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.     

Sintering mechanisms and microstructural development of coprecipitated mullite

Coprecipitated mullite precursor powders of the bulk compositions 78 wt% Al₂O₃+22 wt% SiO₂ (high-Al₂O₃ material) and 72 wt% Al₂O₃+28 wt% SiO₂ (low-Al₂O₃ material) have been used as starting materials. The precursor powders were calcined at 600, 950, 1000, 1250, and 1650 C, and test sintering runs were performed at 1550, 1600, 1650, 1700, and 1750 C. Homogeneous and dense ceramics were obtained from cold isostatically pressed (CIPed) powders sintered in air at 1700 C. Therefore, all further sintering experiments were carried out at 1700 C. After pressureless sintering, sample specimens were hot isostatically pressed (HIPed) at 1600 C and 200 bar argon gas pressure. Sintering densifications of low Al₂O₃ materials ranged between 94% and 95.5%. There was no clear dependency between densification and calcination temperature of the starting powders. High-Al₂O₃ compositions displayed sintering densities which increased from 97% at 600 C calcination temperature to 99% at 950 C calcination temperature. Higher calcination temperatures first caused slight lowering of the sintering density to 95.5% (calcination temperature 1250 C) but later the density strongly decreased to a value of 85% (calcination temperature 1650 C). HIPing of pressureless sintered specimens prepared from powders calcined between 600 and 1100 C yielded 100% density. At the given sintering temperature of 1700 C, the microstructure of sample specimens was influenced by Al₂O₃/SiO₂ ratios and by calcination temperatures of the starting powders. Homogeneous and dense microstructures consisting of equiaxed mullite plus some minor amount of -Al₂O₃ were produced from high-Al₂O₃ powders calcined between 600 and 1100 C. Low-Al₂O₃ sample specimens sintered from precursor powders calcined between 600 and 1100 C were less dense than high-Al₂O₃ materials. Their microstructure consisted of relatively large and elongated mullite crystals which were embedded in a fine-grained matrix of mullite plus a coexisting glass phase. The different microstructural developments of high- and low-Al₂O₃ compositions may be explained by solid-state and liquid-phase sintering, respectively. The microstructure of HIPed samples was very similar to that of pressureless sintered materials, but without any pores occurring at grain boundaries.     

The sinterability of ultrafine WC powders obtained by a CVD method

The sintering behaviour of ultrafine WC powders produced by a CVD method (particle size <0.3m) and commercial WC powders (particle size ~ 1m) is investigated in hydrogen and in vacuum. It has been found that ultrafine WC powders have an extremely high sinterability and give a sintered body with a relative density of 100% by sintering at a considerably lower temperature than normal, such as 1750° C. Also WC powders with a large particle size and a wide-size distribution have a high sinterability caused by the presence of fine particles and the sinterability of WC powders is influenced significantly by the sintering atmosphere. The atmospheric effect is discussed in connection with the heating behaviour of a surface oxide layer and free carbon.     

Supersolidus liquid phase sintering of moulded metal components

The influence of supersolidus liquid phase sintering (SLPS) on the density of sintered components manufactured using a Ni-base superalloy powder (N18) has been studied. A compression moulding technique was employed to simulate the metal injection moulding (MIM) process using coarse N18 powder, with a particle size distribution of 40–63 m, as opposed to fine powders of less than 10m normally used in conventional MIM. The study has demonstrated how the problem of low sintered density, encountered in solid-state sintering using coarse powders, can been overcome by SLPS and that the sintered densities of the N18 powder via the moulding process route were comparable with those produced by conventional die pressing and sintering.     

