Microstructure of cBN-diamond sintered compact prepared by reaction sintering

cBN-diamond composite sintered compacts (diamond content 15–70 wt %) were prepared by reaction sintering at 7–7.5 GPa and 1400–1700 °C for 10–30 min from the starting powder of the hBN-diamond system in the presence of 1 wt % NH₄NO₃ as a volatile catalyst. A fully dense sintered compact with 99% conversion from hBN to cBN was obtained at 7 GPa and 1700 °C after 30 min. An induced transformation from hBN to cBN seemed to occur on the surface of the added diamond seed crystals. Diamond seed crystals (about 30 wt %, grain size 0.2–1.5 m) were found to be well-dispersed in the reaction-bonded cBN matrix. The Vickers microhardness of the sintered compact was 5100 kg mm^–2. The contacts between diamond grains were observed in the sintered compacts containing diamond seed grains of more than 70 wt %. The toughness of the sintered compact tended to increase with decreasing diamond content and the grain size of seed crystals.     

Reaction control of TiB2 formation from titanium metal and amorphous boron

TiB₂ powder was synthesized by a controlled formation reaction from titanium metal and amorphous boron. Precursory TiB₂ formed by the pretreatment of the mixed powder (mole ratio: B/Ti=2.0) at 600° C for 60 min in an argon stream. Hollow TiB₂ powder with an average grain size of 15m was obtained by subsequent heat treatment above 900° C for more than 60 min in an argon stream. The formation reaction of TiB₂ powder was further controlled by pretreatment of the mixed powder at 600° C for 60 min in a hydrogen and argon stream and subsequent heat treatment at 1000° C for 360 min in an argon stream, when hollow-free TiB₂ powder was formed by a milder formation reaction between amorphous boron and the reformed titanium metal with hydrogen diffused lattice.     

Ultralow expansion ceramics in the HfO2-TiO2 system synthesized by an hydrolysis and polycondensation technique

Ultra-refractory ceramics from the HfO₂-TiO₂ system in the range 30–40 mol% TiO₂, with a near-zero thermal expansion, have been synthesized by hydrolysis and polycondensation of titanium alkoxide and hafnium dichloride alcoholic solutions and sintered at moderate temperature. Thermal stability, crystallization, density and microstructure of these materials have been examined. The as-prepared powder, amorphous at room temperature, crystallized quickly when heated at 500 ° C. Entire crystallization occurred after treatment at 1000 °C. Sintering at 1500 °C on cold-pressed samples led to ceramics with weak porosity (7%), low expansion coefficient <1×10^–6 °C^– with a minimum for 30 mol% TiO₂ content. SEM examination on sintered materials at 1500 °C reveals a grain size from 2–6 m, increasing with TiO₂ content.     

Some properties of mullite powders prepared by chemical vapour deposition

The sinterability of mullite (3Al₂O₃·2SiO₂) powder prepared by chemical vapour deposition was examined to improve the conditions for fabricating dense mullite ceramics. The starting powder contained not only mullite, but also a small amount of -Al₂O₃ (Al-Si spinel) and amorphous material. Although the compressed powder was fired at a temperature between 1550 and 1700 °C for 1, 3 and 5 h, the relative densities of the sintered compacts were limited to 90%: (i) due to the creation of pores/microcracks during the solid state reaction (1100–1350 °C), and (ii) due to restriction on the rearrangement of grains because the amount of liquid phase (1550–1700 °C) was insufficient. Calcination of the starting powder was effective for preparation of easily sinterable powder with homogeneous composition. When the compact formed by compressing the calcined powder at 1400 °C for 1 h was fired at 1650 °C for 3 h, the relative density was raised up to 97.2%; moreover, mullite was the only phase detected from the sintered compact. The sintered compact was composed of polyhedral grains with sizes of 1–2 m and elongated grains with long axes of 6 m.     

Synthesis of TiB2 powder from a mixture of TiN and amorphous boron

TiB₂ powder was synthesized by solid state reaction using amorphous boron and TiN as a source of titanium. The TiB₂ formation did not occur at all in a nitrogen atmosphere even at 1400° C. TiB₂ formed above 1100° C in argon and hydrogen atmospheres. The only crystalline phase of TiB₂ powder was favourably synthesized at 1400° C for 360 min in an argon atmosphere from a starting powder with a composition containing excess boron (B/Ti = 2.2). The synthesized powder was well dispersed and had a particle size of 0.5 to 2 µm. The powder activity was evaluated by sintering at 4 G Pa and 1300 to 1600° C for 15 min.     

