crystal structure of the starting powders as well as particle size and specific surface area. The HAp formed on the amorphous-CS was a loose porous layer consisting of uniformly-sized tiny ball-like agglomerated particles, while that formed on the β-CS and α-CS was a dense layer consisting of larger ball-like agglomerated particles.     

Sintering behavior and mechanical properties of hydroxyapatite ceramics prepared from Nile Tilapia (Oreochromis niloticus) bone and commercial powder for biomedical applications

In this work, Nile tilapia (Oreochromis niloticus) bone was calcined at 800 °C for 5 h in an air atmosphere to obtain hydroxyapatite powder (FB powder). The elemental composition, phase structure, and morphology of the FB powder were investigated and compared with commercial hydroxyapatite powder (SM powder). The FB-powder exhibited 1.01 at. % of Mg while the SM-powder showed Mg in ppm-level. Carbonate groups were detected in the two powders. Both HAp and β-tricalcium phosphate (β-TCP) structures were found in the FB powder, but the SM powder exhibit only the HAp phase. Irregular-shaped particles were observed in the FB powder. After the two HAp powders were sintered at 1200 °C and 1250 °C for 2 h (FB-1200, FB-1250, SM-1200, and SM-1250), the β-TCP intensity peaks of the FB-ceramic samples significantly increased with increasing sintering temperature. The highest relative density, well-packed grains, and β-TCP stabilization by Mg at the Ca5 site of the FB-1250 structure were the dominant factors governing the highest mechanical properties. Although high density was observed in the SM-1200 sample, Vickers hardness of the SM-1200 sample is lower than the FB-1250 sample. This may be attributed to the partial decomposition of HAp into β-TCP, α-tricalcium phosphate (α-TCP), and Ca₁₀(PO₄)₆O phases. In addition, the increase of grain size was the main factor that governs the increasing compressive strength and Young's modulus instead of density and phase decomposition of the SM-ceramic samples.     

Preparation and characterization of poly(styrene butylacrylate) latex/nano‐ZnO nanocomposites

Poly(styrene butylacrylate) latex/nano‐ZnO composites were prepared by blending poly(styrene butylacrylate) latex with a water slurry of nano‐ZnO particles, and the effects of certain parameters, such as particle size, dispersant type, dispersing time and others, on the dispersibility, mechanical properties, ultraviolet (UV) shielding and near infrared (NIR) shielding were investigated with transmission electron microscopy (TEM), an Instron testing machine, dynamic mechanical analysis and ultraviolet‐visible‐near infrared (UV‐VIS‐NIR) spectrophotometry. TEM observation showed that dispersants with long chains are better than those with short chains at enhancing the dispersibility of nano‐ZnO particles in a matrix; extending dispersing time also improves the dispersibility of nano‐ZnO particles in a matrix. Instron tests showed that the nanocomposite polymers embedded with nano‐ZnO particles had much higher tensile strength than the corresponding composite polymers with micro‐ZnO particles. As the nano‐ZnO content increased, the temperature of glass transition (T_g) of the nanocomposite polymer embedded with 60 nm ZnO particles first increased then decreased, but 100 nm ZnO and micro‐ZnO particles seemed to have no influence on the T_g of the composite polymers. The better dispersibility of nano‐ZnO particles resulted in higher T_g values. Increasing nano‐ZnO content or dispersibility could enhance the UV shielding properties of the nanocomposite polymers, and 60 nm ZnO particles could more effectively shield UV rays than 100 nm ZnO particles. Micro‐ZnO particles basically had no effect on the UV absorbance of the composite polymers. A blue‐shift phenomenon was observed at 365 nm when nano‐ZnO particles were present in the nanocomposite polymers. NIR analysis indicated that as nano‐ZnO content increased, the NIR shielding of the nanocomposite polymers increased, but the NIR shielding properties seemed to be more influenced by particle size than by the nano‐effect. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1923–1931, 2003     

Laser annealing and surface modification of plasma polymer-metal composite films

Plasma polymer films with encapsulated metal particles were prepared by simultaneous plasma polymerization and metal evaporation. Laser annealing (Nd-YAG, 1064 nm) causes dramatic changes in the particle size and shape without material ablation, but with changes in the surface topography. This results in changes in the optical plasma resonance absorption, as demonstrated by UV-visible-near-infrared (NIR) spectroscopy. The invariable transmission in the UV region of the plasma polymer matrix after laser annealing confirms that there is no material ablation. Transmission electron microscopy (TEM) and scanning electron microscopy (SEM) demonstrated particle size changes and modifications of the plasma polymer surface due to laser annealing.     

