Lead and copper removal from aqueous solutions by porous glass derived calcium hydroxyapatite

A porous glass was prepared by sintering Na₂O-CaO-B₂O₃ glass powder with powdered sodium chloride. Subsequently, the sodium chloride was dissolved in water resulting in a highly porous material. A sample was prepared consisting of 60 vol% glass and 40 vol% salt which both had particle sizes <100 and 400-500 μm, respectively. The sample was sintered at a temperature of 580 °C for 15 min which resulted in an optimum structure with 57.5% porosity and 0.944 MPa compressive strength. Amorphous calcium hydroxyapatite was formed by immersing these materials in 0.1 M K₂HPO₄ solutions at room temperature for 1 day. The porous glass derived hydroxyapatite matrix was then processed for removing lead and copper ions from aqueous solutions. The results showed that the glass derived calcium hydroxyapatite matrix effectively immobilizes lead and copper ions in solution. The adsorption mechanism was investigated by the X-ray Diffraction (XRD) and Scanning Electron Microscopy including Energy Dispersive X-Ray Spectrometry (SEM-EDX).     

Structural and magnetic properties of glass-ceramics containing silver and iron oxide

Glass-ceramics with a nominal composition of 25SiO₂–(50 − x)CaO–15P₂O₅–8Fe₂O₃–2ZnO–xAg (where x = 0, 2 and 4 mol%) have been prepared. Structural features of glass-ceramics have been investigated using X-ray diffraction (XRD) and scanning electron microscope (SEM) techniques. Magnetic properties were studied using vibrating sample magnetometer and Mössbauer spectroscopy. Ca₃(PO₄)₂, hematite and magnetite are formed as major crystalline phases. The microstructure reveals the formation of 25–30 nm size particles. Mössbauer spectroscopy has shown the relaxation of magnetic particles. Saturation magnetization value is increased with an increase of Ag content up to 4 mol%, which has been attributed to the formation of magnetically ordered particles. The antibacterial response was found to depend on Ag ions concentration in the glass matrix and samples with 4 mol% Ag in glass matrix have shown effective antibacterial activity against Escherichia coli.     

ZnFe2O4 thin films from a single source precursor by aerosol assisted chemical vapour deposition

A single source heterobimetallic complex [Fe₂(acac)₄(dmaeH)₂][ZnCl₄] (1) (acac = 2,4-pentanedionate, dmaeH = N,N-dimethylaminoethanol), was synthesized in high yield. The complex was analyzed by melting point, Fourier transfer infrared spectroscopy (FT-IR) and thermogravimetric analysis (TGA). The structure of the cation was established by single crystal X-ray analysis on a derivative, [Fe₂(acac)₄(dmaeH)₂][ZnCl₃(THF)]₂·THF (1a) (THF = tetrahydrofuran). TGA analysis showed that complex (1) undergoes facile thermal decomposition at 450 °C to give ZnFe₂O₄ residue. In-house designed aerosol assisted chemical vapour deposition equipment was used to deposit thin films of ZnFe₂O₄ on fluorine doped SnO₂ coated conducting glass substrate at 450 °C. X-ray diffraction analysis proved the formation of crystalline ZnFe₂O₄ phase and scanning electron microscopy revealed the film morphology with well defined crystalline particles evenly distributed in the range 150-200 nm. The indirect and direct bandgap energies of the thin films were estimated to be 1.76 and 2.10 eV, respectively.     

Apatite phosphates containing heterovalent cations and their application in Knoevenagel condensation

Apatite structure type ortho phosphates of the formula NaLaCa₃(PO₄)₃OH and NaLaSr₃(PO₄)₃OH have been synthesized via a simple solution route. The compounds are isostructural with calcium hydroxyapatite. The phases are characterized by powder X-ray diffraction method and infrared spectroscopy. The unit cell parameters are: for NaLaCa₃(PO₄)₃OH, a = 9.457(3) and c = 6.90(1) Å and for NaLaSr₃(PO₄)₃OH, a = 9.720(3) and c = 7.23(3) Å, respectively. Knoevenagel condensation of selected aldehydes and molecules with activated methylene group is carried out using the phosphates as solid supports. Both phases facilitated the condensation reaction at room temperature in the absence of a solvent. An increase in the yield of the products is noticed when the supports are used with water.     

