Solid state and solution synthesis of Ba(Mg1/3Ta2/3)O3: A comparative study

Ba(Mg_1/3Ta_2/3)O₃ [BMT] dielectric ceramics are prepared by solid state (one step, two step and molten salt synthesis) and wet chemical methods (precipitation, citrate gel and sol-gel). The formation mechanism of BMT in each synthesis technique is discussed. The formation temperature and particle size of the formed BMT were found to be much lesser (in nanometer range) for solution synthesized powders. It is found that synthesis by sol-gel method resulted in the formation of ultra pure nanopowders of BMT at about 600 °C with average crystallite size of about 18 nm where as in solid state synthesis the formation of BMT was formed at about 1100 °C with average crystallite size of 220 nm. On sintering these powders, densification and grain growth of the chemically derived powders were found to be lower than that of solid state synthesized BMT powder. This has resulted in a slight decrease in density and microwave dielectric properties of the solution synthesized BMT samples. It is found that the microwave dielectric properties improved with increase in the average grain diameter of the sintered BMT ceramics.     

Synthesis and characterization of nanocrystalline MgAl2O4 spinel via sucrose process

Nanocrystalline MgAl₂O₄ spinel powder was synthesized using metal nitrates and a polymer matrix precursor composed of sucrose and polyvinyl alcohol (PVA). The precursor and the calcined powders were characterized by simultaneous thermal analysis (STA), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), field emission scanning electron microscopy (FE-SEM) and transmission electron microscopy (TEM). According to XRD results, the inceptive formation temperature of spinel via this technique was between 600 and 700 °C. The calcined powder at 800 °C for 2 h has faced shaped morphology and its crystallite size is in the range of 8-12 nm. Further studies also showed that the amount of polymeric matrix to metal ions has significant influence on the crystallite size of synthesized magnesium aluminate spinel powder.     

Synthesis of nanocrystalline forsterite (Mg2SiO4) powder by combined mechanical activation and thermal treatment

This study investigates the synthesis of single-phase nanocrystalline forsterite powder by mechanical activation with subsequent annealing. To produce forsterite powder, a mixture of talc and magnesium oxide powders was first milled by a planetary ball mill, and then annealed at 1000 and 1200 °C for 1 h. The synthesized powder was characterized by X-ray diffraction (XRD), simultaneous thermal analysis (STA), scanning electron microscopy (SEM), and atomic absorption spectrometry (AAS). The initial temperature of forsterite crystallization was reduced to about 825 °C after 20 h of mechanical activation. The forsterite powder synthesized by 5 h of mechanical activation with subsequent annealing at 1000 °C for 1 h had crystallites 40 nm in size. The particle size of this sample was less than 500 nm.     

Magnetic properties of nano-clusters lanthanum chromite powders doped with samarium and strontium ions synthesized via a novel combustion method

A novel approach to synthesize a single-phase orthorhombic perovskite lanthanum chromite LaCrO₃ clusters doped with Sm³⁺ and Sr²⁺ ions via gel combustion route was reported. The producing materials were synthesized using metal nitrates as oxidizers and triethanol amine (TEA), N-butyl amine (NBA) or ethylene diamine (EDA) as a fuel. The effect of the annealing temperature, type of organic fuel and the variation of the samarium and/or strontium substitution and its impact on crystal structure, crystallite size, microstructure and magnetic properties of the LaCrO₃ powders formed was systematically studied. The results revealed that a well crystalline single phase of pure LaCrO₃ can be achieved at annealing temperature from 800 to 1000 °C for 2 h. Moreover, each organic carrier materials exhibited a different degree of effectiveness in the synthesis of the mixed oxide powders. The crystal structure was influenced by doped Sm³⁺ and/or Sr²⁺ ions. The crystallite size of the produced powders was increased with the increase the annealing temperature, increasing the Sm³⁺ ion and the decrease of Sr²⁺ ion substitution. The microstructures of the produced powders were found to be nanoclusters octahedra-like shaped. The saturation magnetization of the LaCrO₃ powders increased continuously with an increase in the Sm³⁺ ion concentration and it decreased with an increase in the Sr²⁺ ion up to 0.3 at annealing temperature of 1000 °C for 2 h. The maximum saturation magnetization (0.279 emu/g) was achieved at the Sm³⁺ ion molar ratio 0.3 and annealing temperature 1000 °C. Moreover, wide coercivities can be obtained at different synthesis conditions (49.25 to 522  Oe).     

