N. Rameshbabu

X-Ray Peak Profile Analysis of Nanostructured Hydroxyapatite and Fluorapatite

389  Abstract—In present study, X-ray peak profile analysis (XPPA) by modified Williamson-Hall (W-H) models, namely W-H-isotropic strain model (W-H-ISM), W-H-anisotropic strain model (W-H-ASM) and W-H-energy density model (W-H-EDM), was employed to estimate the microstructural parameters such as, crystallite size, lattice strain, lattice deformation stress and deformation energy density from the powder diffraction data obtained for the microwave synthesized hydroxyapatite (HA) and fluorapatite (FA) nanoparticles prepared under identical processing conditions of mixing and aging. The as-prepared powder particles were also characterized by transmission electron microscopy (TEM) method. The average crystallite size values estimated for HA and FA by XPPA were correlated to their respective transmission electron microscopy (TEM) analysis results. In addition, the estimated values of HA and FA were correlated to their in-vitro dissolution characteristics studied by ethylenediamine tetra-acetic acid (EDTA) titrimetric method. It is found that the average crystallite size estimated by W-H models is in good agreement with TEM results. The controlled in-vitro dissolution behavior of FA was found to be resulted out of its higher crystallite size, lower lattice strain and lower dislocation density compared to that of HA.

Influence of microwave power, irradiation time and polymeric additions on synthesis of nanocrystalline hydroxyapatite

Abstract Synthetic hydroxyapatite (HA) has been extensively used as an implant material owing to its excellent osteoconductive properties. The preparation of nanocrystalline HA is of paramount importance as the large surface area of the diminutive crystals makes them very active and consequently strongly affects the properties of it. In this paper, to study the effect of microwave irradiation power and time, nanocrystalline HA was synthesised at different microwave irradiation times (15, 45, 120, 240 and 600 min) and with different microwave powers (800 and 1100 W). This study also investigated the crystallisation of HA in the presence of sodium alginate and alginic acid at different addition levels (5, 10 and 15 wt-% to the final HA). It was found that crystallinity of the HA increases with increasing microwave irradiation time and/or power. Sodium alginate or alginic acid addition during crystallisation of HA decreases the crystal size and crystallinity of the precipitated HA.

MECHANOCHEMICAL SYNTHESIS OF NANOCRYSTALLINE FLUORINATED HYDROXYAPATITE

Synthetic hydroxyapatite (Ca10(PO4)6(OH)2, HA) is an important material used for orthopaedic and dental implant applications. The biological hydroxyapatite in the human bone and tooth is of nano size and differs in composition from the stiochiometric HA by the presence of other ions such as carbonate, magnesium and fluoride, etc. Osseointegration is enhanced by using nanocrystalline HA. This stimulates the interest in synthesizing nanocrystalline HA by different routes and among the methods, mechanochemical seems to form fine grain size and uniform characteristic nanocrystalline materials. Fluorinated hydroxyapatite (FHA, Ca10(PO4)6(OH)2-xFx) possesses higher corrosion resistance in biofluids than pure HA and reduces the risk of dental caries. The present work deals with the synthesis of nanocrystalline FHAs by mechanochemical processing. The nanomaterials were characterized using X-ray powder diffraction (XRD) and transmission electron microscopy (TEM) methods. Nano FHA of about 27-46 nm size was observed. The functional groups present in the FHA powders were ascertained by Fourier transform infrared spectroscopy (FT-IR) and Laser Raman spectroscopy. A gradual decrease in intensity of the OH- band at 655 and 3572 cm-1 has been observed with increasing fluorine substitution. The TEM micrograph shows that the powder is highly agglomerated and particle size is below 50 nm.

Plasma Electrolytic Oxidation and Characterization of Spark Plasma Sintered Magnesium/Hydroxyapatite Composites

Magnesium (Mg)/hydroxyapatite (HA) (10 wt.% and 20 wt.%) composites were prepared by using pure Mg and as synthesized HA powders using the spark plasma sintering (SPS) method. The objective of the present study is to improve the corrosion resistance of spark plasma sintered Mg/HA composites and to ensure that the degradation time of these composites match with that of bone remodeling. Mg and HA powders were ball milled for 2 h and spark plasma sintered at a temperature of 475 °C and pressure of 40 MPa in vacuum. The sintered compacts were further treated by plasma electrolytic oxidation (PEO) in order to improve the corrosion resistance. The structural, microstructural and morphological studies were done using X-ray diffraction, optical microscopy and scanning electron microscopy, respectively. The corrosion resistance of as-sintered and PEO treated Mg/HA composites was studied by potentiodynamic polarization test in a 7.4 pH simulated body fluid (SBF) environment. The corrosion test results of as-sintered composites showed that the corrosion resistance decreases with the increase in percentage of HA in the composite. However, the PEO treated Mg/HA composites have shown delayed onset of degradation. Therefore, it can be hypothesized that the PEO treated Mg/HA composites would serve as bioactive and biodegradable orthopedic implant materials with low corrosion rates.

