Preparation and sintering behaviour of a fine grain BaTiO<Subscript>3</Subscript> powder containing 10 mol% BaGeO<Subscript>3</Subscript>

The formation of solid solutions of the type [Ba(HOC₂H₄OH)₄][Ti_1−x Ge _x (OC₂H₄O)₃] as Ba(Ti_1−x /Ge _x )O₃ precursors and the phase evolution during thermal decomposition of [Ba(HOC₂H₄OH)₄][Ti_0.9Ge_0.1(OC₂H₄O)₃] (1) are described herein. The 1,2-ethanediolato complex 1 decomposes above 589 °C to a mixture of BaTiO₃ and BaGeO₃. A heating rate controlled calcination procedure, up to 730 °C, leads to a nm-sized Ba(Ti_0.9/Ge_0.1)O₃ powder (1a) with a specific surface area of S = 16.9 m²/g, whereas a constant heating rate calcination at 1,000 °C for 2 h yields a powder (1b) of S = 3.0 m²/g. The shrinkage and sintering behaviour of the resulting Ba(Ti_0.9/Ge_0.1)O₃ powder compacts in comparison with nm-sized BaTiO₃ powder compacts (2a) has been investigated. A two-step sintering procedure of nm-sized Ba(Ti_0.9/Ge_0.1)O₃ compacts (1a) leads, below 900 °C, to ceramic bodies with a relative density of ≥90%. Furthermore, the cubic ⇆ tetragonal phase transition temperature has been detected by dilatometry, and the temperature dependence of the dielectric constant (relative permittivity) has also been measured.     

Dielectric Ba(Ti1?xSnx)O3 (x?=?0.13) ceramics, sintered by spark plasma and conventional methods

A two-step sintering approach composed of spark-plasma-sintering (SPS) technique at 1000 °C for 1 min and under a uniaxial pressure of 63 MPa followed by conventional sintering at 1400 °C for 3 h is proposed for synthesis of dense Ba(Ti_0.87Sn_0.13)O₃ ceramics. Starting powders had grain size of about 90 nm and were obtained by co-precipitation. The SPS pellets consist of submicron (300–500 nm) grains. X-ray diffraction analysis of as-prepared Ba(Ti_0.87Sn_0.13)O₃ ceramic shows the occurrence of cubic and tetragonal phase coexistence for the pellets obtained after SPS processing and the presence of only tetragonal phase in the samples after the second (conventional) sintering. Grain uniformity in the final product is high, with average size of ~2 μm. The apparent densities of the sintered pellets at temperature of 1400 °C were ~92% of the theoretical value of Ba(Ti_0.87Sn_0.13)O₃. The ceramics exhibit a high relative dielectric constant of 6,550 and a dielectric loss (tan δ) = 0.078 at Curie temperature of 63 °C and 10 Hz.     

Synthesis and sintering of nano-sized BaSnO<Subscript>3</Subscript> powders containing BaGeO<Subscript>3</Subscript>

The formation of solid solutions of the type [Ba(HOC₂H₄OH)₄][Sn_1−x Ge _x (OC₂H₄O)₃] as BaSn_1−x /Ge _x O₃ precursor and the phase evolution during its thermal decomposition are described in this paper. The 1,2-ethanediolato complexes can be decomposed to nano-sized BaSn_1−x /Ge _x O₃ preceramic powders. Samples with x = 0.05 consist of only a Ba(Sn,Ge)O₃ phase, whereas powders with x = 0.15 and 0.25 show diffraction patterns of both the Ba(Sn,Ge)O₃ and BaGeO₃ phase. The sintering behaviour was investigated on powders with a BaGeO₃ content of 5 and 15 mol%. These powders show a specific surface area of 15.4–15.9 m²/g and were obtained from calcination above 800 °C. The addition of BaGeO₃ reduced the sintering temperature of the ceramics drastically. BaSn_0.95Ge_0.05O₃ ceramics with a relative density of at least 90% can be obtained by sintering at 1150 °C for 1 h. The ceramic bodies reveal a fine microstructure with cubical-shaped grains between 0.25 and 0.6 μm. For dense ceramics, the sintering temperature could be reduced down to 1090 °C, when the soaking time was extended up to 10 h.     