Preparation of LiFePO4/C composite powders by ultrasonic spray pyrolysis followed by heat treatment and their electrochemical properties

LiFePO₄ powders could be successfully prepared from a precursor solution, which was composed of Li(HCOO)·H₂O, FeCl₂·4H₂O and H₃PO₄ stoichiometrically dissolved in distilled water, by ultrasonic spray pyrolysis at 500 °C followed by heat treatment at sintering temperatures ranging from 500 to 800 °C in N₂ + 3% H₂ gas atmosphere. Raman spectroscopy revealed that α-Fe₂O₃ thin layers were formed on the surface of as-prepared LiFePO₄ powders during spray pyrolysis, and they disappeared after sintering above 600 °C. The LiFePO₄ powders prepared at 500 °C and then sintered at 600 °C exhibited a first discharge capacity of 100 mAh g⁻¹ at a 0.1 C charge-discharge rate. To improve the electrochemical properties of the LiFePO₄ powders, LiFePO₄/C composite powders with various amounts of citric acid added were prepared by the present method. The LiFePO₄/C (1.87 wt.%) composite powders prepared at 500 °C and then sintered at 800 °C exhibited first-discharge capacities of 140 mAh g⁻¹ at 0.1 C and 84 mAh g⁻¹ at 5 C with excellent cycle performance. In this study, the optimum amount of carbon for the LiFePO₄/C composite powders was 1.87 wt.%. From the cyclic voltammetry (CV) and AC impedance spectroscopy measurements, the effects of carbon addition on the electrochemical properties of LiFePO₄ powders were also discussed.     

Nanostructure effects on the bioactivity of forsterite bioceramic

Recently, forsterite (Mg₂SiO₄) has been introduced as a possible bioceramics due to its good biocompatibility. It has a better bending strength and fracture toughness than those of commercially available hydroxyapatite ceramics. In this study, nanostructure effects on the bioactivity of forsterite powder were investigated. For synthesizing forsterite powder, talc and magnesium carbonate powders were mechanically activated for various times. Then, the prepared powders were mixed with ammonium chloride (as a catalyst) and annealed at different temperatures. For bioactivity evaluation, the obtained forsterite powders were pressed in the form of tablets and then immersed in simulated body fluid (SBF). The results showed that nanostructure forsterite powder with crystallite size of about 31 nm, unlike micrometer-sized forsterite, possessed apatite formation ability and its bioactivity, biocompatibility, and good mechanical properties make it a suitable candidate for load bearing application in bone implant materials and open new horizons in tissue engineering.     

Luminescence response and CL degradation of combustion synthesized spherical SiO2:Ce nanophosphor

This study was aimed to systematically investigate the luminescence response of SiO₂:Ce³⁺ nanophosphors with different excitation sources. The powders were synthesized by using an urea assisted combustion method. SiO₂:Ce_1m% samples were also annealed at 1000 °C for 1 h in a charcoal environment to reduce incidental Ce⁴⁺ to partial Ce³⁺ ions. High resolution transmission electron microscopy (HRTEM) images of the as synthesized and annealed powder samples confirmed that the particles were spherical and in the size range of 3-8 nm in diameter. X-ray diffraction (XRD) and electron dispersion spectroscopy (EDS) results showed that the SiO₂ was crystalline and pure. Diffused reflectance, photoluminescence (PL) and cathodoluminescence (CL) results of the SiO₂:Ce³⁺ samples were obtained and compared with each other. The CL degradation and the surface reactions on the surface of the SiO₂:Ce³⁺ were studied with X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES). A clear improvement in the chemical stability of the SiO₂:Ce³⁺ annealed at 1000 °C were obtained.     

Effect of sintering temperature on dielectric properties of Ba0.6Sr0.4TiO3–MgO composite ceramics prepared from fine constituent powders

Composite ceramics of Ba_0.6Sr_0.4TiO₃ + 60 wt.% MgO were prepared from fine constituent powders by sintering at 1200–1280 °C. The composite specimens sintered at the relatively low temperatures showed satisfactory densification due to fine morphology of the constituent powders. The elevation of sintering temperature promoted the incorporation of Mg²⁺ into the lattice of the Ba_0.6Sr_0.4TiO₃ phase and grain growth of the two constituent phases. The dependence of the dielectric properties on sintering temperature was explained in relation to the structural evolution. Controlling the sintering temperature of the composite was found to be important to achieve the desired nonlinear dielectric properties. Sintering at 1230 °C was determined to be preferred for the composite in terms of the nonlinear dielectric properties. The specimen sintered at the temperature attained a tunability of 17.3% and a figure of merit of 127 at 10 kHz and 20 kV/cm.     

Synthesis and densification of lutetium pyrosilicate from lutetia and silica

Cerium-doped lutetium pyrosilicate (Lu₂Si₂O₇:Ce) powder was synthesized by solid state reaction of Lu₂O₃ and SiO₂. Stoichiometric mixtures of the starting materials were heat treated at various different temperatures and their phase contents were measured by XRD technique. It was found that the first step in the formation of Lu₂Si₂O₇ (LPS) is the appearance of Lu₂SiO₅ (LSO). This takes place at 1100 °C, fully 300 °C below the first appearance of LPS. Between 1400 and 1500 °C both LSO and LPS coexist in the calcined batch, but by 1550 °C all LSO is completely converted to LPS. LPS formation temperature does not have appreciable effect on the density of the hot pressed samples. Hot pressed samples obtained from powder synthesized at 1650 °C are nearly transparent, although the particle size of the starting powder is higher than that of the powder formed at lower temperatures.     