Synthesis and crystallographic study of Pb-Sr hydroxyapatite solid solutions by high temperature mixing method under hydrothermal conditions

The solid solutions in the system of Pb and Sr hydroxyapatite, Sr_10−xPb_xHAp (x = 0-10), were successfully synthesized by high-temperature mixing method (HTMM) at 160 °C for 12 h under hydrothermal conditions. The samples were characterized by X-ray diffraction, chemical analysis and electron microscopic observation, and the site of the metal ions in the solid solutions was analyzed with the Rietveld method. The lattice constants, both a and c, of the solid solutions varied linearly with Pb content. It was found that Pb ions in the solid solutions preferentially occupied the M(2) site in the apatite structure. HTMM gives Sr-Pb HAp solid solutions much better crystallization. However, due to the formation of intermediate compound of Pb₃O₂(OH)₂ in the Pb(NO₃)₂·4H₂O solution before mixing with (NH₄)₂HPO₄ solution at 160 °C, HTMM causes the decrease of crystallization of the samples with high Pb content.     

Aerosol deposition of silicon-substituted hydroxyapatite coatings for biomedical applications

Silicon-substituted hydroxyapatite (Si-HA) coatings on commercially pure titanium (Ti) were prepared by aerosol deposition using Si-HA powders. Si-HA powders with the chemical formula Ca₁₀(PO₄)_6 − x(SiO₄)_x(OH)_2 − x, having silicon contents up to x = 0.5 (1.4 wt.%), were synthesized by solid-state reaction of Ca₂P₂O₇, CaCO₃, and SiO₂. The Si-HA powders were characterized by X-ray diffraction (XRD), X-ray fluorescence spectrometry, and Fourier transform infrared spectroscopy. The corresponding coatings were also analyzed by XRD, scanning electron microscopy, and electron probe microanalyzer. The results revealed that a single-phase Si-HA was obtained without any secondary phases such as α- or β-tricalcium phosphate for both the powders and the coatings. The Si-HA coating was about 5 µm thick, had a dense microstructure with no cracks or pores, and showed a high adhesion strength ranging from 28.4 to 32.1 MPa. In addition, the proliferation and alkaline phosphatase activity of MC3T3-E1 preosteoblast cells grown on the Si-HA coatings were significantly higher than those on the bare Ti and pure HA coating. These results revealed the stimulatory effects induced by silicon substitution on the cellular response to the HA coating.     

Nanocrystallization of ferroelectric lithium niobate in LiNbO3-SiO2 glasses

Transparent glasses in the (100-x)LiNbO₃-xSiO₂ system where 20 ≤ × ≤ 35, were produced by conventional melt-quenching technique. The quenched samples were amorphous as proved by X-ray diffraction (XRD) technique. Annealing of the quenched samples at temperatures ranging from 580 to 975 °C resulted in the precipitation of lithium niobate nano-crystals. Scanning electron microscopy (SEM) showed the presence of randomly oriented LiNbO₃ nano-crystals dispersed in a continuous glass matrix. The relative dielectric constant (ε_r) was in the range of 80 to 180 and increased with increasing LiNbO₃ concentration. The glass ceramic samples annealed at temperatures up to 600 °C are fully transparent.     

Si-substituted hydroxyapatite nanopowders: Synthesis, thermal stability and sinterability

Synthetic hydroxyapatites incorporating small amounts of Si have shown improved biological performances in terms of enhanced bone apposition, bone in-growth and cell-mediated degradation.This paper reports a systematic investigation on Si-substituted hydroxyapatite (Si 1.40 wt%) nanopowders produced following two different conventional wet methodologies: (a) precipitation of Ca(NO₃)₂·4H₂O and (b) titration of Ca(OH)₂. The influence of the synthesis process on composition, thermal behaviour and sinterability of the resulting nanopowders is studied.Samples were characterised by electron microscopy, induced coupled plasma atomic emission spectroscopy, thermal analysis, infrared spectroscopy, N₂ adsorption measurements, X-ray diffraction and dilatometry. Semicrystalline Si-substituted hydroxyapatite powders made up of needle-like nanoparticles were obtained, the specific surface area ranged between 84 and 110 m²/g. Pure and Si-substituted hydroxyapatite nanopowders derived from Ca(NO₃)₂·4H₂O decomposed around 1000 °C. Si-substituted hydroxyapatite nanopowders obtained from Ca(OH)₂ were thermally stable up to 1200 °C and showed a distinct decreased thermal stability with respect to the homologous pure sample. Si-substituted hydroxyapatites exhibited higher sintering temperature and increased total shrinkage with respect to pure powders. Nanostructured dense ceramics were obtained by sintering at 1100 °C Si-substituted hydroxyapatites derived from Ca(OH)₂.     