Fabrication and mechanical properties of silicon carbide–silicon nitride nanocomposites

A powder mixture of ultrafine –SiC–35 wt% –Si₃N₄ containing 6 wt% Al₂O₃ and 4 wt% Y₂O₃ as sintering additives were liquid–phase sintered at 1800°C for 30 min by hot–pressing. The hot–pressed composites were subsequently annealed at 1920°C under nitrogen–gas–pressure to enhance grain growth. The average grain–size of the sintered bodies were ranged from 96 to 251 nm for SiC and from 202 to 407 nm for Si₃N₄, which were much finer than those of ordinary sintered SiC–Si₃N₄ composites. Both strength and fracture toughness of fine–grained SiC–Si₃N₄ composites increased with increasing grain size. Such results suggested that a small amount of grain growth in the fine–grained region (250 nm for SiC and 400 nm for Si₃N₄) was beneficial for mechanical properties of the composites. The room–temperature flexural strength and fracture toughness of the 8–h annealed composites were 698 MPa and 4.7 MPa · m^1/2, respectively.     

Effects of added c-BN seed crystals on the reaction sintering of c-BN accompanied by a conversion from h-BN to c-BN

Reaction sintering behaviour of c-BN which is accompanied by a conversion from h-BN to c-BN was investigated under high pressure (7 GPa) and temperature (1700°C) conditions for 30 to 60min. A high conversion yield of c-BN in the sintered compact was attained by adding fine-grained c-BN seed crystals (particle size 0.5 to 8m) to h-BN powder in the presence of 1 wt% NH₄NO₃ as a catalyst. An induced transformation from h-BN to c-BN occurs over a large surface area of c-BN seed crystals, which results in the formation of direct interparticle bonding between c-BN grains in the sintered compact. A fully dense sintered compact of c-BN (bulk density 98% theoretical) was obtained from the specimen of 70wt% h-BN with 30wt% added c-BN crystals having a particle size of 0.5m. This c-BN compact had an average microhardness of 5100 kg mm^–2 and a specific dielectric constant of 10.0 at a frequency of 1 MHz.     

SiC matrix composites reinforced with internally synthesized TiB2

A new process of preparing particulate-reinforced ceramic composites by internal synthesis has been developed. SiC powder mixed with TiN and amorphous boron was hot-pressed above 2000° C in an argon atmosphere. The boron molar content in the mixture was designed to be more than twice that of TiN. In the process of hot-pressing, the following reaction took place between 1100 and 1700° C TiN+2B TiB₂+1/2N₂ The synthesis of TiB₂ was followed by the densification of SiC matrix with the aid of the excess boron. The new process provides SiC matrix composites in which fine TiB₂ particulates are dispersed. Compared with hot-pressed monolithic SiC, the composite containing 20 vol % TiB₂ exhibits a 80% increase in fracture toughness and about the same flexural strength of 490 MPa at 20° C in air and 750 MPa at 1400° C in a vacuum.     

Sinterability of magnesium-oxide powder containing spherical agglomerates

The magnesium-oxide (MgO) powders were prepared by calcining basic magnesium carbonate (4MgCO₃·Mg(OH)₂·4H₂O; BMC) powder at a temperature between 600°C and 1200°C for 1 to 5 h. The resulting MgO powders contained spherical agglomerates with diameters of 10–50 m; the external shapes of these BMC agglomerates remained unchanged even after the calcination. With increasing compaction pressure, the densification of MgO powder compacts proceeded by (i) the rearrangement of agglomerates (50 MPa), (ii) the collapse of agglomerates (50–100 MPa), and (iii) the closer packing of primary particles (100 MPa). The MgO compact was fired at 1400 °C for 5 h. The relative density of the sintered MgO compact whose starting powder was prepared by calcining the BMC at 1000°C for 3 h attained 98.0%. The bending strength of this sintered MgO compact attained 214 MPa.     