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.     

Factors affecting CO oxidation over nanosized Fe2O3

Nanocrystallite iron oxide powders with different crystallite sizes were prepared by co-precipitation route. The prepared powders with crystallite size 75, 100 and 150 nm together with commercial iron oxide (250 nm) were tested for the catalytic oxidation of CO to CO₂. The influence of different factors as crystallite size, catalytic temperature and weight of catalyst on the rate of catalytic reaction was investigated using advanced quadrupole mass gas analyzer system. It can be reported that the rate of conversion of CO to CO₂ increased by increasing catalytic temperature and decreasing crystallite size of the prepared powders. The experimental results show that nanocrystallite iron oxide powders with crystallite size 75 nm can be recommended as a promising catalyst for CO oxidation at 500 °C where 98% of CO is converted to CO₂. The mechanism of the catalytic oxidation reaction was investigated by comparing the CO catalytic oxidation data in the absence and presence of oxygen. The reaction which was found to be first order with respect to CO is probably proceeded by adsorption mechanism where the reactants are adsorbed on the surface of the catalyst with breaking OO bonds, then CO pick up the dissociated O atom forming CO₂.     

Morphological investigation of sub-micron FePO4 and LiFePO4 particles for rechargeable lithium batteries

Microstructural variations of amorphous FePO₄ and LiFePO₄ (the latter obtained by chemical lithiation of the former) as a result of the annealing temperature have been studied by Thermogravimetric Analysis (TGA)/Differential Thermal Analysis (DTA), chemical analysis, Brunauer-Emmet-Taylor (BET) and Scanning Electron Microscopy (SEM) techniques. Round-shaped amorphous FePO₄ particles 40-80 nm in size are obtained after heating (at 400 °C) amorphous FePO₄·2H₂O in air (previously prepared by a precipitation route). On further heating at 650 °C, in air, crystalline trigonal FePO₄ of crystallite size <200 nm is formed. Round-shaped amorphous LiFePO₄ particles 40-80 nm in size crystallize by heating at 550 °C in Ar+5%H₂ for 3 h. After thermal treatment, LiFePO₄ particles are interconnected by necks, which resembled a sintering process. The particle size of LiFePO₄ increases with an increase of temperature up to 750 °C, but an abnormal growth is evident at annealing temperatures above 650 °C. DTA analysis showed two exothermic peaks at 547 and 768 °C for FePO₄ due to phase transitions, whereas for LiFePO₄ two exothermic effects at 496 and 567 °C are shown.     

Corrosion resistance enhancement of Ni–P electroless coatings by incorporation of nano-SiO2 particles

Composite coatings were prepared using hypophosphite reduced electroless nickel bath containing 7 g/L SiO₂ nano-particles at pH 4.6 ± 0.2 and temperature 90 ± 2 °C. Deposition rate for SiO₂ nano-composite coatings was 10–12 μm/h. The amount of SiO₂ nano-particles co-deposited in the Ni–P matrix was around 2 wt.%. The analyzes of coating compositions, carried out by Energy Dispersive Analysis of X-ray (EDAX), showed that plain Ni–P and Ni–P/nano-SiO₂ deposits contained around 8 wt.% phosphorus. The X-ray diffraction (XRD) pattern of Ni–P/nano-SiO₂ coating was very similar to that of plain electroless Ni–P coating, whose structure was also amorphous.     

High temperature annealing of micrometric Zn2SiO4:Mn phosphor powders in fluidized bed

Micrometric Zn_1.8Mn_0.2SiO₄ phosphor powders prepared by spray pyrolysis have been annealed between 900 and 1200 °C under ambient air atmosphere to investigate their luminescence properties. Two original gas-solid fluidization processes have been tested in order to limit sintering phenomena, and the post-treated products have been compared with those annealed using a conventional process in crucible. The crystallinity, the size distribution, the outer morphology and the luminescence properties of powders before and after treatment have been analysed. Massive sintering phenomena occur in crucible from 1000 °C, whereas the original granulometry and spherical morphology are preserved till 1100 °C in fluidized bed. The luminescence efficiencies are comparable for the three processes and shown to be maximal after annealing at 1200 °C. It has been established that residual ZnO and manganese ions at oxidation state higher than 2+, still present after treatment at 1100 °C, are detrimental to good luminescence efficiency. Both disappear from samples post-treated at 1200 °C.     