Influence of glass addition and sintering temperature on the structure,mechanical properties and dielectric strength of high-voltage insulators

Soda-lime glass as a substituent for the feldspar was used to prepare high-tension electrical porcelain by standard chemical solid reaction technique. The effect of glass substitution and sintering temperature on the physical properties, microstructure, hardness, modulus of rupture, flexural strength and Dielectric breakdown strength were examined. Zero water absorption (WA %) and apparent porosity (AP %) were achieved for the samples with glass content >15 wt.% sintered at 1100 °C. The apparent density was found to increase with sintering temperature. The Vicker’s micro-hardness increased with both glass addition and sintering temperature. Both of the modulus of rupture (MOR) and flexural strength (σ_f) had maxima values at 15 wt.% glass addition. The structure and morphology were characterized by X-ray diffraction and scanning electron microscope (SEM). It showed the formation of mullite needles at sintering temperature of 1100 °C, which enhanced the mechanical and electrical properties of the porcelain. The dielectric breakdown strength increased with sintering temperature and glass addition. The highest dielectric strength was found at 10 wt.% of glass addition depending on the Na₂O and Fe₂O₃ content.     

Study of glass-nanocomposite and glass–ceramic containing ferroelectric phase

Transparent glass nanocomposite in the pseudo binary system (100 − x) Li₂B₄O₇–xBaTiO₃ with x = 0 and 60 (in mol%) were prepared. Amorphous and glassy characteristics of the as-prepared samples were established via X-ray powder diffraction (XRD) and differential scanning calorimetry (DSC) respectively. The precipitated BaTiO₃ nanocrystal phase embedded in the glass sample at x = 60 mol% was identified by transmission electron microscopic (TEM). The optical transmission bands at 598 and 660 nm were assigned to Ti³⁺ ions in tetragonal distorted octahedral sites. The precipitated Li₂B₄O₇, BaTi(BO₃)₂ and BaTiO₃ nanocrystallites phases with heat-treatment at 923 K for 6 h (HT923) in glass–ceramic were identified by XRD, TEM and infrared absorption spectroscopy. The as-prepared at x = 60 mol% and the HT923 samples exhibit broad dielectric anomalies in the vicinity of the ferroelectric-to-paraelectric transition temperature. The results demonstrate that the method presented may be an effective way to fabricate ferroelectric host and development of multifunctional ferroelectrics.     

Comparative study of the corrosion behaviour of plasma nitrocarburised AISI 4140 steel before and after post-oxidation

In this study, the corrosion behaviour of plasma nitrocarburised AISI 4140 steel before and after post-oxidation was investigated. Plasma nitrocarburising was carried out at 530 °C, 570 °C and 630 °C for 5 h in an atmosphere consisting of 80 vol.% N₂, 17 vol.% H₂ and 3 vol.% CO₂. After nitrocarburising, plasma post-oxidation was performed at 450 °C for 1 h in a gas mixture of 50 vol.% O₂ and 50 vol.% H₂. The microstructure of the treated samples was characterized using X-ray diffraction, scanning electron microscopy and surface roughness techniques. Dynamic polarization test was also used to evaluate the corrosion resistance of the samples. The results indicated that the compound layer was composed of ε-Fe_2–3(N, C) and γ′-Fe₄(N, C) phases. The amount of ε-Fe_2–3(N, C) phase increased as the treatment temperature rose from 530 °C to 570 °C and decreased at 630 °C. The X-ray diffraction patterns of post-oxidized samples confirmed the formation of the highest amount of magnetite after post-oxidation of samples that had been nitrocarburised at 570 °C as compared with the samples that had been treated at 530 °C and 630 °C. Nitrocarburising at 570 °C followed by post-oxidation also provided the highest corrosion resistance among all treatment conditions.     

