Synthesis of SmAlO<Subscript>3</Subscript> nanocrystalline powders by polymeric precursor method

SmAlO₃ nanocrystalline powders were successfully synthesized by the polymeric precursor method using ethylenediaminetetraacetic acid as a chelating agent. The precursor and the derived powders were characterized by thermogravimetry analysis (TG) and differential scanning calorimetry analysis (DSC), infrared spectroscopy (IR), X-ray diffractometry (XRD) and transmission electron microscopy (TEM). The results showed that pure SmAlO₃ powder with orthorhombic perovskite structure could be synthesized at 800°C for 2 h without formation of any intermediate phase. The average particle size of the powder synthesized at 900°C was as low as 28 nm. Subsequently, the bulk SmAlO₃ ceramics were prepared at various sintering temperatures using the synthesized powders calcined at 900°C for 2 h as starting materials. The sintering experiments indicated that the sample sintered at 1550°C for 2 h exhibited the highest relative density of 97.2% and possessed the best microwave dielectric properties of ε _r=20.94, Q×f=78600 GHz and τ _f=−71.8 ppm/°C.     

Influence of sintering temperature and pH on the phase transformation,particle size and anti-reflective properties of RHA nano silica powders

Nano silica powders were synthesized from rice husk ash, the most silica-rich raw material, using alkaline extraction followed by acid precipitation. The phase transformation during sintering, the influence of sintering temperature and pH on the particle size and anti-reflective properties of nano silica were investigated. The results showed that the amorphous SiO₂ sintered at 600°C were transformed to a cristobalite structures completely during the sintering process at 800°C and 1100°C. With the increasing sintering temperature and pH, the particle size distributions (d₅₀) were increased respectively in the range of 62–84, 192–240, and 283–329?nm at sintering temperatures of 600°C, 800°C, and 1100°C. When the sintering temperatures were increased at 1100°C, 98.15% and 96.84% of transmittances were obtained respectively at the highest and lowest points of the anti-reflection band and could be used for anti-reflective applications.     

Preparation and properties of Ba1−xCaxTiO3 nanopowders obtained by mechanochemical synthesis

ABSTRACT

The calcium-substituted barium titanate nanopowders Ba_1?xCa_xTiO₃ (0.2 ≤ x ≤ 0.3) have been obtained at room temperature by mechanochemical synthesis. The formation of the perovskite phase was controlled by X-ray diffraction studies at various milling duration. The powders possess the perovskite crystallographic structure directly after milling longer than 10 h. The dielectric properties of the ceramics obtained by sintering of the nanopowders were investigated in the temperature range between 300 and 500 K. The temperature dependence of permittivity exhibited a single anomaly, which corresponds to the ferroelectric–paraelectric phase transition.     

Preparation and characteristics of?a?BaO–Al2O3–B2O3–SiO2–La2O3 glass ceramic via spray pyrolysis

The characteristics of a BaO–Al₂O₃–B₂O₃–SiO₂–La₂O₃ glass ceramic prepared by spray pyrolysis were studied. Glass powders with spherical shape and amorphous phase were prepared by complete melting at a preparation temperature of 1 500°C. The mean size and geometric standard deviation of the powders prepared at the temperature of 1 500°C were 0.6 μm and 1.3. The glass powders had similar composition to that of the spray solution. The glass transition temperature (T _g) of the glass powders was 600.3°C. Two crystallization exothermic peaks were observed at 769.3 and 837.8°C. Densification of the specimen started at a sintering temperature of 600°C, in which Ba₄La₆O(SiO₄)₆ as main crystal structure was observed. Complete densification of the specimen occurred at a sintering temperature of 800°C. The specimens sintered at temperatures above 800°C had main crystal structure of BaAl₂Si₂O₈.     

Phase evolution and effect of pre-heating temperature on the characteristics of PZT thin films grown by using a triol sol--gel route

Lead zirconate titanate (PZT) films were fabricated on Pt(111)/Ti/SiO₂/Si(100) using the triol sol--gel method. The effect of the pre-heating temperature on the phase transformations, microstructures, electrical properties and ferroelectric properties of the PZT thin films was investigated. Randomly-oriented PZT thin films pre-heated at 400°C for 10?min and annealed at 600°C for 30?min showed well-defined ferroelectric hysteresis loops with a remanent polarization of 26.57?µC?cm^?2 and a coercive field of 115.42?kV?cm^?1. The dielectric constant and dielectric loss of the PZT films were 621 and 0.0395, respectively. The microstructures of the thin films are dense, crack-free and homogeneous with fine grains about 15–20?nm in size.     