An improvement in processing of hydroxyapatite ceramics

Hydroxyapatite ceramics have been fabricated via two different processing routes, a conventional processing route and an emulsion-refined route. The conventional precipitation processing of powder precursors for hydroxyapatite ceramics results in the formation of hard particle agglomerates, which degrade both the compaction and densification behaviour of the resultant powder compacts. An emulsion-refinement step has been shown to be effective in softening particle agglomerates present in the conventionally processed powder precursor. As a result, the emulsion-refined powder compact exhibits both a higher green density and a higher sintered density than the un-refined powder compact, on sintering at temperatures above 800 °C. The effect of powder agglomeration on densification during both the initial and later stage of sintering is discussed. The attainable sintered density of the conventionally processed material was found to be limited by the presence of hard powder agglomerates, which were not effectively eliminated by the application of a pressing pressure of 200 MPa. These hard powder agglomerates, which form highly densified regions in the sintered ceramic body, commenced densification at around 400 °C which is more than 100 °C lower than the densification onset temperature for the emulsion-refined powder compact, when heated at a rate of 5 °C min^–1. The inter-agglomerate voids, manifested by the differential sintering, resulted in the formation of large, crack-like pores, which act as the strength-limiting microstructural defects in the conventionally processed hydroxyapatite. A fracture strength of 170±12.3 MPa was measured for the emulsion-refined material compared to 70±15.4 MPa for the conventionally processed material, when both were sintered at 1100 °C for 2 h.     

HIP-sinteredβ- and mixedα-β sialons densified with Y2O3 and La2O3 additions

Various fully dense sialon materials sintered by the glass-encapsulated hot isostatic pressing technique were synthesized using Y₂O₃ and/or La₂O₃ as sintering aids. Constant molar amounts of the oxide mixtures were added in the ratios Y₂O₃/La₂O₃:100/0, 75/25, 50/50, 25/75, 0/100. The samples were sintered at two different temperatures, 1550 and 1825° C. At the lower temperature, unreacted-Si₃N₄ was present in the samples in addition to-sialon and secondary phases. The samples sintered at 1825° C showed that yttrium but not lanthanum favoured-sialon formation. The amount of intergranular phase increased by about 50% when Y₂O₃ was replaced by La₂O₃. The La-sialon ceramics have as good an indentation fracture toughness as the Y-sialon ceramics, about 5 MPam^–1/2, but the Vicker's hardness is slightly lower, being 1400 kg mm^–2 at a 98 N load.     

Synthesis and Properties of Willemite,Zn2SiO4, and M2+:Zn2SiO4 (M = Co and Ni)

Fine particles of willemite, -Zn₂SiO₄, were prepared by both solution combustion and sol-gel methods. Both processes yield single-phase, large-surface area (26- and 78-m²/g), sinteractive willemite powders. Thermal evolution of crystalline phases was studied using X-ray powder diffraction patterns. The combustion method favors low-temperature formation of willemite compared to the sol-gel method. The powders, when uniaxially pressed and sintered at 1300°C, achieved 78–80% theoretical density. The microstructures of the sintered body show the presence of equiaxed 0.5- to 4-m grains. Blue pigments of willemite doped with Co²⁺ and Ni²⁺ were also prepared by the combustion process.     

Functionally gradient titanium-aluminide composites produced by laser cladding

The laser surface cladding of Ti-Al/TiB₂ composites was investigated as a means of producing a functionally gradient material on a commercially pure Ti substrate. Single and double layers were produced. The processing parameters were: 1.7 kW laser power, 3 mm beam diameter, 3–22 mms^–1 traverse speeds, 2.2–6.2 g min^–1 powder flow rates. The results showed that functionally gradient Ti-Al/TiB₂ systems 2 mm thick, with a progressive increase in the Al content from 0 to 35 wt% Al (50 at % Al) could be produced by vertically overlapping two clad layers using powder mixtures of selected compositions. Microstructural and compositional characterization were performed on single-layer and two-layer clads. Preliminary wear testing carried out on a laser surface Ti-Al/TiB₂ single-clad layer and on commercial-purity titanium demonstrated the beneficial effect of laser cladding on the wear resistance.     

Preparation and densification of superconducting YBa2Cu3Ox ceramics

The solid-state reaction method to form the superconducting oxide YBa₂Cu₃O _x was studied. It was found that the starting cupric and yttrium components accelerated the decomposition of the BaCO₃ component. At a constant heating rate of 10 ° Cmin^–1 in thermogravimetric analysis, the temperature of complete decomposition,T _f, was lowered from greater than 1000 ° C in pure BaCO₃ to between 915 and 985 ° C. The effectiveness in decreasingT _f can be ranked in the order of oxalate, carbonate and oxide. The highest sintered density achieved in this study was 6.03 g cm^–3 (/_th = 95%) at 990 ° C and 5.85 g cm^–3 (/_th = 92%) at 960 ° C. The source of cupric ion had the largest effect on densification. The use of cupric carbonate resulted in a consistently high Archimedes density of about 6.00gcm^–3 and large dimensional shrinkage of about 20% at 990 ° C for 12h. In contrast, the use of cupric oxide gave the lowest density and smallest shrinkage. Within the same powder lot, higher sintered density and smaller dimensional shrinkage were observed in samples with higher initial green density and compaction pressure. However, the data suggested that the enhanced densification and higher density achieved by the use of cupric carbonate and oxalate cannot be accounted for by the different physical characteristics of the powders and the mechanics of powder compaction, measured collectively by the green density.     