Effect of ZrO2 content on the mechanical properties and microstructure of HAp/ZrO2 nanocomposites

This paper presents the effect of Zirconia (ZrO₂ =?0, 5, 10, 15, 20 and 25?wt%) on the mechanical properties and micro structural studies of Hydroxyapatite (Ca₁₀(PO₄)₆(OH)₂) (HAp) nano composites. HAp and Zirconia nano composites of 20–40?nm were produced using High Energy Ball milling at 300?rpm for 1?h. X-ray diffraction studies showed that the crystallite and grain size gradually decreased with the increase in ZrO₂ content till 20?wt%, after which there was a sudden raise in both parameters. A dominant ZrO₂ phase was observed in X-ray diffraction studies of sintered samples. Mechanical properties were found to significantly improve on adding 20?wt% of ZrO₂ at 1200?°C. However, the addition of 25?wt% of ZrO₂ powder decreased the mechanical properties of HAp. The reduction could be due to the increase in grain size and dominant smaller particles of ZrO₂. The improved mechanical properties were correlated with the observed micro structural features.     

Effect of pH on the Carbonate Incorporation into the Hydroxyapatite Prepared by an Oxidative Decomposition of Calcium–EDTA Chelate

In this study, the carbonate incorporation into the hydroxyapatite (HAp) lattice under various pH conditions was investigated. Crystalline-sodium and carbonate-containing calcium HAp (NaCO₃HAp) powders were prepared using an oxidative decomposition of calcium–EDTA chelates in a sodium phosphate solution with hydrogen peroxide. The powders obtained were characterized by X-ray diffraction, infrared spectroscopy, thermal gravimetric analysis, scanning electron microscopy, energy-dispersive X-ray spectroscopy, and elemental analysis. Depending on pH, spherical particles approximately 3.5 μm in diameter or hexagonal prismatic particles measuring 3–9 μm in length were obtained. Various characterization techniques showed that the precipitates were a single-phase NaCO₃HAp. The carbonate content and the lattice parameters of the HAp were a function of solution pH. Maximum carbonate incorporated into the HAp lattice was at pH=10, corresponding to lattice parameters of a =0.93880 nm and c =0.69070 nm. Furthermore, spectroscopic analyses indicate that the as-prepared samples are B-type carbonated HAp, in which carbonate ions occupy the phosphate sites. After heat treatment at 965°C, most of the carbonate is removed from the HAp lattice.     

Design and preparation of composite coatings with increased reflectivity under high-energy continuous wave laser ablation

High-energy continuous wave (CW) laser ablation can cause severe damage to structural materials in an extremely short time, which generates considerable concern in terms of material safety. For the purpose of reducing or even eliminating such laser-induced damage, a novel composite coating consisting of a boron-modified phenolic formaldehyde resin incorporating ZrC and SiC has been designed and prepared. The experimental results reveal that ZrC and SiC are rapidly oxidized to ZrO₂ and SiO₂ respectively, leading to the formation of a white ceramic layer consisting of ZrO₂ particles and melted SiO₂. After ablation at 1000 W/cm² for 50 s, elemental analysis indicates that no Si can be found in the central ablation zone because of gasification. A relatively compact ZrO₂ layer is formed through the sintering of adjacent ZrO₂ particles, which effectively improves the reflectivity of the coating from 7.3% (before ablation) to 63.5% (after ablation). The high reflectivity greatly reduces the absorption of laser energy. In addition, no obvious ablation defects are observed in the composite coating. The excellent anti-laser ablation performance of the coating makes it a promising system for protecting a material against the effects of long-term CW laser ablation.     

Production of silicon containing particles by laser induced reaction of silane with methane,ethane and acetylene

Silicon containing ultrafine particles (Si and SiC) have been obtained by pulsed IR laser irradiation of gaseous SiH₄/hydrocarbon (CH₄, C₂H₆ and C₂H₂) mixtures. The chemical composition and structure of the powders formed were determined by scanning and transmission electron microscopy (SEM and TEM), X-ray diffraction (XRD) and I.R. and UV-v spectroscopy. The particles are small, uniform, loosely agglomerated spheres with a mean size of approximately 19 nm. To complete the characterisation of these ultrafine silicon-containing particles, the X-ray absorption spectra (XAS) were obtained using synchrotron radiation at the silicon absorption K-edge. We show that the use of pulsed laser radiation results in the generation of amorphous Si and crystalline SiC particles depending on the gas mixtue used, among other parameters such as composition of the mixture, laser fluence, pressure and number of laser pulses.     