Structural evolutions of the mechanically alloyed Al<Subscript>70</Subscript>Cu<Subscript>20</Subscript>Fe<Subscript>10</Subscript> powders

Elemental mixtures of Al, Cu, Fe powders with the nominal composition of Al₇₀Cu₂₀Fe₁₀ were mechanically alloyed in a planetary ball mill for 80 h. Subsequent annealing of the as-milled powders were performed at 600–800°C temperature range for 4 h. Structural characteristics of the mechanically alloyed Al₇₀Cu₂₀Fe₁₀ powders with the milling time and the heat treatment were investigated by X-ray diffraction (XRD), differential scanning calorimeter (DSC) and differential thermal analysis (DTA). Mechanical alloying of the Al₇₀Cu₂₀Fe₁₀ did not result in the formation of icosahedral quasicrystalline phase (i-phase) and a long time milling resulted in the formation of β-Al(Cu,Fe) solid solution phase (β-phase). The i-phase was observed only for short-time milled powders after heat treatment above 600°C. The β-phase was one of the major phases in the Al₇₀Cu₂₀Fe₁₀ alloy. The w-Al₇Cu₂Fe₁ phase (w-phase) was obtained only after heat treatment of the short-time milled and unmilled samples. The present investigation indicated that a suitable technique to obtain a large amount of quasicrystalline powders is to use a combination of short-time milling and subsequent annealing.     

Effect of processing on dielectric properties of (0.95)PbZr0.52Ti0.48O3–(0.05)BiFeO3

An effort has been made to synthesize solid solution of a composition with x=0.05 in the system (1?x)PbZr_0.52Ti_0.48O₃–(x)BiFeO₃ by the sol–gel method. XRD patterns of the pure PZT and BFO modified PZT samples have shown single phase formation. The effects of substitution of BFO on dielectric properties of PZT have been studied in the frequency range 10 Hz to 100 kHz and temperature range from RT to 773 K. The density was optimized by sintering the BFO modified PZT samples at different temperatures in four batches, S1, S2, S3 and S4. P–E hysteresis loop measurements for all the samples have shown almost saturated polarization. It has been observed that sample S2, sintered at 950 °C, exhibits superior dielectric properties of the four samples. The occurrence of weak ferromagnetism, observed in the M–H hysteresis loop, indicates coupling between ferroelectricity and magnetism. Impedance analysis has revealed that all the samples, sintered at different temperatures, have a different grain resistance. A large change in ac conductivity around T _c has been observed in all the samples.     

Preparation of Y<Subscript>2</Subscript>Ti<Subscript>2</Subscript>O<Subscript>7</Subscript> pyrochlore using high-energy ball milling and their structural,thermal and conducting properties

Pyrochlore-structured materials are very important materials due to their structural and conducting properties. These properties can be further modified by changing processing conditions. In the present study, pyrochlore (Y₂Ti₂O₇) is synthesized using high-energy ball milling. During various stages of ball milling, the ball-milled powder is taken for investigating the structural and thermal properties. The replacement of Ti₂O₃ by TiO₂ in nominal composition leads to lower ball milling duration to form Y₂Ti₂O₇. Differential thermal analysis showed the single exothermic peak below 800 °C, which indicates formation of disordered pyrochlore phase. The as prepared powders (40-h ball milled) were compacted and heat treated at 1,450 °C for 12 h. The conductivity of sintered sample is found to be one order higher than earlier reported pure Y₂Ti₂O₇ pyrochlore.     

