Sintering studies on submicrometre-sized Y-Ba-Cu-oxide powder

The isothermal sintering behaviour of submicrometre-sized (<50 nm) powders of single-phase YBa₂Cu₃O _x (123) and unreacted stoichiometric mixture of submicrometre-sized (<50 nm) powders of BaCO₃, Y₂O₃ and CuO (which on calcination at 1173 K gives YBa₂Cu₃O _x ) was investigated through dilatometry under different sintering atmospheres. The sintering rate of the powder compacts was impeded by the presence of oxygen. The activation energies,Q, of sintering were determined to be 1218 kJ mol^–1 in argon, 1593 kJ mor^–1 in air and 2142 kJ mol^–1 in oxygen. A decrease in the apparent sintered density with increasing oxygen partial pressure was also observed. X-ray diffraction and thermal analyses (thermogravimetry and differential thermal analysis) showed no reaction during sintering of the single-phase product. Pellets fabricated from uncalcined powder exhibit two stages of sintering, one between 1073 and 1173 K having an activation energyQ=627kJ mol^–1, and a second one above 1173 K withQ=383.7 kJ mol^–1. A.c. susceptibility, resistivity and critical current density were determined as a function of the temperature of the sintered samples.     

Low-temperature sintering of zinc oxide varistors

High-field varistors in the system ZnO-CoO-MnO-Bi₂O₃ were fabricated using powders prepared by a previously developed coprecipitation process. Following calcination, the powders were compacted and densified by conventional pressureless sintering at temperatures below 750° C in air, The effects of sample green density, sintering temperature, and grain-growth inhibitor on densification and microstructure development were investigated. Addition of aluminium at the 125 p.p.m level was used to inhibit grain growth. Samples with densities >0.98 theoretical and grain sizes <1m were fabricated by high-pressure cold-isostatic pressing followed by sintering at 730° C. For comparison, typical commercial varistor devices have grain sizes of about 20 m and switching fields of approximately 2 kV cm^–1 after sintering at 1200 to 1400° C. As a result of the fine grain size, our high-field varistors had switching fields of 45 kV cm^–1 at a current density of 10 A cm^–2. Consistent with earlier work on extremely high-density varistors (>0.98 theoretical) prepared from similar powders, nonlinearity coefficients of about 10 were measured for current densities between 2.5 and 10 A cm^–2.     

Calcining influence on the powder properties of hydroxyapatite

The effect of different calcination temperatures on the powder characteristics and the sintered density of synthetic hydroxyapatite (HA) powders, produced using two different processing routes, was examined. Powders were produced by either drying, milling and sieving an as-precipitated HA or by spray-drying a slurry of precipitated HA. Calcining the two powders at temperatures between 400 and 1000 °C did not significantly affect the powder particle size. The specific surface areas of the two powders, however, were reduced from 70–80 m²/g for a calcination temperature of 400 °C to approximately 5–7 m²/g for 1000 °C. Analysis of the surfaces of the HA powders using scanning electron microscopy (SEM) illustrated the coarsening and subsequent sintering of the sub-micron crystallites that constitute a powder particle as the calcination temperature increased, corresponding to the decrease in surface area of the powders. The sintered densities of the final ceramics were not significantly affected by calcining the powders. Microhardness measurements of ceramics prepared from powders calcined at different temperatures showed no significant variations with calcination temperature or powder processing method. The results of this study have illustrated that for applications where HA may be used in powder form, for example in plasma-spraying and for the production of HA-polymer composites, calcining the HA will significantly affect the powder properties, namely the surface area and morphology of the powders. For applications requiring HA in a dense ceramic form, for example as granules or blocks, calcining the powders does not significantly affect the properties of the final ceramic.     

Synthesis and characterization of (Sr1−x′K2x)Zr4(PO4)6 ceramics

Single phase (Sr_1–x K_2x )Zr₄(PO₄)₆, where x lies between 0.0 and 1.0, ceramic powder with a submicron scale particle size has been synthesized successfully at calcination temperatures as low as 650–750°C by a sol-gel technique. The formation of the powder strongly depends on calcination temperature, but is independent of solution pH in the studied range. Dilatometric measurement shows an ultra-low linear coefficient of thermal expansion of 0.1×10^–6°C^–1 when x=0.5 at temperature intervals of 25–1000°C. Thermal conductivity and flexural strength of the materials were determined at ambient temperature to be 1.0 Wm^–1K^–1 and as high as 280 MPa, respectively, indicating that this material can be an excellent candidate in many applications, especially those subjected directly to severe environments.     