Sintering and electromagnetic properties of BaFe12O19 ferrite prepared by co-precipitation method

BaFe₁₂O₁₉ (BaM) was synthesized through the co-precipitation route. Pure phase BaM was formed after calcination of precipitated powder at 900 °C. BaM was sintered at three different temperatures; 1100, 1200, and 1300 °C to study the sintering kinetics by varying the sintering time from 1 to 4 h. Apparent porosity decreased, and bulk density increased with increasing sintering temperature and period. A bulk density of about 4.6 g/cm³ was achieved after sintering at 1300 °C/4 h. The rate-controlling mechanism of BaM densification was the diffusion of oxygen, and the activation energy for the sintering process was 274 kJ/mol. The grain size of BaM increased with rising sintering temperatures. Permittivity increased from about 11 to 17 and the permeability increased from about 10 to 16 with the increase in sintering temperature from 1100 to 1300 °C. Saturation magnetization was also enhanced to about 69 emu/g after sintering at 1300 °C/4 h. Therefore, BaM ferrite synthesized through the co-precipitation route can be effectively used for high-frequency applications after sintering at 1300 °C.

     

Preparation and phase development of yttria-doped ceria coated TZP powder

This paper presents a simple technique for preparation of yttria-doped ceria (YDC) coated tetragonal zirconia polycrystal (3Y-TZP) powder and its phase development upon firing. The coating solution was prepared using yttrium nitrate hexahydrate and cerium nitrate hexahydrate as starting reagents. Thermochemical reactions of the coated powder were studied using TGA and FTIR while phase development upon firing was examined using XRD. Inward diffusion of the coating YDC into the TZP particles was monitored by observing the change of crystal structure and lattice parameter as a function of sintering temperature and time. At sintering temperature of 1300 °C for 1 h, crystal structure of the sample was still tetragonal (t-ZrO₂). Increasing sintering time to 5 h at 1300 °C, diffusion of YDC into TZP particles occurred drastically and the structure was changed to cubic (c-ZrO₂) as indicated by the disappearance of (002)/(200) peak splitting. Increasing sintering temperature to 1400 and 1500 °C, however, resulted in the co-existence of tetragonal and cubic phases as indicated by the appearance of triples around 72.5–74° 2θ and also the decrease of cubic lattice parameter. When the sintering temperature was further increased to 1600 °C, lattice parameter was only slightly changed, suggesting that inward diffusion of YDC reached saturation point around this temperature.     

Sintering behaviour of silicon nitride powders produced by carbothermal reduction and nitridation

In this study, the sintering behaviour of silicon nitride (Si₃N₄) powders (having in situ form sintering aids/self-sintering additives) produced directly by the carbothermal reduction and nitridation (CRN) process is reported. The sintering of as-synthesised α-phase Si₃N₄ powders was studied, and the results were compared with a commercial powder. The α-Si₃N₄ powders, as-received contains magnesium, yttrium or lithium–yttrium-based oxides that were shaped with cold isostatic pressing and tape casting techniques. The compacts and tape casted samples are then pressureless-sintered at 1650–1750 °C for up to 2 h. After sintering, the density and the amount of β-phase formation were examined in relation to the sintering temperature and time. The highest density value of 3.20 g cm^?3 was obtained after only 30 min of pressureless sintering (at 1700 °C) of Si₃N₄ powders produced by CRN from silica initially containing 5 wt.% Y₂O₃. Silicon nitride powders produced by the CRN process performed similarly or even better than results from the pressureless sintering process compared with the commercial one.     

Martensitic transformation behaviors of rapidly solidified Ti–Ni–Mo powders

For the fabrication of bulk near-net-shape shape memory alloys and porous metallic biomaterials, consolidation of Ti–Ni–Mo alloy powders is more useful than that of elemental powders of Ti, Ni and Mo. Ti₅₀Ni_49.9Mo_0.1 shape memory alloy powders were prepared by gas atomization, and transformation temperatures and microstructures of those powders were investigated as a function of powder size. XRD analysis showed that the B2–R–B19 martensitic transformation occurred in powders smaller than 150 μm. According to DSC analysis of the as-atomized powders, the B2–R transformation temperature (T_R) of the 25–50 μm powders was 18.4 °C. The T_R decreased with increasing powder size, however, the difference in T_R between 25–50 μm powders and 100–150 μm powders is only 1 °C. Evaluation of powder microstructures was based on SEM examination of the surface and the polished and etched powder cross sections and the typical images of the rapidly solidified powders showed cellular morphology. Porous cylindrical foams of 10 mm diameter and 1.5 mm length were fabricated by spark plasma sintering (SPS) at 800 °C and 5 MPa. Finally these porous TiNi alloy samples are heat-treated for 1 h at 850 °C, and then quenched in ice water. The bulk samples have 23% porosity and 4.6 g/cm³ density and their T_R is 17.8 °C.     