Spherical shape BaO-ZnO-B<Subscript>2</Subscript>O<Subscript>3</Subscript>-SiO<Subscript>2</Subscript> glass powders prepared by spray pyrolysis

Fine-sized BaO-ZnO-B₂O₃-SiO₂ (BZBS) glass powders were directly prepared by high temperature spray pyrolysis. The hollow glass powders prepared at low preparation temperature of 1000 °C had a low density of 2.65 g/cm³. However, the densities of the BZBS powders obtained at preparation temperatures of 1200 and 1400 °C were each 3.92 and 4.13 g/cm³. The mean size of the BZBS glass powders prepared by spray pyrolysis at preparation temperature of 1400 °C was 0.98 μm. The glass transition temperature (T_g) of the prepared BZBS glass powders was 518.9 °C. The dielectric layers formed from the prepared BZBS glass powders with a dense structure had a clean surface and a dense inner structure without voids at the firing temperature of 580 °C. The transparencies of the dielectric layers formed from the prepared BZBS glass powders were higher than 90% within the visible range. PACS 42.70.Ce; 85.60.Pg; 71.55.Jv     

Phase formation and dielectric properties of (Pb0.925Ba0.075)(Zr1− x Ti x )O3 ceramics prepared by the solid-state reaction method

Lead barium zirconate titanate [(Pb_0.925Ba_0.075)(Zr_{1? x} Ti _x )O₃] ceramics with 0?≤?x?≤?1 were prepared by the solid-state reaction method. The calcination temperatures were between 800°C and 1000°C for 1?h and the sintering temperature was 1200°C for 3?h. It was found that the structure of the calcined powders and sintered pellets was in an orthorhombic phase for x?=?0; a rhombohedral phase for x?=?0.25 and a tetragonal phase for 0.5?≤?x?≤?1. The c/a ratio increased with an increase in the x content. The average particle size and density slightly decreased with an increase in the x content, while the average grain size, linear shrinkage, and Curie temperature increased when the x content increased.     

Neutron diffraction study of the interaction of iron with amorphous fullerite

The amorphous fullerite C₆₀ has been prepared by mechanical activation (grinding in a ball mill), and its interaction with iron during sintering of powders with 0–95 at % Fe has been studied. After sintering in the range 800–1200°C under a pressure of 70 MPa, the samples have nonequilibrium structures different from the structures of both annealed and quenched steels. In this case, the carbon phase, i.e., amorphous fullerite, undergoes a polyamorphous transition to amorphous graphite. It has also been shown that the interaction of amorphous fullerite with iron is weaker compared to crystalline fullerite or crystalline graphite.     

Genesis,structural, and transport properties of La<Subscript>2</Subscript>Mo<Subscript>2-x</Subscript>W<Subscript>x</Subscript>O<Subscript>9</Subscript> prepared via mechanochemical activation

Fast oxide-ion conductors La₂Mo_2-xW_xO₉ (x = 0–1) have been prepared using mechanochemical activation (MA) of starting oxides in a high-power planetary ball mill. Studies of La₂Mo_2-xW_xO₉ genesis and structural properties using thermal analysis, XRD, SEM, IR, and Raman spectroscopy have revealed that MA results in the formation of an amorphous precursor, while the cubic β-phase is formed after calcination at 700–900 °C. Due to a high dispersion of powders, high-density pellets of W-LAMOX ceramics have been obtained already after sintering at 950 °C. Their electrical conductivity measured by the impedance spectroscopy depends on the W concentration being sufficiently high (up to 5.6?10^?3 S/cm at 630 °C) at temperatures below 650 °C.     

Effect of low-temperature high-pressure sintering on BiFeO3 density,electrical magnetic and structural properties

Single-phase multiferroic BiFeO₃ (BFO) powders were prepared by hydrothermal microwave synthesis and dense BiFeO₃ ceramics were fabricated for the first time by the low-temperature high-pressure (LTHP) sintering technique. Effect of sintering temperature ranging from 400 to 800 °C (3 min and 10 min) and pressure of 3–8 GPa on structural, microstructural, electric and magnetic properties were investigated through X-ray diffraction, scanning electron microscope (SEM), electrochemical impedance spectroscopy (EIS), density and magnetic measurements. The results highlighted that LTHP sintering method, thanks to the high pressure involved, requires lower temperature and shorter time than other techniques, avoiding BiFeO₃ phase degradation. SEM images show that for short experimental time (t = 3 min) the average grain size of the sintered samples was approximately the same size of raw powder. Extending the sintering time up to 10 min the grain growth phenomena occurred. Moreover the results indicate that the best obtained density value was around 98% of theoretical density. The dielectric behavior of BiFeO₃ ceramics was not significantly influenced by the LTHP sintering conditions. Magnetic measurements showed that ceramic BiFeO₃ is weakly ferromagnetic at room temperature.     