Nanosized hydroxyapatite powders derived from coprecipitation process

Nanosized hydoxyapatite (Ca₁₀(PO₄)₆(OH)₂ or HA) powders were prepared by a coprecipitation process using calcium nitrate and phosphoric acid as starting materials. The synthesized powders were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and Brunauer-Emmett-Teller (BET) specific area measurment techniques. Single phase HA, with an average grain size of about 60 nm and a BET surface area of 62 m²/g, was obtained. No grain coarsening was observed when the HA powders were heated at 600°C for 4 hours. HA ceramics were obtained by sintering the powders at temperatures from 1000°C to 1200°C. Dense HA ceramics with a theoretical density of 98% and grain size of 6.5 m were achieved after sintering the HA powders at 1200°C for 2 hours. HA phase was observed to decompose into tricalcium phosphate when sintered at 1300°C. The microstructure development of the sintered HA ceramics with sintering temperature was also characterized and discussed.     

Effect of powder characteristics on the sinterability of hydroxyapatite powders

The effect of different sintering conditions on the sintered density and microstructure of two different hydroxyapatite (HA) powders was examined. The powder characteristics of a laboratory synthesized HA powder (Lab HA) were low crystallinity, a bimodal particle size distribution, a median particle size of 22 m and a high specific surface area (SSA) of 63 m²/g. By contrast, a commercial calcined HA (commercial HA) was crystalline and had a median particle size of 5 m and a low SSA of 16 m²/g. The different powder characteristics affected the compactability and the sinterability of the two HA powders. Lab HA did not compact as efficiently as commercial HA, resulting in a lower green density, but the onset of sintering of powder compacts of the former was approximately 150 °C lower than the later. The effect of compaction pressure, sintering temperature, time and heating rate on the sintered densities of the two materials was studied. Varying all these sintering conditions significantly affected the sintered density of commercial HA, whereas the sintered density of Lab HA was only affected significantly by increasing the sintering temperature. The Vickers hardness, H_v, of Lab HA was greater than commercial HA for low sintering temperatures, below 1200 °C, whereas for higher sintering temperatures the commercial HA produced ceramics with greater values of hardness. These trends can be related to the sinterability of the two materials.     

Analysis of local heat transfer properties of tape-cast AlN ceramics using photothermal reflectance microscopy

Photothermal reflectance microscopy was applied to the analysis of local thermal diffusivity on tape-cast AlN ceramics. The materials were obtained from three different commercial powders, two sintering temperatures (1750 and 1800 °C), and 3 wt % Y₂O₃ sintering aid. Owing to the high spatial resolution of the technique (30 m in the present case), measurements in different positions on the sample surface were carried out. In this way a study of the homogeneity of thermal properties was performed.     

Sintering of aluminium nitride: Particle size dependence of sintering kinetics

The effect of particle size (0.78 4.4 m) on the sintering kinetics of AIN powder was investigated in the temperature range from 1600 to 2000° C and the results were analysed on the basis of vacancy diffusion models. The mechanisms of sintering are discussed.Fractional shrinkage is proportional to the nth power of soaking time with n = 0.20 for 4.4 m and 1.5 m powders and 0.33 for 0.78 m powder. For the 0.78 m powder at 1900° C, however, n decreases gradually as grain growth proceeds. The experimental activation energy for sintering is between 92 kcal/mole for 4.4 m and 129 kcal/mole for 0.78 m powder. Unlike this activated energy, the rate of sintering and the diffusion constant calculated from it increase drastically with decrease of particle size; the derived diffusion constant for 1.5 m powder is 10¹ to 10² times larger than that of 4.4 m powder, and for 0.78 m powder the diffusion constant is estimated to be still higher.The particle-size dependence of parameter n and the diffusion constant seems to be caused by a variation in predominant diffusion mechanisms; namely, bulk diffusion in coarse powder and surface or grain-boundary diffusion in fine powder.     

Infrared transmission of sintered 3 mol% Y2O3-ZrO2 gel

Translucent ZrO₂ film was successfully prepared by gelling hydrothermally produced nano-ZrO₂ powders. The film (300 m thick) was found to transmit light to 6.5 m (40% transmission) when sintered at 1200 °C, but transmission was totally lost after sintering at 1300 °C for 1 h. Residual organic material such as urea, which was used for preparing the powder, dominated the transmission of the film in the region between 1.3 and 4.5 m when sintered below 1000 °C. When sintered above 1000 °C, the microstructure controlled the transmission. Both organic residuals and the microstructure of the zirconia were found to determine the transmission in 4.5–6.5 m region.     