Coprecipitation-derived mullite and mullite-zirconia composites

Precursor powders of mullite-zirconia (0–40 wt% ZrO₂) were prepared by a hydroxide coprecipitation method and their behaviour during calcination between room temperature and 1500 °C was studied using thermal analysis, X-ray diffraction and electron microscopy. The only crystalline phases present in the precalcined powders were bayerite and gibbsite, and these were stable up to 250 °C. Powders containing ZrO₂ were initially amorphous, but on calcination between 250 and 850 °C produced different crystalline phases at temperatures which depended on the amount of zirconia present. Thus in the case of mullite-40 wt% ZrO₂, zirconia crystallized at about 850 °C and was stable up to 1200 °C, when it reacted with free silica to form zircon (ZrSiO₄). Mullite formed above 1250 °C at the expense of zircon and remained stable at higher temperatures. The oxide powders were very homogeneous, and on sintering produced ceramics with a fine-grained uniform microstructure. The powders were very reactive and could be sintered conventionally to near-theoretical density at 1600–1700 °C without sintering aids. The fracture strength of mullite was about 275 MPa, and this could be improved to 350 MPa by hot isostatic pressing the presintered bodies. Addition of zirconia enhanced the sintering kinetics as well as the fracture strength of mullite.     

Thermoanalytical characteristics of powders in dental cast investment

The present study examined the thermal properties of phosphate-bonded investments, a gypsum-bonded investment and an experimental investment powder when the basic powders were heated to high temperatures by simultaneous differential thermal analysis (DTA) and thermogravimetry (TG). The phosphate-bonded investments showed values of about 59 kcal mol^–1 (247 kJ mol^–1) (thermal decomposition of NH₄H₂PO₄) and about 11 kcal mol^–1 (46 kJ mol^–1) (formation of NH₄MgPO₄). Thermal reactions occurred clearly on the DTA-TG curves for the investment powders, using powders of NH₄H₂PO₄, and MgO with NH₄H₂PO₄/MgO = 1 as main components in the investment.     

Fine yellow α-SiAlON:Eu phosphors for white LEDs prepared by the gas-reduction–nitridation method

Yellow-emitting α-SiAlON:Eu²⁺ phosphors were synthesized by the gas reduction and nitridation of a homogeneous oxide precursor in a CaO–Al₂O₃–SiO₂–Eu₂O₃ system at 1400–1450 °C using an NH₃–CH₄ mixture gas as a reduction–nitridation agent. The precursor was prepared by a sol–gel process using a low-cost nitrate, tetraethyl orthosilicate and citric acid as the starting materials. The effects of reaction parameters such as heating rate, temperature, holding time and CH₄ content on the composition, microstructure and photoluminescence of the prepared powders were investigated. Nearly single-phase α-SiAlON was successfully synthesized by the one-step gas reduction and nitridation without the need for post-annealing at a higher temperature. The prepared powders consisted of relatively well-dispersed and uniform crystals with a hexagonal shape. The photoluminescence spectra of Eu-doped Ca-α-SiAlON phosphors excited by near-ultraviolet or blue light showed a broad, yellow emission band at 500–700 nm, which agrees well with that obtained from phosphors prepared by the conventional solid-state reaction.     

The influence of microstructure on the thermal conductivity of aluminium nitride

Starting from three different commercial powders, AIN materials were densified by pressureless sintering under various temperature and time values in order to investigate the influence of microstructure on thermal conductivity. The influence of the sintering aids (3 wt% Y₂O₃ and 2 wt% CaC₂) and of the forming processes (cold isostatic pressing and thermocompression of tape cast pieces) were also been evaluated. Thermal conductivity increased with the purity level of the starting powder and with an increasing the sintering temperature and soaking time. The highest thermal conductivity values (196 Wm^–1 K^–1) were obtained with the purest powder and high temperature (1800 °C) sintering over long periods (6 h). No influence on thermal conductivity was detected from the forming technique.     