Effect of ZrO2 addition on crystallization behaviour, porosity and chemical-mechanical properties of a CaO-TiO2-P2O5 microporous glass ceramic

2-6 mol% ZrO₂ was added to a base glass composition of P₂O₅ 31.25, CaO 43.75, TiO₂ 25 (mol%) at the expense of TiO₂. The prepared glasses were crystallized to bulk glass ceramics containing the major phases of β-Ca₃(PO₄)₂ and CaTi₄(PO₄)₆. DTA was utilized to determine the appropriate phase separation-nucleation and crystallization temperatures. The crystalline products and resulting microstructures were examined by XRD and SEM. The β-Ca₃(PO₄)₂ phase was dissolved out by leaching the resulting glass ceramics in HCl, leaving a porous skeleton of CaTi₄(PO₄)₆. It was shown that ZrO₂ addition resulted in reduction of volume porosity and mean pore diameter while the specific surface area was increased. The smallest median pore diameter and largest surface area were 8.6 nm and 32 m² g⁻¹ respectively obtained for the specimen containing 6 mol% ZrO₂. The ZrO₂ addition also improved the chemical durability and bending strength of porous glass ceramics.     

Synthesis of nano-sized hydroxyapatite powders through solution combustion route under different reaction conditions

Calcium hydroxyapatite, Ca₁₀(PO₄)₆(OH)₂ (HAp) was synthesized by combustion in the aqueous system containing calcium nitrate-diammonium hydrogen orthophosphate with urea and glycine as fuels. These ceramics are important materials for biomedical applications. Thermo-gravimetric and differential thermal analysis were employed to understand the nature of synthesis process during combustion. Effects of different process parameters namely, nature of fuel (urea and glycine), fuel to oxidizer ratio (0.6-4.0) and initial furnace temperature (300-700 °C) on the combustion behavior as well as physical properties of as-formed powders were investigated. A series of combustion reactions were carried out to optimize the reaction parameters for synthesis of nano-sized HAp powders. The combustion temperature (T_f) for the oxidant and fuels were calculated to be 896 °C and 1035 °C for the stoichiometric system of urea and glycine respectively. The stoichiometric glycine-calcium nitrate produced higher flame temperature (both calculated and measured) and powder with lower specific surface area (8.75 m²/g) compared to the stoichiometric urea-calcium nitrate system (10.50 m²/g). Fuel excess combustion in both glycine and urea produced powders with higher surface area. Nanocrystalline HAp powder could be synthesized in situ with a large span of fuel to oxidizer ratio (φ) in case of urea system (0.8 < φ < 4) and (0.6 < φ < 1.5) for the glycine system. Calcium hydroxyapatite particles having diameters ranging between 20 nm and 120 nm could be successfully synthesized through optimized process variable.     

Synthesis and photoluminescence properties of Eu-doped γ-Ca3(PO4)2

Eu³⁺-doped (1% and 3%) γ-Ca₃(PO₄)₂ was synthesized by high-pressure and high-temperature experimental method and the samples were characterized by X-ray diffraction. The luminescence properties of samples were investigated by emission and excitation spectra. The excitation spectra of Eu³⁺-doped γ-Ca₃(PO₄)₂ showed that samples were mainly attributed to Eu³⁺–O²⁻ charge-transfer band at 270 nm, and some sharp lines were also attributed to Eu³⁺ f–f transitions in near-UV regions with the strongest peaks at 395 nm. Under the 395 nm excitation, the intense red emission peak at 611 nm was observed. The strongest line (395 nm) in excitation spectra of those phosphors matched well with the output wavelength of UV InGaN-based light-emitting diodes (LEDs) chip. The luminescent properties suggested that Eu³⁺-doped γ-Ca₃(PO₄)₂ might be regarded as a potential red phosphor candidate for near-UV LEDs.     

Study on Raman line at 1080.2 cm in ZnO thin films prepared under high RF power

ZnO thin films were prepared on glass or on homo-buffer/glass by a RF magnetron sputtering method at RF power of 100-550 W. The structural and Raman characteristics of the films were analyzed by X-ray diffraction and Raman scattering. There appeared a sharp peak of 1080.2 cm⁻¹ near the A₁(2LO) mode (1156 cm⁻¹) of ZnO in the Raman spectra when the RF power was higher than 300 W. In this case, the (100) peak of ZnO film appeared obviously. It was speculated that the Raman mode at 1080.2 cm⁻¹ was induced by the ordered distribution of Zn_i defects in ZnO lattice.     

