A study on the phase transformation of the nanosized hydroxyapatite synthesized by hydrolysis using in situ high temperature X-ray diffraction

The biodegradable hydroxyapatite (HA) was synthesized by hydrolysis and characterized using high temperature X-ray diffraction (HT-XRD), differential thermal analysis and thermogravimetry (DTA/TG), and scanning electron microscopy (SEM). The in situ phase transformation of the HA synthesized from CaHPO₄·2H₂O (DCPD) and CaCO₃ with a Ca / P = 1.5 in 2.5 M NaOH_(aq) at 75 °C for 1 h was investigated by HT-XRD between 25 and 1500 °C. The HA was crystallized at 600 °C and maintained as the major phase until 1400 °C. The HA steadily transformed to the α-tricalcium phosphate (α-TCP) which became the major phosphate phase at 1500 °C. At 700 °C, the minor CaO phase appeared and vanished at 1300 °C. The Na⁺ impurity from the hydrolysis process was responsible for the formation of the NaCaPO₄ phase, which appeared above 800 °C and disappeared at 1200 °C.     

Characterization and synthesis of KTa0.1Nb0.9O3 particles via high temperature mixing method under hydrothermal conditions

KTa_0.1Nb_0.9O₃ (KTN) particles with an orthorhombic perovskite structure have been synthesized via a high temperature mixing method (HTMM) under hydrothermal conditions. The obtained samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), transmission electron microscopy (TEM), selected area electron diffraction (SAED), and high-resolution transmission electron microcopy (HRTEM). The influence of alkaline concentration and solvent composition on the phase structure and morphology of the obtained powders was investigated. The results show that the well-crystallized KTN powders with sizes of 200–500 nm are successfully prepared at temperatures as low as 240 °C when the KOH concentration is 2.0 M and the isopropanol/water (I/W) volume ratio equals to 100/0.     

Carbonate loss from two magnesium-substituted carbonated apatites prepared by different synthesis techniques

This study was aimed at the investigation of the thermal stability of Mg-substituted carbonated apatites over the wide temperature range. Two different apatites were studied, which were prepared by either precipitation from aqueous solution or by solid–liquid interaction. The following methods were employed: FTIR spectroscopy of the condensed gas phase to evaluate the CO and CO₂ release with increasing temperature, FTIR of the solid residue after heating, XRD analysis, thermogravimetry and scanning electron microscopy. Decomposition behavior was shown to depend significantly on the synthesis method. Wet-synthesized powders are significantly less thermally stable compared with those prepared by solid–liquid interaction. Intensive release of carbon oxides from the former was observed at 300 °C, whereas the latter powder was relatively stable up to temperature about 1000 °C.     

Biomimetic synthesis of hierarchical crystalline hydroxyapatite fibers in large-scale

Crystalline hierarchical hydroxyapatite [Ca₁₀(PO₄)₆(OH)₂, HAp)] fibers were successfully synthesized via a biomimetic route by using cotton cloth as a natural bio-template. The effects of pH value, aging time, ultrasonic cleaning time, and calcination temperature on the purity and morphology of the resulting hydroxyapatite (HAp) were monitored by scanning election microscope (SEM), X-ray diffraction (XRD), and infrared spectrophotometer (IR) to obtain an optimized reaction condition, namely, pH 9, ultrasonic cleaning for 1 min, aging for 24 h, and calcination at 600 °C for 4 h. We found that the natural cellulose could not only control the morphology of HAp but also lower its phase transformation temperature. The impact of this method lies in its low cost and successful production of large-scale patterning of three-dimensional hierarchical HAp fibers.     