Study of (Bi4−x La x ) Ti3O12 Powders and Ceramics Prepared by Sol-Gel Method

La-modified (Bi_4–x La _x )Ti₃O₁₂ (abbreviated as BLT) powders were prepared by sol-gel processing methods. The powders were characterized by differential thermal analysis (DTA) and laser-diffraction particle-size analysis. The (Bi_4–x La _x )Ti₃O₁₂ ceramics were prepared from the powders and characterized by X-ray diffraction (XRD). The results indicate that the sol-gel method can be used to prepare nanometer powder for the new types of BLT ferroelectric ceramics. The solid reaction of BLT powders occurs at 730°C approximately resulting in the growth of BLT grain. The average grain size may be varied in the range 60–500 nm, depending on the calcination temperature of the powders. The (Bi_4–x La _x )Ti₃O₁₂ ceramics prepared from the powders were polycrystalline materials with completely monoclinic (Bi_4–x La _x )Ti₃O₁₂ phase.     

Low-temperature synthesis of Y2SiO5:Eu powders using mesoporous silica and their luminescence properties

This paper reports the synthesis of Eu³⁺ ions-doped Y₂SiO₅ (Y₂SiO₅:Eu³⁺) powders by mesoporous template route. Using mesoporous silica SBA-15 as silica source, Y₂SiO₅:Eu³⁺ powders were prepared by solid-state reaction at a calcination temperature of 1300 °C without fluxes. The prepared Y₂SiO₅:Eu³⁺ powders were characterized by X-ray diffraction, scanning electron microscope, nitrogen adsorption-desorption isotherms, and photoluminescence spectroscopy. The results show that the crystalline Y₂SiO₅:Eu³⁺ particles are dense and have a morphology similar to SBA-15. The low calcination temperature is attributed to the high reactive activity of SBA-15 with large surface area and non-crystalline structure. The Y₂SiO₅:Eu³⁺ powders prepared at a low calcination temperature show luminescence properties similar to the reported results of Eu³⁺ doped-Y₂SiO₅ samples prepared at high temperatures.     

Fabrication and optical properties of NUV-emitting SiO2–SrB4O7:Eu glass–ceramic thin films

SiO₂–SrB₄O₇:Eu²⁺ glass–ceramic thin films were fabricated for possible application in near ultraviolet (NUV) emitting devices. Nano-sized SrB₄O₇:Eu²⁺ powders were prepared by a Pechini-type sol–gel method and a subsequent ball-milling treatment. The powders showed NUV emissions centered at 367 nm, upon irradiation with UV of shorter wavelengths, due to an allowed 4f⁶5d¹ → 4f⁷ electronic transition of Eu²⁺ ions. The glass–ceramic thin films were prepared by dip-coating of tetraethylorthosilicate (TEOS) solutions dispersed with the nano-sized SrB₄O₇:Eu²⁺ powders and a subsequent heat-treatment. It was found that the glass–ceramic thin films had relatively high thermal stability up to 800 °C in terms of the Eu²⁺ emissions. SiO₂ layers surrounding SrB₄O₇:Eu²⁺ appeared to be effective for the surface passivation of the phosphor particles.     

Doped Tl-1223 Superconductors

Doped Tl-1223 superconductors of the composition Tl_aBi_bPb_cBa_nSr_2–nCa₂Cu₃O_y (a = 0.50 – 0.76, b = 0, 0.16 and 0.3, c = 0.5, 0.24 and 0, n = 0.15 – 0.4) were prepared from oxidic Ba-Sr-Ca-Cu precursor material. Upon calcination of the tartrate gels or the nitrates, the respective amounts of Tl₂O₃, PbO and Bi₂O₃ were added to the oxidic powders by milling. The samples were sintered in silver foil. The specimens consisted predominantely of the Tl-1223 phase with small amounts of Tl-1212 and secondary phases. Tc₍₀₎-values ranged between 115 K and 119 K with transition widths around 1 K. Transport critical current densities up to 1.4 kA cm^–2 at 77 K were measured for the assintered samples. Texturing was obtained by repressing and resintering of the superconducting material followed by annealing at 750°C for 50 h in flowing oxygen. The transport critical current densities could be improved up to 7 kA cm^–2 by the thermomechanical treatment. Microstructural studies yielded information on the alignment of the superconducting grains, on secondary phases and the porosities.     