Tin dioxide nanoparticles: Reverse micellar synthesis and gas sensing properties

Tin dioxide (SnO₂) nanoparticles have been synthesized by reverse micellar route using cetyltrimethyl ammoniumbromide (CTAB) as the surfactant. Monophasic tin dioxide (SnO₂) was obtained using NaOH as the precipitation agent at 60 °C, however, when liquor NH₃ was used as precipitating agent then crystalline SnO₂ nanoparticles are obtained at 500 °C. SnO₂ prepared using NaOH show crystallite size of 4 and 12 nm after heating at 60 and 500 °C respectively using X-ray line broadening studies. Transmission electron microscopy (TEM) studies show agglomerated particles of sizes 70 and 150 nm, respectively. The grain size was found to be 6-8 nm after heating the precursor obtained (using liquor NH₃) at 500 °C by X-ray line broadening and the TEM studies. Dynamic light-scattering (DLS) studies show the aggregates of SnO₂ nanoparticles with uniform size distribution. Mössbauer studies show an increase of s-electron density at the Sn sites compared to bulk SnO₂ and a finite quadrupole splitting indicative of lowering of symmetry around tin atoms. The gas sensing characteristics have also been investigated using n-butane which show high sensitivity and fast recovery time.     

Fast and efficient synthesis of ZSM-5 in a broad range of SiO2/Al2O3 without using seeding gel

ZSM-5 zeolite were synthesized in a wide range of SiO₂/Al₂O₃ molar ratios at temperature ranging from 220 to 230 °C without adding seeding gel in 4-6 h of autoclavation time.     

Grain growth and microstructural evolution of yttrium aluminum garnet nanocrystallites during calcination process

An yttrium aluminum garnet (YAG) precursor precipitate was synthesized by urea method using yttria (Y₂O₃) and aluminum nitrate (Al(NO₃)₃·9H₂O) as raw materials. The fresh wet precipitate was dried by supercritical carbon dioxide (CO₂) fluid and the resulting powder was calcined at temperatures from 600 to 1600 °C. Crystallization of YAG was detected at 800 °C, and completed at 900 °C. HRTEM images of the YAG product obtained above 900 °C revealed crystallographically specific oriented attachment along the [1 1 2] direction. Based on the observation of the particle morphology a possible growth mechanism of YAG nanoparticles was presented. The fast increase on the average crystallite size of YAG at temperatures from 900 to 1300 °C is attributed to the crystallographically specific oriented attachment growth process. As the growth process proceeds at higher temperatures, oriented attachment based growth becomes less important because of the increase on particle size, and the self-integration assisted by the Ostwald ripening becomes dominant.     

The effect of solution temperature on the microstructure and tensile properties of Al–15%Mg2Si composite

The effect of different solution temperatures has been investigated on the microstructure and tensile properties of in situ Al–Mg₂Si composite specimens were subjected to solutionizing at different temperatures of 300 °C, 350 °C, 400 °C, 450 °C, 500 °C, 550 °C and 580 °C for holding time of 4 h followed by quenching. The microstructural studies of the polished and etched samples by scanning electron microscopy (SEM) in the solution condition indicated that the increase in the temperature changes the morphology of both the primary and secondary Mg₂Si phases. Solutionizing led to the dissolution of the Mg₂Si particles and changed their morphology. Tensile test results indicated that ultimate tensile strength (UTS) gradually decreased upon solutionizing from 300 to 550 °C while further increase in the temperature followed by a sharp decrease in UTS up to 580 °C solutionizing temperature. It was found that the elongation has become three times greater in comparison to the as-cast state. Elongation results showed an increase up to 500 °C and then reduced temperatures of 550 and 580 °C. Fractographic analysis revealed a cellular nature for the fracture surface. On the cellular fracture surface, the features of both brittle and ductile fracture were present simultaneously. As a result of solution treatment the potential sites for stress concentration and crack initiation areas were reduced due to softening of the sharp corners and break up of eutectic network respectively, while increase in the number of fine dimples rendered the nature of fracture to ductile and also increased elongation.     

Microwave-assisted synthesis of barium molybdate by a citrate complex method and oriented aggregation

BaMoO₄ powders, which have scheelite type structure, were successfully synthesized at low temperatures by a modified citrate complex method assisted by microwave irradiation. The citrate complex precursors were heat-treated at temperatures from 300 to 500 °C for 3 h. Crystallization of the BaMoO₄ powders were detected at 350 °C, and completed at a temperature of 400 °C. TEM image of the BaMoO₄ product obtained above 400 °C revealed spindle-rods-like or flake-like morphology. The anisotropic growth habit of BaMoO₄ leads to the oriented aggregation, which is attributed to the high chemical potentials of the intrinsic structure of BaMoO₄. The BaMoO₄ powder prepared at 500 °C showed the strongest photoluminescent intensity.