Synthesis and characterization of nanocrystalline Nd3+-doped gadolinium scandium aluminum garnet powders by a gel-combustion method

Nd³⁺-doped gadolinium scandium aluminum garnet (Nd:GSAG) precursor was synthesized by a gel combustion method using metal nitrates and citric acid as raw materials. The structure and morphology of the precursor and the sintered powders were studied by means of X-ray diffraction (XRD), infrared spectroscopy (IR) and transmission electron microscopy (TEM). The results showed that the precursor transformed into pure GSAG polycrystalline phase at about 800 °C, and the powders sintered at 800–1000 °C were well-dispersed with average particle sizes in the range of 30–80 nm. Optical properties of Nd:GSAG nano-powders were characterized by using photoluminescence spectroscopy. The highest photoluminescence intensity was achieved for the powder sintered at 900 °C.     

Preparation and characterization of selenite substituted hydroxyapatite

Selenite-substituted hydroxyapatite (Se-HA) with different Se/P ratios was synthesized by a co-precipitation method, using sodium selenite (Na₂SeO₃) as a Se source. Selenium has been incorporated into the hydroxyapatite lattice by partially replacing phosphate (PO₄^3 ?) groups with selenite (SeO₃^2 ?) groups. X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), and transmission electron microscopy (TEM) techniques reveal that substitutions of phosphate groups by selenite groups cause lower carbonate groups occupying at phosphate sites and change the lattice parameters of hydroxyapatite. The powders obtained are nano-crystalline hydroxyapatite when the Se/P ratios are not more than 0.1. The particle shape of Se-HA has not been altered compared with selenite-free hydroxyapatite but Se-incorporation reduces the crystallite size. The crystallinity was reduced as the Se/P ratios increased until amorphous phase (Se/P = 0.3) appeared in the Se-HA powder obtained, and then another crystal phase presented as calcium selenite hydrate (Se/P = 10). In addition, the sintering tests show that the Se-HA powders with the Se/P ratio of 0.1 have thermal stability at 900 °C for 2 h; hence they have great potential in the fabrication of bone repair scaffolds.     

Coral-like hydroxy sodalite particles from rice husk ash as silica source

Coral-like hydroxy sodalite (HS) particles were prepared from rice husk ash as silica source in the presence of other aqueous-based precursor materials following a simple process under hydrothermal condition at 90 °C for 15 h. The particles obtained at 90 °C for different times (6, 10 and 15 h) were characterized by X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy and field emission scanning electron microscopy (FESEM). The HS crystals along with a small amount of zeolite A particles were observed at 90 °C/6 h while phase pure HS particles were obtained at 90 °C for 10 and 15 h. The characteristic vibration bands of the HS particles were confirmed by FTIR spectroscopy. FESEM images showed that the HS particles obtained at 90 °C/15 h were coral-like morphology which were formed through the self-assembly of the smaller particles generated at the initial stage of reaction (6 and 10 h) under the same experimental conditions. A proposed mechanism for the formation of coral-like HS particles was also illustrated.     

Properties of sintered glass-ceramics prepared from plasma vitrified air pollution control residues

Air pollution control (APC) residues, obtained from a major UK energy from waste (EfW) plant, processing municipal solid waste, have been blended with silica and alumina and melted using DC plasma arc technology. The glass produced was crushed, milled, uni-axially pressed and sintered at temperatures between 750 and 1150 °C, and the glass-ceramics formed were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Mechanical properties assessed included Vickers's hardness, flexural strength, Young's modulus and thermal shock resistance. The optimum sintering temperature was found to be 950 °C. This produced a glass-ceramic with high density (～2.58 g/cm³), minimum water absorption (～2%) and relatively high mechanical strength (～81 ± 4 MPa). Thermal shock testing showed that 950 °C sintered samples could withstand a 700 °C quench in water without micro-cracking. The research demonstrates that glass-ceramics can be readily formed from DC plasma treated APC residues and that these have comparable properties to marble and porcelain. This novel approach represents a technically and commercially viable treatment option for APC residues that allow the beneficial reuse of this problematic waste.     