Effect of Laser Fluence on the Structural,Morphological and Optical Properties of 2H-PbI<Subscript>2</Subscript> Nanoparticles Prepared by Laser Ablation in Ethanol

The effect of laser fluence on the optical, structural and morphological properties of PbI₂ nanoparticles NPs synthesized by pulsed laser ablation in ethanol was studied. The direct optical energy gap of PbI₂ NPs prepared at various laser fluences was in the range of (3–3.3 eV) at room temperature. Three absorption peaks related to surface plasmon resonance at 337, 435 and 507 nm are observed. XRD results show that all the grown PbI₂ NPs are polycrystalline in nature and the formation of hexagonal structure 2H-polytype was observed at laser fluence of 3.6 J/cm². The surface morphology of PbI₂ NPs investigated by SEM revealed formation of hexagonal, platelet-like and spherical NPs morphologies. TEM images showed formation of spherical particles with size varied from 10 to 75 nm depending on the laser fluence. PL measurement shows emission of broad peak centered at 350 nm and increasing the laser fluence results in red shift. The Raman spectra of PbI₂ NPs revealed existence of five vibration modes situated at 74, 96,106, 169 and 213 per cm. FT-IR investigation showed a broad band at 3383 per cm indexed to symmetric stretching vibration of Pb–I clusters and band at 725 per cm related to bending mode of O–H.     

N-doped TiO2 nanoparticles obtained by a facile coprecipitation method at low temperature

N-doped TiO₂ nanoparticles (NPs) were synthesized using a facile synthesis route by coprecipitation method. The effect of the HNO₃ volume and calcination temperature on the structural, morphological, optical and surface properties of the N-doped TiO₂ NPs was studied. X-ray diffraction analysis showed particles of nanometric size (< 16 nm), which are consistent with HR-TEM micrographs. A slight shift of the absorption edge to higher wavelengths is observed as the HNO₃ volume and calcination temperature increases. Both X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FT-IR) show the presence and stability of nitrogen in the N-doped TiO₂ structure. The photocatalytic activity of the N-doped TiO₂ NPs was assessed by testing the degradation of rhodamine B (RhB) under ultraviolet (UV) and visible light.     

Nanoparticles of zinc stannates (ZTO): Synthesis,characterization and electrical behavior in oxygen and acetone vapors

Zinc stannate (ZTO) ceramic powders were synthesized by a modified Pechini method. The nanoparticles synthesized at 900 °C were characterized using thermal analysis (TGA/DTA), infrared (IR), UV–Vis absorption and Raman spectroscopies, photoluminescence (PL), X-ray diffraction (XRD), and transmission electron microscopy (TEM). Characterization revealed a mixture of phases of perovskite-type ZnSnO₃ and spinel cubic Zn₂SnO₄, with a primary particle size of <50 nm, and a gap energy of ~4.10 eV. Using the obtained ceramic powders, green pieces were formed by slip casting and sintered at 1200 °C and 1400 °C. Finally, the effect of the presence of oxygen and acetone atmospheres on the electrical response of the sintered ZTO pieces at 1200 °C was evaluated. The tests showed an appreciable variation in the resistance of the samples on altering the nature of the atmosphere of the gas surrounding the piece, indicating good sensory capacity of the ZTO pieces to these gases.     

Study of cationic UV curing and UV laser ablation behavior of coatings sensitized by novel sensitizers

To improve the laser ablation performance of cycloaliphatic epoxide cationic UV curable coatings, two novel reactive sensitizers were synthesized and characterized and their effect on coating properties examined. The sensitizers were synthesized based on the reaction between naphthalene or anthracene derivatives and monomers or oligomers used in the coating system. HPLC and GC-MS confirmed the formation of the desired products. Three coating systems based on cycloaliphatic epoxide with either oxetane or polycaprolactone polyol were formulated with the reactive sensitizers. The sensitized coatings had higher conversion during UV curing in the oxetane containing formulation and did not deter the curing in the polyol containing formulation. Better UV laser ablation performance was observed in all sensitized coatings compared to the controls. Coatings with the anthracene based sensitizer even had better laser ablation performance than a commercial polyimide. The sensitized coatings had higher hardness, T_g and crosslink density while the adhesion and solvent resistance were not affected. An optimal amount of sensitizer was found for each coating formulation in terms of UV curing behavior. The relationship between coating T_g and laser ablation behavior was investigated and it was found that the higher the T_g and crosslink density, the poorer the laser ablation performance.     

Ultrafine and nanosized MoSi2 powders by SHS process with a reduction stage

Suggested are basic principles for fabrication of fine MoSi₂ powders by SHS process with a reduction stage. Investigated was the influence of green composition, stoichiometric ratio, inert NaCl additive, and synthesis conditions on the structure/properties of thus fabricated MoSi₂ powders. With increasing amount of added NaCl, the mean size of MoSi₂ crystallites was found to decrease. The fabricated MoSi₂ powders represented the agglomerates formed by the crowds of smaller (200 nm) and larger (up to 1–3 μm) particles. The powders were characterized by SEM, XRD, and chemical analysis.