Formation of a single-phase Ti3AlC2 from a mixture of Ti,Al and TiC powders with Sn as an additive

A high purity of Ti₃AlC₂ powder has been synthesized by pressureless sintering a mixture of Ti/Al/TiC/Sn (Sn as a sintering additive) powders with a mole ratio of 1:1:1:0.1 in the temperature range of 1350–1500 °C for 10 min in an Ar atmosphere. Sn is an effective additive and its effect on the formation of Ti₃AlC₂ has been discussed. The formation mechanism of Ti₃AlC₂ has been proposed. X-ray diffraction analysis and scanning electron microscopy were used to characterize the samples.     

On sinterability of Cu-coated W nanocomposite powder prepared by a hydrogen reduction of a high-energy ball-milled WO3-CuO mixture

Cu-coated W nanocomposite powder was prepared by a combination of high-energy ball-milling of a WO₃ and CuO mixture in a bead mill and its two-stage reduction in a H₂ atmosphere with a slow heating rate of 2 °C/min. STEM-EDS and HR-TEM analyses revealed that the microstructure of the reduced W–Cu nanocomposite powder was characterized by ~50-nm W particles surrounded by a Cu nanolayer. Unlike conventional W–Cu powder, this powder has excellent sinterability. Its solid-phase sintering temperature was significantly enhanced, and this led to a reduction in the sintering temperature by 100 °C from the 1,200 °C required for conventional nanocomposite powder. In order to clarify this enhanced sintering behavior of Cu-coated W–Cu nanocomposite powder, the sintering behavior during the heating stage was analyzed by dilatometry. The maximum peak in the shrinkage rate was attained at 1,073 °C, indicating that the solid-phase sintering was the dominant sintering mechanism. FE-SEM and TEM characterizations were also made for the W–Cu specimen after isothermal sintering in a H₂ atmosphere. On the basis of the dilatometric analysis and microstructural observation, the possible mechanism for the enhanced sintering of Cu-coated W composite powder in the solid phase was attributed to the coupling effect of solid-state sintering of nanosized W particle packing and Cu spreading showing liquid-like behavior. Homogeneous and fully densified W–20 wt% Cu alloy with ~180 nm W grain size and a high hardness of 498 Hv was obtained after sintering at 1,100 °C.     

Low-temperature synthesis of Sr<Subscript>0.3</Subscript>Ba<Subscript>0.7</Subscript>Nb<Subscript>2</Subscript>O<Subscript>6</Subscript> ultrafine powder and its characteristics

Ultrafine strontium barium niobate (Sr_0.3Ba_0.7Nb₂O₆, SBN30) powders were prepared by urea method starting from a precursor solution constituting of Sr (NO₃)₂, Ba (NO₃)₂, NbF₅, urea and polyvinyl alcohol (PVA) as surfactant. Their structural behavior and morphology were examined by means of X-ray diffractometry (XRD) and Scanning electron microscopy (SEM). The results showed that the SBN30 powders crystallized to a pure tetragonal phase at annealing temperatures as low as 750 °C. The average particle size of SBN powders subjected to 750 °C was of the order of 150–300 nm. With increasing calcination temperature,however, the average particle size of the calcined powders increased. The SBN30 ceramic prepared from urea method can be sintered at temperature as low as 1,225 °C. The transition temperature from the ferroelectric phase to the paraelectric phase and the relative dielectric permittivity of the SBN30 powder were less than the corresponding values of the bulk ceramic. The permittivity and loss tangent (tan δ) at room temperature (1 kHz) was found to be 930 and below 0.025.     

A simple sol–gel technique for preparing hydroxyapatite nanopowders

HA powder was prepared using a sol–gel method with phosphoric pentoxide (P₂O₅) and calcium nitrate tetrahydrate (Ca(NO₃)₂·4H₂O). The effect of sintering temperatures on crystalline degree and composition of the HA phase, and also the effect of aging times on crystal size of the HA powder were studied using XRD and TEM. It was found that at sintering temperatures ranging from 600 to 900 °C, the dominant phase in the powders was HA with small amounts of calcium oxide and β-tricalcium phosphate (β-TCP) at 800 and 900 °C, and only HA phase was observed at 600 and 700 °C. 10–15 nm HA powders were obtained using this technique. This technique has an advantage over other sol–gel methods in more simple and shorter time because of no requiring pH value control and long hydrolysis time.     