Preparation and application of the 3C–SiC substrate to piezoelectric micro cantilever transducers

This study examines the fabrication process and mechanical properties of piezoelectric films with the substrate, which is made from silicon carbide. After depositing the PZT thick film on silicon carbide substrate and silicon substrate respectively, it was shown that silicon carbide substrate formed a stable interface with PZT thick film up to 950?°C, compared with silicon substrate. In addition, the dielectric constant of the PZT thick film sintered at 950?°C on a silicon carbide substrate was 843, and this value was about over 25 % improved value compared with that on a silicon substrate. A thick film piezoelectric micro transducer of a micro cantilever type was fabricated by using a multifunctional 3C–SiC substrate. The fabricated micro cantilever was a micro cantilever with multiple thin films on either silicon or silicon carbide substrate. The piezoelectric thick-film micro cantilever that was fabricated by using a SiC substrate showed excellent mechanical and thermal properties. The piezoelectric micro cantilever on the SiC substrate shows an excellent sensitivity towards the change of mass compared with the piezoelectric micro cantilever on the Si substrate.     

Processing pathway effects in CoCrCuNi+X (Fe,Mn) high-entropy alloys

A parallel study of mechanical alloying and solidification was carried out on FCC high-entropy alloys (HEAs) CoCrCuNi, CoCrCuFeNi and CoCrCuMnNi to investigate the effects of each processing methods on the resulting microstructure, crystal structure and microhardness. Elemental powders were mechanically alloyed followed by spark plasma sintering (SPS) at 800°C and 900°C to achieve densified discs, while arc melting was carried out from bulk pieces of the elemental metals followed by furnace annealing at 800°C and 900°C for 5?h. Both processing routes resulted in a primary FCC phase with secondary Cu-rich FCC segregation as interdendrites for the solidified alloys and particle boundaries for the SPS alloys, with the exception of a small amount of σ phase present in the SPS processed alloys. The solidification of the CoCrCuNi, CoCrCuFeNi and CoCrCuMnNi HEAs resulted in typical dendritic microstructure, followed by the precipitation of a small Cr-rich phase in the CoCrCuMnNi alloy after annealing. The grain size of the mechanically alloyed powder was approximately 20?nm from the Scherrers equation and the SPS processed HEAs consisted of a Cu-rich phase in the particle boundaries, forming cobblestone-like microstructure. The microhardness was examined in the as-cast, annealed and SPS states. It was found that the SPS processed samples had an increased microhardness by a factor of 2.5.     

Effect of sintering temperature on the elemental diffusion and electrical conductivity of SrTiO<Subscript>3</Subscript>/YSZ composite ceramic

The 50 vol% SrTiO₃/yttria-stabilized zirconia (YSZ) composite ceramic was prepared through powder sintering route in 1400～1500 °C. Only the cubic YSZ and SrTiO₃ phases are detected in all the sintered ceramics, and the typical XRD peak positions of both phases have varied dramatically. The grain sizes and relative densities of all specimens increase evidently with the sintering temperature. The width of the SrTiO₃/YSZ interfacial region increases from 100.4 to 468.8 nm as the sintering temperature rises from 1400 to 1500 °C. The total electrical conductivities of the sample sintered at 1500 °C are remarkably higher than those at 1400 and 1450 °C, while the ion transference numbers drop from 0.837 to 0.731 with sintering temperature from 1400 to 1500 °C. The variations in the electrical properties above can be interpreted based on the effects of sintering temperature on the elemental diffusions during the sintering process.     

Low temperature processing of dense samarium-doped CeO<Subscript>2</Subscript> ceramics: sintering and intermediate temperature ionic conductivity

Samarium-doped Ceria powders for solid electrolyte ceramics were synthesized by a combustion process. Cerium nitrate and samarium nitrate were used as the starting materials, and glycine was used as fuel. Decomposition of unburned nitrogen and carbon residues was investigated by simultaneous thermogravimetry analysis and differential thermal analysis experiments. The X-ray diffraction results showed that the single-phase fluorite structure forms at a relatively low calcination temperature of 800 °C. X-rays patterns of the SDC powders revealed that the crystallite size of the powders increases with increasing calcination temperature. The sintering behavior results showed that more than 96% of the relative density is obtained for powders sintered at 1,100 °C for 8 h. The alternating current impedance spectroscopy results showed that the SDC15 sample sintered at 1,100 °C has ionic conductivity of 0.015 Scm⁻¹at 650 °C in air. The present work results have indicated that glycine–nitrate route is a relatively low-temperature preparation technique to synthesize SDC powders with a high sinterability and a good ionic conductivity. Paper presented at the Third International Conference on Ionic Devices (ICID 2006), Chennai, Tamilnadu, India, Dec. 7–9, 2006.     