Development of NiFe-CNT and Ni3Fe-CNT nanocomposites by mechanical alloying

NiFe-CNT and Ni₃Fe-CNT nanocomposites were fabricated by high energy mechanical alloying method. X-ray diffraction (XRD) analysis, scanning electron microscopy (SEM) and optical microscopy were employed for evolution of phase composition, morphology and microstructure of the powder particles. Ball milled powders were heat treated at 500 °C for 1 h to release the milling induced stresses. Bulk samples were prepared by sintering of cold pressed (300 MPa) samples at 1040 °C for 1 h. XRD patterns of powders, as-milled and after annealing at 500 °C did not show any peak related to CNTs or excess phases due to the interaction between CNTs and matrix. SEM micrographs showed that the addition of CNTs caused a reduction of powder particles size. The hardness value of as-milled NiFe and Ni₃Fe powders reach to 660 and 720 HV, respectively. According to optical microscopy evaluations, the amount and size of the porosities of the composites bulk samples decreased in comparison with matrix ones.     

Bioactivity of calcium phosphate coatings prepared by electrodeposition in a modified simulated body fluid

The purpose of this study was to investigate bioactivity of calcium phosphate coatings prepared by electrodeposition in a modified simulated body fluid (SBF). Calcium phosphates were electrodeposited on commercially pure titanium substrates in the modified SBF at 60 °C for 1 h maintaining the cathodic potentials of − 1.5 V, − 2 V, and − 2.5 V (vs. SCE). Subsequently, the calcium phosphate coatings were transformed into apatites during immersion in the SBF at 36.5 °C for 5 days. The apatites consisted of needle-shaped crystallites distributed irregularly with different grain sizes. As the coatings were electrodeposited at higher cathodic potential, the crystallite of the apatites got denser and the grain sizes of the apatites became bigger during subsequent immersion in the SBF. However, as the coatings were electrodeposited at higher cathodic potential, the coatings were transformed into apatites with lower crystallinity and the Ca/P atomic ratio of the apatites got higher than 1.67, that of stoichiometric hydroxyapatite, after subsequent immersion in the SBF. In addition, CO₃²⁻ ions contained in the modified SBF were incorporated in the calcium phosphate coating during electrodeposition and had an influence on transforming the calcium phosphate into bonelike apatite during subsequent immersion in the SBF showing that CO₃²⁻ incorporated in the apatites disturbed crystallization of the apatites. These results revealed that the coating electrodeposited at − 2.0 V (vs. SCE) in the modified SBF containing CO₃²⁻ ions was the most bioactive showing transformation into carbonate apatite similar to bone apatite.     

Solute cluster size effect on the fatigue crack propagation resistance of an underaged Al–Cu–Mg alloy

The effect of Cu–Mg cluster size and number density on the fatigue fracture behavior of Al–Cu–Mg alloy with various aging conditions was investigated by means of transmission electron microscopy (TEM), atom probe tomography (APT), scanning electron microscopy (SEM) and fatigue testing. Results showed that the fatigue crack propagation (FCP) resistances of 170 °C/1 h and 170 °C/8 h samples were higher than that of 170 °C/0.5 h sample due to increased number density of great size Cu–Mg co-clusters (>50 atoms). These large clusters were harder to dissolve during cycle deformation, thus reduced the cyclic softening effect and enhanced the FCP resistance. Moreover, as aging prolonged, the critical shear stress (τ_m) of co-clusters by modulus hardening increased from 10.2 (MPa) in 170 °C/0.5 h sample to 12.4 in 170 °C/1 h sample and 12.1 in 170 °C/8 h sample. Thus the force required for the movement of dislocations impeded by co-clusters, as well as the resistance of FCP caused by co-clusters, in 170 °C/1 h and 170 °C/8 h sample was higher than that in 170 °C/0.5 h sample. The 170 °C/8 h sample possessed the lower FCP resistance than 170 °C/1 h sample because of the existence of S′ phase. S′ phase was a kind of semi-coherent unshearable precipitate and hence reduced the planar-reversible slip.     