Effect of Electrolyte Chemistry on the Structural, Morphological and Corrosion Characteristics of Titania Films Developed on Ti-6Al-4V Implant Material by Plasma Electrolytic Oxidation

The present work is aimed at the optimisation of an electrolyte system for the development of an oxide layer on Ti-6Al-4V implant material by plasma electrolytic oxidation (PEO) process, to improve its corrosion resistance under 4.5 pH osteoclast bioresorption and 7.4 pH simulated body fluid physiological conditions. All the PEO experiments were conducted for 12 min in constant current mode by a DC power supply unit with 7 different electrolyte systems consisting of methodically varied concentrations of tri-sodium ortho phosphate (Na3PO4.12H2O), sodium meta silicate (Na2SiO3.9H2O) and potassium hydroxide (KOH). The phase composition of the fabricated oxide coatings was analyzed by X-ray diffraction (XRD) technique. The morphology and thickness of the coatings were determined by scanning electron microscopy (SEM) and the corrosion characteristics were assessed by potentiodynamic polarization and electrochemical impedance spectroscopic techniques. The XRD results demonstrated that the oxide coatings mainly consisted of anatase and rutile phases with different proportions. While the average surface pore size was in the range of 3 to 6 µm, the thickness of the coating varied from 5 to 20 µm. A significant improvement in the corrosion resistance and an added capacitive nature was observed for the PEO treated Ti-6Al-4V implant material compared to that of the untreated. The variation in the proportions of anatase and rutile phases, the surface pore size distribution, the thickness of the coating and the corrosion characteristics of the developed coatings were correlated with the composition and concentration of the electrolyte system. Of the seven different electrolyte systems employed in the present study, the one consisting of 10 g Na3PO4.12H2O, 2 g Na2SiO3.9H2O and 2 g of KOH was established to be an optimized electrolyte system for developing oxide coatings on Ti-6Al-4V to minimise corrosion and thereby reduce the metal ion release under physiological conditions.

Solar photocatalytic activity of nitrogen doped TiO2 coating by micro-arc oxidation

ABSTRACT Nitrogen doped porous TiO2 (N-TiO2) coating was developed from titanium nitride (TiN) by micro-arc oxidation (MAO), whereas TiN was prepared by plasma nitriding on commercially pure (Cp) titanium. The surface roughness of the N-TiO2 coating was greater than that of the TiO2 coating due to different MAO processing parameters. The band gap energy of N-TiO2 coating was reduced to 2.92 eV compared to TiO2 coating. The band gap energy reduction of N-TiO2 was attributed to nitrogen doping and the mixture of anatase, rutile and new phase (TiN0.30). The photoluminescence study demonstrated that the recombination rate of photo-generated electron–hole pairs of TiO2 was significantly suppressed after doping with nitrogen. N-TiO2 exhibited higher photocatalytic activity towards methylene blue dye degradation than to pure TiO2 coating. The recyclability test of N-TiO2 coating showed constant photocatalytic efficiency after the fourth run. Hence, N-TiO2 porous coating could be a promising material for immobilised solar photocatalytic applications.

PHOTOCATALYTIC AND ANTIBACTERIAL ACTIVITY OF TITANIUM, FLUORINE AND SILVER CO-SUBSTITUTED HYDROXYAPATITE

Synthetic hydroxyapatite (HA), an analogue of the mineral component of bone tissue has been widely used in medicine as bone replacing material. To impart specific properties, HA can be chemically modified by anionic and cationic substitutions during synthesis. Thus the present study was focused in synthesizing nanocrystalline Ti, Ag and F co-substituted HA by microwave synthesis. The prepared powders were characterized by XRD and FTIR for their crystal size, cystallinity and functional groups respectively. XRD spectra reveal that crystal size of prepared powders was in the range of 21–25 nm in as synthesized condition and 45–51 nm in 900 ˚C heat-treated condition. Complete decomposition of HA to tri calcium phosphate was observed for Ti substituted HA powder after heat-treatment. Addition of F improved the thermal stability of Ti substituted HA as indicated by predominant phase of HA after heat-treatment. The photocatalytic activity of co-substituted HA powders was examined by degradation of methylene blue (5 × 10−5 M concentration) under visible light irradiation and the results were compared with pure HA. The degradation efficiency of co-substituted HA with respect to methylene blue was twice as high as that of pure HA. Ti and Ag has improved the visible light photocatalytic activity of HA, further F co-substitution has not affected the photocatalytic activity of substituted HA. The antibacterial effect of prepared powders was observed against 1 × 105 cells/mL of Escherichia coli using spread plate method at 24 h incubation period. Ag co-substituted HA showed complete inhibition of growth of Escherichia coli. Thus, among Ti, Ti-F, Ti-F-Ag substituted HA powders, Ti-F-Ag co-substituted HA with excellent visible light photocatalytic activity and anti-bacterial property is expected to be a potential candidate for biomedical applications.