Stainless steel foams made through powder metallurgy route using NH4HCO3 as space holder

Stainless steel (316) foams of varying porosities have been made through powder metallurgy route using NH₄HCO₃ as a space holder. Green compacts of stainless steel powder with NH₄HCO₃ were sintered at two different temperatures: 1100 °C and 1200 °C. At higher sintering temperatures, neighboring stainless steel powders fused together to form polycrystalline grain structure with iron–chromium intermetallic phases segregated along the grain boundaries. Whereas, the fusion of neighboring stainless steel powders was limited around the particle–particle contact only when the green compacts were sintered at 1100 °C, which resulted in a larger amount of microporosities in the cell wall. These foams exhibited strain hardening behavior in the plateau region under compressive loading. The yield stress and the flow stress (at lower strain levels) of foams, sintered at 1100 °C were higher. But, the reverse is true for the flow stress at higher strain levels. The exponents and the coefficients of the power law relationships varied with sintering temperature and strain levels.     

Preparation and characterization of the bismuth sodium titanate (Na0.5Bi0.5TiO3) ceramic doped with ZnO

This study investigates effects of the zinc oxide (ZnO) addition and the sintering temperature on the microstructure and the electrical properties (such as dielectric constant and loss tangent) of the lead-free piezoelectric ceramic of bismuth sodium titanate (Na_0.5Bi_0.5TiO₃), NBT, which was prepared using the mixed oxide method. Three kinds of starting powders (such as Bi₂O₃, Na₂CO₃ and TiO₂) were mixed and calcined. This calcined NBT powder and a certain weight percentage of ZnO were mixed and compressed into a green compact of NBT–ZnO. Then, this green compact of NBT–ZnO was sintered to be a disk doped with ZnO, and its characteristics were measured. In this study, the calcining temperature was 800 °C, the sintering temperatures ranged from 1000 to 1150 °C, and the weight percentages of ZnO doping included 0.0, 0.5, 1.0, and 2.0 wt%. At a fixed wt% ZnO, the grain size increases with increase in the sintering temperature. The largest relative density of the NBT disk obtained in this study is 98.3% at the calcining temperature of 800 °C, the sintering temperature of 1050 °C, and 0.5 wt% ZnO addition. Its corresponding dielectric constant and loss tangent are 216.55 and 0.133, respectively.     

Low temperature fabrication of magnesium phosphate cement scaffolds by 3D powder printing

Synthetic bone replacement materials are of great interest because they offer certain advantages compared with organic bone grafts. Biodegradability and preoperative manufacturing of patient specific implants are further desirable features in various clinical situations. Both can be realised by 3D powder printing. In this study, we introduce powder-printed magnesium ammonium phosphate (struvite) structures, accompanied by a neutral setting reaction by printing farringtonite (Mg₃(PO₄)₂) powder with ammonium phosphate solution as binder. Suitable powders were obtained after sintering at 1100°C for 5 h following 20–40 min dry grinding in a ball mill. Depending on the post-treatment of the samples, compressive strengths were found to be in the range 2–7 MPa. Cytocompatibility was demonstrated in vitro using the human osteoblastic cell line MG63.     

Effect of B2O3 and CuO additions on the sintering temperature and microwave dielectric properties of 3Li2O–Nb2O5–3TiO2 ceramics

The effects of B₂O₃–CuO (BCu, the weight ratio of B₂O₃ to CuO is 1:1) addition on the sintering behavior, microstructure, and the microwave dielectric properties of 3Li₂O–Nb₂O₅–3TiO₂ (LNT) ceramics have been investigated. The low-amount addition of BCu can effectively lower the sintering temperature of LNT ceramics from 1125 to 900 °C and induce no obvious degradation of the microwave dielectric properties. Typically, the 2 wt% BCu-added ceramic sintered at 900 °C has better microwave dielectric properties of ε _r  = 50.1, Q × f = 8300 GHz, τ _f  = 35 ppm/°C. Silver powders were cofired with the dielectric under air atmosphere at 900 °C. The SEM and EDS analysis showed no reaction between the dielectric ceramic and silver powders. This result shows that the LNT dielectric materials are good candidates for LTCC applications with silver electrode.     