Carbonate and fluoride incorporation in synthetic apatites: Comparative effect on physico-chemical properties and in vitro bioactivity in fetal bovine serum

CO₃- and/or F-substituted apatites have been considered as potential bone substitution material for dental and orthopedic applications. The objective of this study was to compare physico-chemical properties and in vitro bioactivity in fetal bovine serum (FBS) of apatites containing CO₃ and/or F. The results showed that CO₃ and F in apatites have opposite effects on crystallinity and solubility. Calcium deficient hydroxyapatite (HA) and F-substituted apatite (FA) partially transformed to beta-tricalcium phosphate (β-TCP) at temperature 950 °C. After immersion in FBS for 10 days, calcium deficient HA, FA, and CO₃-substituted apatite (CHA) and CO₃- and F-substituted apatite (CFA) pellet surfaces all showed formation of apatite.     

Effect of phase transformation and intermetallic compounds on the microstructure and tensile strength properties of diffusion-bonded joints between Ti–6Al–4V and AISI 304L

The occurrence of a phase transformation and the effect of intermetallic compounds on the microstructure and tensile strength properties of diffusion-bonded (DB) joints between Ti–6Al–4V and AISI 304L were studied in the temperature range of 875–950 °C with an interval of 25 °C, a bonding time of 60 min and pressures of 4 MPa and 8 MPa. A maximum tensile strength of 242.6 MPa, was observed for diffusion-bonded joints that were processed at a temperature of 900 °C, bonded for 60 min at a pressure of 4 MPa and annealed for 2 h at 750 °C. Optical microscopy and scanning electron microscopy (SEM) were used to examine the grain growth and the fine details of the interface structure. Energy dispersive X-ray analysis (EDAX) and X-ray diffraction analysis (XRD) revealed the existence of intermetallic compounds and corroborated the phase transformation.     

Synthesis and characterization of nanoporous hydroxyapatite using cationic surfactants as templates

Nanoporous hydroxyapatite was synthesized utilizing cationic surfactants as templates. The effects of cetyltrimethylammonium bromide and reaction temperatures on the phase and morphology of HA were investigated by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and transmission electron microscopy (TEM). The thermal stability of nanoporous structures was studied by XRD and thermal analyzers (TGA/DTA), while the pore structure of HA was observed using high resolution TEM. It was found that the pore size was about 1 nm, and the pore structure of HA was thermally stable up to 700 °C and the pore size did not change with reaction temperature and CTAB:PO₄^3? ratio. The possible formation mechanism of nanoporous structure was proposed.     

Lead sulfide quantum dots embedded in mesoporous material by ion-exchange method

We present a new, simple procedure for the synthesis of lead sulfide quantum dots (QDs) via an ion-exchange reaction. The samples were obtained by sulfidation of the Pb²⁺ ion-exchanged MCM-41 in a Na₂S solution at 25 °C. The final product was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), UV–vis spectroscopic, infrared spectroscopy (IR) and BET (Brunauer–Emmert–Teller) experiments. Exciton absorption peak at higher energy than the fundamental absorption edge of bulk lead sulfide indicate quantum confinement effects in quantum dots as a consequence of their small size. XRD pattern showed the presence of PbS QDs with the size of ~ 2 nm.     

Nanostructured hydroxyapatite powders produced by a flame-based technique

In this work we reported the production of hydroxyapatite (HA) powder, one of the most studied calcium phosphates in the bioceramics field, using a cost-effective apparatus, composed by three major components: the atomization device, the pilot and main flames and finally the powder collector system. Calcium acetate and ammonium phosphate, diluted in ethanol and water, were used as salts in the precursor solution. The Ca/P molar ratio in the precursor solution was 1.65, equivalent to biological hydroxyapatite. After its production and collection, HA powder was calcined at 600 °C for 2 h. X-ray diffraction analysis pointed to the formation of crystalline hydroxyapatite powders. Carbonate was identified in the powders by Fourier-transform infrared (FTIR) spectroscopy. Scanning electronic microscopy (SEM) showed that the powders were composed of spherical primary particles and secondary aggregates, with the morphology unchanged after calcination. By transmission electronic microscopy (TEM), it was observed that the crystallite size of the primary particles was 24.8 ± 5.8 nm, for the calcined powder. The specific surface area was 15.03 ± 6.4 and 26.50 ± 7.6 m²/g, for the as-synthetized and calcined powder respectively.     