Structural characterization and optical properties of Cd(1−x)MnxSe thin films

Stoichiometric bulk ingot materials of the ternary mixture Cd_(1−x)Mn_xSe (0.05 ≤ x ≤ 0.9) were prepared by direct fusion of the constituent elements in vacuum sealed silica tubes. X-ray diffraction studies indicate that the investigated samples exhibited a hexagonal structure. The lattice parameters varied linearly with Mn content, following Vegard's law. Thin films were deposited by thermal evaporation from the pre-synthesized ingot material, onto glass substrates. X-ray and electron diffraction studies on the as-deposited and annealed films revealed an amorphous-to-crystalline phase transition at T_a ≈ 423 K. EDAX studies on the prepared films show that the as-deposited films are nearly stoichiometric. The transmittance and reflectance of the deposited Cd_(1−x)Mn_xSe films were measured at normal light incident in the wavelength spectral range 500-2500 nm. Analysis of the transmittance spectra in the entire wavelength range allowed the determination of the refractive index. The dispersion parameters have been calculated, from which the static refractive index as well as static dielecric constant were calculated. Analysis of the absorption coefficient of the investigated films revealed the existence of both the allowed direct and forbidden direct optical transition mechanisms. The corresponding energies were estimated.     

Electrodeposition of SmS optical thin films on ITO glass substrate

SmS optical thin films were deposited on the surface of ITO glass with an electrodeposition method using aqueous solution containing SmCl₃·6H₂O and Na₂S₂O₃·5H₂O. The phase composition was analyzed by X-ray diffraction (XRD) and microstructure of the film was characterized by atomic force microscope (AFM). It is showed that SmS thin film could be obtained in the solution with n(Sm)/n(S) = 1:4, pH = 4.0 and annealing in Ar atmosphere at 200 °C for 0.5 h. The as-prepared thin films on the ITO glass exhibit a dense microstructure. The band gap of the thin film has been found to be 3.6 eV.     

Rapid formation of lead magnesium niobate-based ferroelectric ceramics via a high-energy ball milling process

Pyrochlore-free nano-sized 0.90Pb(Mg_1/3Nb_2/3)O₃(PMN)-0.10PbTiO₃(PT) and 0.65PMN-0.35PT powders were synthesized from oxides via a high-energy ball milling process. Single perovskite phase PMN-PT were readily formed from the oxide mixture after milling for only 2 h. The grain size calculated from X-ray diffraction (XRD) patterns of all samples is about 20 nm, which is in agreement with the observation from scanning electron microscopy (SEM) (20-50 nm). PMN-PT ceramics were obtained by sintering the milled powders at temperature from 1000 to 1100°C for 2 h. The dielectric, ferroelectric properties of the PMN-PT ceramics derived from the synthesized powders were comparable with the reported results in the literature.     

Low temperature aqueous chemical synthesis of CdS sensitized ZnO nanorods

Cadmium sulfide nanoparticles (CNPs) sensitized zinc oxide nanorod arrays (ZNRs) were synthesized in the two step deposition process at relatively low temperature. The vertically aligned ZNRs were grown on the conducting glass substrates (FTO) using aqueous chemical method, followed by the deposition of CNPs at 70 °C using chemical bath deposition (CBD) technique. The samples were characterized by optical absorption, X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), X-ray photoelectron spectroscopy (XPS) and photoluminescence spectroscopy (PL). Further, the photoelectrochemical (PEC) performance of ZNRs with and without CNPs sensitization was tested in Na₂S-NaOH-S and Na₂SO₄ electrolyte, respectively. When the CNPs are coated on the ZNRs, the optical absorption is enhanced and band edge is shifted towards visible region (525 nm) as compared with ZNRs (375 nm). The sample sensitized with CNPs shows higher photoelectrochemical (PEC) performance with maximum short circuit current of (I_sc) 2.60 mA/cm².     

Characterization of nanostructured photosensitive (NiS)x(CdS)(1−x) composite thin films grown by successive ionic layer adsorption and reaction (SILAR) route

Recently ternary semiconductor nanostructured composite materials have attracted the interest of researchers because of their photovoltaic applications. Thin films of (NiS)_x(CdS)_(1−x) with variable composition (x = 1-0) had been deposited onto glass substrates by the successive ionic layer adsorption and reaction (SILAR) method. As grown and annealed films were characterised by X-ray diffraction, scanning electron microscopy and EDAX to investigate structural and morphological properties. The (NiS)_x(CdS)_(1−x) films were polycrystalline in nature having mixed phase of rhombohedral and hexagonal crystal structure due to NiS and CdS respectively. The optical and electrical properties of (NiS)_x(CdS)_(1−x) thin films were studied to determine compsition dependent bandgap, activation energy and photconductivity. The bandgap and activation energy of annealed (NiS)_x(CdS)_(1−x) film decrease with improvement in photosensitive nature.