Defects induced ferromagnetism in Mn doped ZnO

Single phase Mn doped (2 at%) ZnO samples have been synthesized by the solid-state reaction technique. Before the final sintering at 500 °C, the mixed powders have been milled for different milling periods (6, 24, 48 and 96 h). The grain sizes of the samples are very close to each other (～32±4 nm). However, the defective state of the samples is different from each other as manifested from the variation of magnetic properties and electrical resistivity with milling time. All the samples have been found to be ferromagnetic with clear hysteresis loops at room temperature. The maximum value for saturation magnetization (0.11 μ_B/Mn atom) was achieved for 96 h milled sample. Electrical resistivity has been found to increase with increase in milling time. The most resistive sample bears the largest saturation magnetization. Variation of average positron lifetime with milling time bears a close similarity with that of the saturation magnetization. This indicates the key role played by open volume vacancy defects, presumably zinc vacancies near grain surfaces, in inducing ferromagnetic order in Mn doped ZnO. To attain optimum defect configuration favorable for ferromagnetism in this kind of samples proper choice of milling period and annealing conditions is required.     

Influence of sintering temperature on properties of BNKLLT–6 wt% BCTZ binary lead-free piezoelectric ceramic prepared through the solid-state combustion technique

In this work, a new binary 94 wt%[Bi_0.5(Na_0.68K_0.22Li_0.1)_0.5TiO₃ + 0.10 wt% of La₂O₃]–6 wt% [(Ba_0.85Ca_0.15)(Ti_0.90Zr_0.10)O₃] [BNKLLT–6 wt% BCTZ] ceramic was fabricated by the solid-state combustion technique and glycine was used as the fuel. The effect of sintering temperature in the range of 1075–1175 °C for 2 h on phase evolution, microstructure and electrical properties was investigated. The phase formation exhibited a coexistence structure between rhombohedral and tetragonal at low sintering temperature. As the sintering temperature increased, the phase formation changed to pseudo-cubic phase. The average grain size of the ceramics was increased with the increasing sintering temperature. Density, ?_r, ?_SA and T_FA of BNKLLT–6 wt% BCTZ ceramics increased while the T_SA decreased when the sintering temperature increased up to 1125 °C, while after this temperature the opposite trends occurred. At a sintering temperature of 1125 °C, the BNKLLT-6 wt% BCTZ sample showed the highest theoretical density (95.8%), maximum dielectric constant ?_SA (5278), highest d₃₃ (227 pC/N) and fair ferroelectric properties (P_r = 24.5 µC/cm² and E_c = 15.45 kV/cm).     

Studies on highly resistive ZnO thin films grown by DC-discharge-assisted pulsed laser deposition

It was found that by changing the substrate temperature from room temperature to ～850 °C, ZnO thin films with widely varying resistivity values could be grown on sapphire substrates using DC-discharge-assisted pulsed laser deposition (PLD) in oxygen ambient. The resistivity of the film grown at room temperature was too high to measure using our existing setup. However, as the growth temperature was increased from 550 °C to 750 °C, the resistivity first decreased slowly from ～14.0 to 4.4 Ω?m and then dropped suddenly to get saturated at ～2.0×10^?3 Ω?m as the growth temperature was further increased. In contrast to these, when there was no DC-discharge, the variation of resistivity for ZnO thin films grown by PLD was marginal up to the substrate temperature of ～850 °C. The reason for these observations was found to be the combined effects of reduction in donor defect densities like oxygen vacancies and zinc interstitials, introduction of acceptor type defects like interstitial oxygen and zinc vacancies, and the resultant poor carrier mobility at lower growth temperatures. At higher growth temperatures (800 °C and above), the appearance of oxygen vacancies and increase in mobility due to better crystalline quality were found to be responsible for reducing the resistivity. The PL of these films had significant emission in the green and red regions of the spectrum due to the aforesaid defect related transitions. Such highly resistive and luminescent films might be suited for applications such as resistive RAM, UV-photo detector, TFT, piezoelectric, transparent phosphor, and broadband LED applications.