In situ fabrication of titanium carbide particulates-reinforced iron matrix composites

Titanium carbide (TiC) particulates-reinforced iron matrix composites were prepared by in situ fabrication method combining an infiltration casting with a subsequent heat treatment. The effects of different heat treatment times (0, 1, 6 and 11 h) at 1138 °C on the phase evolution, microstructural features, and properties of the composites were investigated. The as-prepared composites were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and microhardness and wear resistance tests. The XRD results showed that the composites consisted of graphite, α-iron and titanium carbide after heat treatment at 1138 °C for 11 h. The SEM observation revealed that the formed TiC particulates were homogenously distributed in the iron matrix. The average microhardness of the composite heat treated at 1138 °C for 6 h increased depending upon the region: 209 HV_0.1 (iron matrix) < 787 HV_0.1 (titanium wire) < 2667 HV_0.1 (composite region). After being heat treated at 1138 °C for 11 h, the composite indicated no considerable change in microhardness value, and the average microhardness of the composite region was about 2354 HV_0.1. The highest microhardness value obtained for the composite region was due to the formation of titanium carbide particulates as reinforcement phase within the iron matrix. Relative wear resistance was determined by a pin-on-disc wear test technique under different loads, and as a result, the composites containing higher volume fraction of hard titanium carbide particulates presented higher wear resistance compared with the unreinforced gray cast iron.     

Low temperature synthesis of hydroxyapatite nano-rods by a modified sol–gel technique

Hydroxyapatite (HAp) nano-rods were successfully synthesized by a modified sol–gel method using a solution of CaCl₂·2H₂O in water, along with a solution of H₃PO₄ in triethylamine and NH₄OH as starting materials. The Ca/P molar ratio was maintained at 1.67. The sol obtained was dried in an oven for 2 days at 100 °C after being dialyzed for 12 h. Pellets were made from the crystalline powders and immersed in simulated body fluid (SBF) to check its biocompatibility after 15, 45 and 180 days of immersion. The HAp powders and pellets were characterized by X-Ray Diffraction crystallography (XRD), Fourier transform Infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and Transmission electron microscopy (TEM). The HAp nano-rods had an average diameter of 25 nm and length 110–120 nm. Immersion of the HAp pellets in SBF led to the formation of a highly porous interconnecting HAp layer on the surface. The porosity increased with increase in immersion time.     

Photoluminescent properties of LiInO2 nanocrystals

Synthesis and luminescence properties of LiInO₂ nanocrystals by the sol–gel process were investigated. The products were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), photoluminescence spectroscopy and absorption spectra. The well-crystallized tetragonal LiInO₂ can be obtained by heat treatment above 600 °C from XRD. The excitation wavelengths at about 246 nm were associated with charge transfer between In and O with In³⁺ ions in octahedral coordination. The PL spectra excited at 246 nm have a broad and strong emission band maximum at 391 nm, corresponding to the self-activated luminescence. The optical absorption spectra of the 600 °C sample exhibited the band gap energies of 3.7 eV.     

Preparation of nanostructured nickel aluminate spinel powder from spent NiO/Al2O3 catalyst by mechano-chemical synthesis

In this paper, the possibility of mechano-chemical synthesis, as a single step process for preparation of nanostructured nickel aluminate spinel powder from NiO/Al₂O₃ spent catalyst was investigated. Powder samples were characterized in terms of composition, morphology, structure, particle size and surface area using complementary techniques such as X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), differential thermal analysis (DTA) and volumetric adsorption of nitrogen. It was found that formation of spinel was possible after 60 h of milling with no heat treatment. Additionally, influence of mechanical activation on the heat treatment temperature was discussed. It was observed that heat treatment of 15 h milled sample at 1100 °C is enough to produce nickel aluminate spinel. A product of direct mechanical milling showed higher value of surface area (42.3 m²/g) and smaller crystallite size (12 nm) as compared to the heat treated product.