Effect of Plasma Electrolytic Surface Treatment on the Corrosion Characteristics of the Ti-6Al-4V in Acidic, Industrial and Marine Environments

Titanium and its alloys find wide range of applications in aerospace, marine and automobile industries due to their excellent properties like high strength to weight ratio and good mechanical behaviour. Accordingly, the structural parts made of these alloys are being exposed to different corrosive environments. Therefore, the electrochemical stability of these structural parts needs to be significantly improved for their extended life time and effective functioning. The objective of the present work is to examine the effect of plasma electrolytic surface treatment in improving the corrosion resistance of Ti-6Al-4V in simulated acidic (0.5M H2SO4), marine (3.5% NaCl) and sulphur containing industrial (0.5M Na2SO4) environments. PEO is a relatively new technique for producing ceramic coatings on light metal alloys by employing higher voltage and current than anodizing. The Ti-6Al-4V was surface treated by plasma electrolytic oxidation (PEO) technique for 12 min under optimized conditions of electrical processing parameters and electrolyte chemistry. The logically selected electrolyte system consisting of 10 g of tri-sodium ortho phosphate (Na3PO4.12H2O), 2 g of sodium meta silicate (Na2SiO3.9H2O) and 2 g of potassium hydroxide (KOH) in 1 L of double distilled water was employed. The decisively optimized electrical parameters were fixed as 75% for the duty cycle, 1500 Hz for the pulse frequency and 0.1 A/cm2 for the current density. The phase composition of the resulted coating was analyzed by the X-ray diffraction (XRD) technique. The coating thickness and the elemental composition of the coating were assessed using a scanning electron microscope (SEM) equipped with energy dispersive spectroscopy (EDS). The corrosion characteristics were determined by potentiodynamic polarization and electrochemical impedance spectroscopic (EIS) measurements. The XRD results demonstrated that the resulted coatings consisted of both anatase and rutile phases. The SEM results showed a coating thickness of about 15 µm and a canal like surface morphology with inter-connected open pores over the coating surface. The potentiodynamic polarization test results, in general, showed a minimum of about two orders of magnitude improvement in the corrosion resistance of the treated Ti-6Al-4V compared to that of the untreated in all the three corrosive environments. The EIS test results exhibit comparatively higher AC impedance and higher bode angle over the entire frequency range indicating an improved corrosion resistance of the surface treated Ti-6Al-4V. Thus the plasma electrolytic surface treatment with optimized process parameters, made the Ti-6Al-4V electrochemically stable by significantly improving its corrosion resistance in all the three environmental conditions.

The Role of Electrolyte Additives on the Corrosion Behavior of Ceramic Coatings Formed on ZM21 Magnesium Alloy by Plasma Electrolytic Oxidation

The present study emphasizes the effect of addition of sodium citrate (C6H5Na3O7.2H2O) and sodium tungstate (Na2WO4.2H2O) to a silicate based electrolyte system on the corrosion behavior of PEO treated ZM21 magnesium alloy. The phase composition of the as-developed coating was evaluated by X-ray diffraction (XRD) analysis, while its surface morphology, thickness and elemental distribution were observed using scanning electron microscopy (SEM) and energy-dispersive spectroscopy (EDS). Potentiodynamic polarization tests were done in 3.5 wt% NaCl solution to analyze the corrosion behavior of the ceramic coatings in simulated marine environment. The results of XRD showed that the phase composition of all coatings comprised of Mg2SiO4 and MgO irrespective of the additive used. In addition to Mg, Si and O, the presence of W, C in EDS spectrum indicated that these elements were incorporated into the coating from the electrolyte system containing tungstate and citrate. The corrosion test results revealed that the PEO coatings obtained in tungstate containing electrolyte solution showed higher corrosion resistance than those formed in citrate containing electrolyte solution.

Experimental Investigation on Synthesis of Nanocrystalline Hydroxyapatite by the Mechanochemical Method

Mechanochemical synthesis is a simple and effective method to prepare ceramic compounds with nanosize. The present work was aimed at investigating the application of the mechanochemical method to synthesize nanocrystalline hydroxyapatite (HA). The shortest milling time required for synthesizing HA, using Ca (OH)2 and (NH4)2HPO4 as precursor materials was also established. The synthesized samples were characterized using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and transmission electron microscopy (TEM) to determine the phases evolved, functional groups present and to assess the size and morphology of the particles, respectively. Further, the thermal stability of the synthesized powders was investigated by heating to a temperature of 900 °C with a dwell time of 2 h. The broadening of the XRD peaks was used to find out the crystallite size and Williamson-Hall plots were used to estimate the lattice strain. The XRD and FTIR results demonstrated that the complete formation of the HA phase by mechanochemical method has started within a milling time of 30 min using Ca (OH)2 and (NH4)2HPO4 as precursors and the Ca/P ratio of the HA increased with increasing milling time. The TEM micrographs demonstrated that the HA particles are nanosized, non-spherical and highly agglomerated.