Magnetic properties of hydrothermally synthesized strontium hexaferrite as a function of synthesis conditions

Fine particles of strontium hexaferrite, SrFe₁₂O₁₉, with a narrow size distribution have been synthesized hydrothermally from mixed aqueous solutions of iron and strontium nitrates under different synthesis conditions. The relationship between the synthesis variables (temperature, time and alkali molar ratio) and the magnetic properties has been investigated. The results have shown that, as the synthesis temperature increases, the saturation magnetization of the particles increases up to a plateau and the coercivity decreases. As the alkali molar ratio R(=OH^–/NO ₃ ^– ) increases, the coercivity decreases and goes through a local minimum, while the saturation magnetization increases and goes through a local maximum. Increasing the synthesis time from 2 h to 5 h has no significant effect on the saturation magnetization, but decreases the coercivity. An anisotropic sintered magnet with a high saturation magnetization value of 67.26 e.m.u g^–1 (4320 G) has been fabricated from the hydrothermally synthesized powders.Relationship between the c.g.s and S.I.units which are used in this paper are as follows: 1 erg = 10^–7 J, 1 e.m.u. cm^–3 = 12.57×10^–7 Wom^–2 (tesla), 1 oersted (Oe) = 79.6 A m^–1, 1 G = 10^–4 tesla (T).     

Flash calcines of kaolinite: Effect of process variables on physical characteristics

The physical transformation of powdered kaolinite associated with rapid dehydroxylation during flash calcination has been followed using pycnometry, thermogravimetry, electron microscopy, X-ray powder diffraction and infrared spectroscopy. 116 partially dehydroxylated kinetically-frozen calcines were produced in a laboratory flash calciner covering the following ranges of process variables: calciner temperature 700–1000 °C, rate of heating to calciner temperature 4700–15000 Ks^–1, residence time at the calciner temperature 0.1–1.5 s, He or N₂ calciner atmosphere. From the analyses of these calcines a picture of the changes in physical characteristics caused by flash heating of kaolinite has emerged and is described.     

Growth of ultra-fine cobalt ferrite particles by a sol–gel method and their magnetic properties

Ultra-fine CoFe₂O₄ particles are fabricated by a sol–gel method and magnetic and structural properties of powders are investigated. Cobalt ferrite powders fired at and above 450 °C have only a single-phase spinel structure and behave ferrimagnetically. Powders annealed at 350 °C have a typical spinel structure and are of the paramagnetic and ferrimagnetic nature, simultaneously. With X-ray diffraction and Mossbauer spectroscopy measurements, the formation of nano-crystallized particles is confirmed when cobalt ferrite is annealed at 200 °C. In addition, the transition from the paramagnetic to the ferrimagnetic state is observed in samples fired at 200 °C as the measuring temperature decreases from the room to liquid nitrogen temperature. The magnetic behaviour of CoFe₂O₄ powders fired at and above 350 °C shows that an increase of the annealing temperature yields a decrease in the coercivity and, in contrast, an increase in the saturation magnetization. The maximum coercivity and the saturation magnetization of cobalt ferrite powders prepared by the sol–gel method are 2020 Oe and 76.5 e.m.u. g^–1, respectively.     

Dispersion of ZrO2 particles in aqueous suspensions by ammonium polyacrylate

The effects of poly anionic-electrolyte (ammonium polyacrylate, PAA) as a dispersant on two kinds of ZrO₂ (monoclinic and yttria-doped tetragonal zirconia) aqueous suspensions were examined by the measurements of-potential and viscosity, the sedimentation test and the determination of the wet point and flow point of the powders. Additions above 2.5 wt% PAA to zirconia gave a negative high-potential above –30 mV, and then –45 and –30 mV were obtained for monoclinic and tetragonal zirconia above 5 wt% PAA, respectively. A high negative-potential above –30 mV was retained with 5 wt% PAA for a change in pH over a wider range (pH 6 to 10 for monoclinic ZrO₂, 7 to 9 for tetragonal ZrO₂) in comparison to that of ZrO₂ without dispersant. The increase of the-potential resulted in a decrease in the viscosity. The evaluation of dispersion by the sedimentation test was correlated well with the value of-potential and the viscosity of the suspensions. The presence of native positive charge of monoclinic and tetragonal zirconia powders required an excess amount of PAA to attain dispersion of the suspension. There was a small difference in the least amount of PAA required to attain good dispersion between monoclinic and tetragonal ZrO₂. The difference was also indicated by changes of the flow point on PAA addition. Addition of 0.1% PAA to monoclinic ZrO₂ and 0.25 wt% to tetragonal ZrO₂ gave a maximum value of the flow point, whereas the positive-potential fell to zero. Measurement of the flow point was a simple and useful technique for rapid evaluation of a required amount of dispersant for ZrO₂ suspensions.     