Densification and microstructural developments during the sintering of aluminium silicon carbide

Densification and microstructural developments during the sintering of aluminum silicon carbide (Al₄SiC₄) were examined. Two types of Al₄SiC₄ powders were prepared by the solid-state reactions between: (i) Al, Si, and C at 1600°C for 10 h (designated as Al₄SiC₄(SSR)), and (ii) chemically-vapour deposited ultrafine Al₄C₃ and SiC powders at 1500°C for 4 h (Al₄SiC₄(CVD/SSR)). The specific surface areas of the Al₄SiC₄(SSR) and Al₄SiC₄(CVD/SSR) powders were 2.7 and 15.5 m² · g^–1, respectively. Relative densities of the pressureless-sintered Al₄SiC₄(SSR) and Al₄SiC₄(CVD/SSR) compacts were as low as 60–70% for firing temperatures between 1700°C and 2000°C. The relative densities of Al₄SiC₄(SSR) and Al₄SiC₄(CVD/SSR) compacts could be enhanced using the hot-pressing technique; the relative density of the Al₄SiC₄(SSR) compact hot-pressed at 1900°C for 3 h was 97.0% whereas that of the Al₄SiC₄(CVD/SSR) compact hot-pressed at 1900°C for 1 h attained 99.0%. The former microstructure was composed of plate-like grains of width 10–30 m and thickness 10 m whilst the latter microstructure was comprised of equiaxed grains with a typical diameter of 10 m. Densification of the Al₄SiC₄(CVD/SSR) compacts appeared to be promoted compared to the Al₄SiC₄(SSR) compact and this was attributed to the higher surface area, reduced agglomeration of the starting primary particles, and more homogeneous chemical composition.     

Sol-emulsion-gel synthesis of hollow mullite microspheres

Hollow mullite microspheres were obtained from emulsified diphasic sols by an ion extraction method. The surfactant concentration and viscosity of the sols were found to affect the characteristics of the derived microspheres. The gel and calcined microspheres were investigated by using thermogravimetry analysis (TGA), differential thermal analysis (DTA), Fourier transformed infrared spectroscopy (FTIR), X-ray diffraction (XRD), optical and scanning electron microscopy (SEM) and particle size analysis. TGA indicated the removal of most of the volatiles, i.e. 30.77 wt% up to about 500°C. Crystallization of the Si-Al spinel at 900°–970°C in gel microspheres was confirmed by DTA and XRD. XRD results also showed the formation of orthorhombic mullite at 1200°C. FTIR indicated the sequence of transformations taking place during heat-treatment of gel microspheres at different temperatures. The optical and scanning electron microscopy confirmed the spherical morphology of the gel and calcined particles. Formation of hollow microspheres with a single cavity was identified by SEM. The particle size distribution of the mullite microspheres calcined at 1300°C/1h exhibited a size range of 6–100 m with an average particle size (d ₅₀) of 22.5 m.     

Microwave and conventional sintering of rapidly solidified Al2O3-ZrO2 powders

The Al₂O₃-ZrO₂ eutectic composition was rapidly solidified, forming amorphous and crystalline structures. The as-quenched material was crushed and pressed into pellets which were sintered conventionally or with microwaves. Conventional and microwave sintering at temperatures up to 1600 °C resulted in a microstructure where 100–200 nm ZrO₂ grains were present intergranularly in the -Al₂O₃ grains. Larger ZrO₂ grains (1 m) were found intergranularly. The as-quenched lamellar structure spheroidized during sintering at high temperatures. Boron contamination of the powders resulted in more homogeneous and dense as-fired samples but promoted the ZrO₂ tetragonal-to-monoclinic transformation, which was attributed to increased grain boundary diffusivity. Conventional sintering at low temperatures resulted in the formation of rods of an Al₂O₃-rich phase which grew from a low-melting B₂O₃-rich liquid.     