Study of the sintering properties of plasma synthesized ultrafine SiC powders

A study on the sintering of ultrafine SiC powders synthesized from elemental Si and CH₄ using radio frequency (r.f.) induction plasma technology is reported. The powder had a particle size in the range of 40 to 80 nm and was composed of a mixture of α and β-SiC. It was subjected to pressureless sintering in an induction furnace in the presence of different sintering aids. With the addition of B₄C (2.0 wt% B) by mechanical mixing, the powders could only be partially densified, with the highest value of 84.5% of theoretical density being achieved at 2170 °C for 30 min. Through the use of “in-flight” boron doping of the powder during the plasma synthesis step (1.65 wt % B), the ultrafine powder obtained could be densified to above 90% of its theoretical density at 2050 °C for 30 min. The addition of oxide sintering aids (7.0 wt % Al₂O₃ + 3.0 wt % Y₂O₃) by mehanical mixing produced sintered pellets of 95% of theoretical density at 2000 °C for 75 min. The Vicker’s microhardness of the sintered pellets in this case was as high as 31.2 GPa. In order to improve our understanding of the basic phenomena involved, extensive microstructural (scanning electron energy microscopy: SEM), physical (shrinkage, weight loss, porosity, hardness) as well as chemical analysis (prompt gamma neutron activation analysis (PGNAA), energy dispersive spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA)) was carried out. This helped establish a relationship between the properties of the as-synthesized powder and their sintering properties. The influences of sintering temperature, sintering time, additive concentration, and powder purity on the densification behaviour of the plasma-synthesized powders was investigated. The results were compared with data obtained using commercial powder. This revised version was published online in November 2006 with corrections to the Cover Date.     

Effect of synthesis conditions on the preparation of BiFeO<Subscript>3</Subscript> nanopowders using two different methods

Bismuth orthoferrite (BiFeO₃) nanoparticles have been synthesized via the co-precipitation and the oxalate precursor methods. Effects of Bi source, annealing temperature, Bi/Fe molar ratio, oxalic acid ratio and Mn²⁺ ion on the crystal structure, crystallite size, microstructure and magnetic properties of the produced powders were systematically studied. The results revealed that bismuth oxychloride and iron oxide were formed using chlorides sources. A single phase of BiFeO₃ was formed from as-made samples with Bi/Fe molar ratio 1.1 using nitrate sources and annealed at 500 and 600 °C for 2 h via the two pathways. The pure BiFeO₃ phase appeared as spherical and pseudocubic-like structure using the co-precipitation and the oxalic acid precursor routes, respectively. A high saturation magnetization (3.94 emu/g) was achieved for powder formed from the oxalate precursor route with Bi/Fe molar ratio 1.0 annealed at 600 °C for 2 h as the result of the formation of Bi₂₅FeO₃₉. Moreover, Mn²⁺ ion addition affected BiFeO₃ properties due to the formation of Bi₂Fe₂Mn₂O₁₀. Hence, the saturation magnetization and the coercive force of BiFeO₃ were improved substantially by substitution of Mn²⁺ ions (BiFe_1-XMn_XO₃, X = 0.1–0.2).     

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.     

High voltage SnO<Subscript>2</Subscript> varistors prepared from nanocrystalline powders

In this study, SnO₂-based varistors were prepared from mechanically activated nanocrystalline powders. Nanocrystalline powders were derived by subjecting the initial powders to intensive high-energy activation with different times and ball to powder ratio. The effect of activation parameters on the powder properties and sintering temperature, as well as microstructural, micro-electrical and macro-electrical properties of the final specimens was evaluated. Varistors derived from high-energy mechanical activation exhibit a higher density (98.3% relative density) and more refined microstructure upon sintering at 1,300 °C in comparison varistors prepared from conventional powders. Breakdown voltage and nonlinear coefficient were increased up to 24 kV/cm and 45 respectively.     

Preparation and characterization of hydroxyapatite synthesized from oyster shell powders

The ready availability and the low cost of oyster shells, which is composed predominantly of calcium carbonate with rare impurities, along with natural wastes are attractive features for converting the biological material into hydroxyapatite (HA) powders for biomedical applications. The HA powder was synthesized using oyster shell powders and dicalcium phosphate dihydrate (CaHPO₄·2H₂O, DCPD) through ball milling and subsequently heat treatment. The HA was initiated through sintering the 1-h milled sample at 1000 °C for 1 h, while pure HA phase is formed after sintering the 10-h milled sample. The as-prepared samples, obtained after 5 or 10 h of milling and then heat-treating at 1000 °C for 1 h, contain the phase of β-tricalcium phosphate (β-TCP). Moreover, the result of FTIR analysis showed that the as-prepared HA sample is A- and B-type carbonate-containing calcium phosphates. The as-synthesize HA powder containing trace elements Mg and Sr exhibited good crystallinity (96.3%) and high phase-purity.