Effect of excess Pb on formation of perovskite-type 0.67Pb(Mg<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>)O<Subscript>3</Subscript>-0.33PbTiO<Subscript>3</Subscript> powders synthesized through a sol–gel process

Perovskite-type 0.67Pb(Mg_1/3Nb_2/3)O₃-0.33PbTiO₃ (PMNT) powders were fabricated by using a sol–gel process. Excess Pb(CH₃COO)₂·3H₂O (0, 2, 5, 10 or 15 mol%) was added to starting materials to compensate PbO loss from volatilization during heat treatment. X-ray diffraction (XRD) was employed to investigate the effect of excess Pb on the perovksite phase formation of the PMNT powders. It was found that the optimal level of the excess Pb content is 5 mol%. When the raw materials contained 5 mol% excess Pb, the PMNT powders of purest perovskite form was obtained at the calcination temperature of 850 °C. In the PMNT powders, most part of the intermediate phase was Pb-rich pyrochlore Pb₂Nb₂O₇ which was transformed into perovskite phase after calcination at 650 °C, while the residual pyrochlore phase was Pb-deficient Pb₃Nb₄O₁₃ which required calcination at a higher temperature (650–850 °C) to transform into perovskite phase. Compared with the conventional solid-state reaction methods and the solution-based methods reported previously, the present sol–gel route is better at synthesizing PMNT powders of perovskite phase at a low temperature.     

Effect of partially oxidized Ti powders on the microstructure and PTCR characteristics of (Ba,Sr)TiO3

Rutile TiO₂ (a=4.594 å and c=2.958 å) phase was formed on the outer region of Ti powders after oxidation at 600 °C for 1–300 h. Porous (Ba,Sr)TiO₃ ceramics were fabricated by adding partially oxidized Ti powders (4–8 vol %) into (Ba,Sr)TiO₃ powders, and showed excellent positive temperature coefficient of resistivity (PTCR) characteristics after paste-baking treatment at 580 °C in air. The PTCR characteristics of the porous ceramics were mainly attributed to the adsorption of oxygen at the grain boundaries. The microstructure and electrical properties of the porous (Ba,Sr)TiO₃ ceramics containing the partially oxidized Ti powders oxidized at 600 °C for different oxidation times (1–300 h) were investigated.     

Influence of the calcining temperature on the sintering and properties of PZT ceramics

Niobia-doped PZT powders were prepared by both hydroxide and oxalate coprecipitation methods. The resulting amorphous powders were calcined at two different temperatures (550 and 700 °C) and the morphology and size of the calcined particles were studied. It was found that hydroxide powders, when calcined at 700 °C, gave 98% theoretical density,d _th, bodies at a sintering temperature as low as 1100°C in air. The high agglomeration present in oxalate powders strongly retarded densification. Of the piezoelectric properties, ak _p higher than 60% and ad ₃₃ constant of 360 × 10^–12 CN^–1 were measured. Dielectric parametersT _c andk _3T, 310° C and 1100, respectively, were determined.     

Preparation of molybdenum and tungsten carbides from solution derived precursors

Synthesis principles have been developed for the preparation of solution derived precursors that can be selectively converted to desired refractory materials, as powders, fibres or thick films. The precursors are prepared from aqueous or ethylene glycol solutions containing a pyrolysable organic compound (carbonaceous gel or saccharose) and a soluble molybdenum or tungsten compound (peroxo acid or ethylene glycolate). The concentrated solutions exhibit rheological properties that allow fibre drawing and production of thick films. The sequence of the high temperature reactions – pyrolysis, reduction, carburization – was investigated by thermal gravimetric analysis (TGA), X-ray analysis and nitrogen adsorption. Because of the high homogeneity of the reactants, carbon and transition metal suboxides in the pyrolysed precursors, the observed carburization temperatures (800–1200 °C) are lower than those used industrially. Most of the intermediate and final products–carbon/oxide composites, Mo(C, O), Mo₂C, W₂C, and WC – are materials of a high Brunauer–Emmett–Teller (BET) surface area (50–200 m² g^–1).