Pressureless sintered ATZ and ZTA ceramic composites

Alumina-20 wt% zirconia (ATZ) and zirconia-20 wt% alumina (ZTA) composites were prepared by conventional sintering of commercial powders, with average particle sizes in the range 0.35–0.70 m. Sintering at 1650 °C for 4 h resulted in final densities up to 96%. Bending strength and hardness increased with the final density. The tetragonal volume fraction was strongly dependent on both the final density and tetragonal grain size. The relatively high fracture toughness of 9 MPa m^1/2 was associated with the highly dense microstructure consisting of tetragonal grains of the critical size.     

High pressure consolidation of B6O-diamond mixtures

Sintered composites in the B₆O-xdiamond (x= 0–80 vol%) system were prepared under high pressure and high temperature conditions (3–5 GPa, 1400–1800°C) from the mixture of in-laboratory synthesized B₆O powder and commercially available diamond powder with various grain sizes (<0.25, 0.5–3, and 5–10 m). Relationship among the formed phases, microstructures, and mechanical properties of the sintered composites was investigated as a function of sintering conditions, added diamond content, and grain size of diamond. Sintered composites were obtained as the B₆O-diamond mixed phases when using diamond with grain sizes greater than 0.5 m, while the partial formation of the diamond-like carbon was observed when using diamond grain sizes less than 0.25 m. Microhardness of the sintered composite was found to increase with treatment temperature and pressure, and the fracture toughness slightly decreased. A maximum microhardness of H _v57 GPa was measured in the B₆O-60 vol% diamond (grain size < 0.25 m) sintered composite under the sintering conditions of 5 GPa, 1700°C and 20 min.     

The laser surface-alloying of iron with carbon

Observations are reported on the structure of iron, laser surface-alloyed with carbon. Repeated laser surface-melting of iron pre-coated with DAG graphite has produced layers containing up to 6 wt % C, showing fine-scale white iron structures. Eutectic regions (interlamellar spacing 0.5m) have been shown by transmission electron microscopy to consist of Fe₃C + ferrite, the latter having formed by decomposition of austenite during solid state cooling. Regions of fine pearlite (spacing 55 nm) have also been observed. Carbon diffusion into the substrate during alloying produces a zone containing austenite and martensite.     

Study on barium titanate ceramics prepared by various methods

Barium titanate (BaTiO₃) ceramics have been fabricated using powders prepared by sol-gel, coprecipitation and mixed oxide methods. The powders prepared by sol-gel and coprecipitation have average crystallite diameters of 100 nm and 300 nm, respectively while the diameter of the mixed oxide powder is 1–3 m. When sintered at the same temperature of 1320°C, the three BaTiO₃ ceramics have very different grain size, with the one prepared by the mixed oxide method having the largest grain size of 20 m. The dielectric permitivity increases as the grain size of the ceramic becomes smaller. The room temperature (25°C) dielectric permittivity, pyroelectric and piezoelectric properties of these ceramics have been measured as functions of the poling field. The BaTiO₃ ceramic fabricated from nanosized powder derived from the coprecipitation method is found to have the smallest grain size and better properties than prepared from the sol-gel route, and is thus a good candidate for use in devices that required thick (10 to 20 m) ferroelectric films.     

Fabrication of hollow glass microspheres in the Na2O-B2O3-SiO2 system from metal alkoxides

Hollow glass microspheres (HGS) for laser fusion targets were fabricated in the system Na₂O-B₂O₃-SiO₂ from NaOCH₃, B(OCH₃)₃ and Si(OC₂H₅)₄. Gel powders prepared from metal alkoxides and urea liberate H₂O, CO₂ and NH₃ gases, evolution of which takes place completely at about 500° C. The precursor of HGS is formed by the encapsulation of these gas components in the glass layer formed at the surface of the powder. HGS are produced from the gel powders having both a melting temperature lower than about 1000° C and a viscosity at that temperature lower than 10⁵ P. In the Na₂O-B₂O₃-SiO₂ system, the compositions from which HGS are produced are those containing 55–75 wt% SiO₂ and 0–20 wt% B₂O₃. HGS ranging from 100–500m diameter and 0.5–7.0m wall thickness are obtained by change of urea content.     

Preparation and characterization of perovskite ceramic powders by gelcasting

Perovskite La0.6Sr0.4Co0.8Fe0.2O3– (LSCF) powders have been successfully synthesized from oxide and carbonates based on the principle of gelcasting. Phase-forming temperature is very dependent on the ball-milling process during the suspension preparation. As the ball-milling time is increased, the temperature of phase formation decreases, therefore the perovskite powder obtained has a larger Brunaver–Emmett–Teller (BET) specific surface area. The grain sizes were around 1 m at 1000°C and 2 m at 1100°C from scanning electron microscopy (SEM) photographs. The perovskite powders have good sinterability: the sintering densities of ceramic bodies shaped with as-prepared powders were investigated. SEM photos show that sintered ceramics exhibit a well defined morphology in the packing and sintering of particles. The oxygen permeance of disc shaped samples, with a thickness ranging from 1.02 to 1.98 mm was 6.39 × 10–8–1.99 × 10–8 mol cm–2 s–1 at 900°C indicating that LSCF ceramics have high oxygen permeation. It can be concluded that gelcasting is a simple and effective method for preparing practical multicomponent perovskite powders.     

Thermoelectric properties of fine-grained sintered (Bi2Te3)25-(Sb2Te3)75 p-type solid solution

P-type semiconductor alloy compacts of the composition (Bi₂Te₃)₂₅-(Sb₂Te₃)₇₅ with grain size (L) in the range 30 > L > 20 m, 20 > L > 15 m, 15 > L > 10 m, 10 > L > 5 and L < 5 m were prepared by cold press at a pressure of 77 × 10⁷ Nm^–2. The samples were sintered at 673 K. Measurements of the Seebeck coefficient, electrical resistivity and thermal conductivity were carried out. The experimental results show that the Seebeck coefficient increases, but not much from the single crystal. The electrical resistivity increases in particular for the size L < 5 m with a reduction in grain size. The total thermal conductivity seriously decreases as grain size decreases. It is concluded that the figure of merit of the compacted alloy would be significantly improved through the use of fine-grained powders of size 30–10 m.     

Formation of plate-like lanthanum-β-Aluminate crystal in Ce-TZP matrix

The reaction route and morphology of lanthanum--aluminate (LBA) crystals formed in Ce-TZP matrix were studied by examining the crystal phase changes and the microstructures in relation to the heat-treatment time, heat-treatment temperatures and the particle size of raw Al₂O₃ powders. In the Ce-TZP matrix, the LBA crystal was formed by the reaction between La₂O₃ and Al₂O₃ through the LaAlO₃ phase as the intermediate. La₂Zr₂O₇ forms at 800 °C and remains in the temperature range 800–1500 °C, and LaAlO₃ forms between 1200 and 1400 °C. The LaAlO₃ reacts with Al₂O₃ to form LBA above 1500 °C. The diffusion of La³⁺ through the La₂Zr₂O₇ phase was faster than that of Al³⁺. The morphology of LBA crystals was dependent on the particle size of the starting raw Al₂O₃ particle. When submicrometre size Al₂O₃ (0.4m) particles were used as the starting particles, anisotropic, plate-like LBA crystals, about 10m long, were formed during heat treatments. On the other hand, Al₂O₃ of larger grain sizes (3.6, 10.3m) yield conglomerates of LBA crystals. The size of the conglomerates is similar to that of the raw Al₂O₃ particle. The dependence of the morphology of LBA on the particle size of Al₂O₃ can be attributable to the sintering process of the Ce-TZP matrix, leading to the control of the mechanical properties of Ce-TZP ceramics with LBA crystals.