Sintering and crystallization of mullite powder prepared by sol-gel processing

Mullite powder with the stoichiometric composition (3Al₂O₃.2SiO₂) was synthesized by a sol-gel process, followed by hypercritical drying with CO₂. Within the limits of detection by X-ray diffraction, the powder was amorphous. Crystallization of the powder commenced at 1200 °C and was completed after 1 h at 1350 °C. In situ X-ray analysis showed no intermediate crystalline phases prior to the onset of mullite crystallization and the pattern of the fully crystallized powder was almost identical to that of stoichiometric mullite. The synthesized powder was compacted and sintered to nearly theoretical density below 1250 °C. The microstructure of the sintered sample consisted of nearly equiaxial grains with an average size of 0.2 m. The effect of heating rate (1–15 °C min^–1) on the sintering of the compacted powder was investigated. The sintering rate increased with increasing heating rate, and the maximum in the sintering curve shifted to higher temperatures. The sintering kinetics below 1150 °C can be described by available models for viscous sintering.     

Formation and hot isostatic pressing of ZrO2 solid solution in the system ZrO2-Al2O3

In the system of ZrO₂-Al₂O₃, cubic ZrO₂ solid solutions containing up to 40 mol% Al₂O₃ crystallize at low temperatures from amorphous materials prepared by the simultaneous hydrolysis of zirconium and aluminium alkoxides. At higher temperatures, they transform into tetragonal solid solutions. Metastable ZrO₂ solid solution powders containing 25 mol% Al₂O₃ have been sintered at 1000–1150 °C under 196 M Pausing the hot isostatic pressing technique. The solid solution ceramics consisting of homogeneous microstructure with an average grain size of 50 nm exhibited a very high fracture toughness of 23 MN m ^–1.5. They have been characterized by X-ray diffraction and electron probe surface analyses.     

Deposition and microhardness of SiC from the Si2Cl6-C3H8-H2-Ar system

We obtained SiC coating layers on a graphite substrate using hexachlorodisilane (Si₂Cl₆, boiling point 144° C) as a silicon source and propane as a carbon source. We examined the deposition conditions, contents of carbon, silicon and chlorine in the deposits, and the microhardness. Mirror-like amorphous silicon layers were deposited in the reaction temperature range 500 to 630° C. well-formed silicon carbide layers with good adherency to the substrate were obtained above 850° C. The lowest deposition temperature of SiC was estimated to be 750 to 800° C. The Vickers microhardness of the SiC layer was about 3800 kg mm^–2 at room temperature and 2150 kg mm^–2 at 1000° C.     

Electrical properties of polycrystalline ZnO : Cu obtained from freeze-dried ZnO+copper(II) acetate powders

Highly homogeneous mixtures of powders containing ZnO and monohydrated copper(II) acetate, (CH₃COO)₂CuH₂O, AcCuH₂O were obtained by freeze drying. Thermal analysis and high-temperature X-ray diffraction showed that pure freeze-dried AcCuH₂O powder decomposed to CuO, in air, at temperatures above 325 °C. Due to the polymeric nature of AcCuH₂O, the powder mixtures were compacted without pressing additives. Pellets with ZnO+x mol % Cu (x=0.05, 0.5, and 5.0) compositions were sintered in air from 750 to 1150 °C for 1 h. After sintering, the density, shrinkage and mass loss increased as the concentration of AcCuH₂O increased. A microstructural analysis of samples sintered at 950 °C for 1 h revealed Cu-doped ZnO grains with Cu-clusters of x=5.0 mol % Cu; the J–E curves showed that both the breakdown electric field, E_br, and the nonlinearity coefficient, , increased as x increased from 0.05 to 0.5. Complex acceptor defects involving Cu⁺ _Zn in the grain boundary are believed to have compensated for the n-type conductivity of the ZnO grains, giving rise to high E_br values.     

Barium hexaferrite magnet by topotactic reaction method

A new topotactic sintering method using Fe₂O₃ (obtained from FeO · OH) and BaCO₃ is developed for preparing cheaper grain oriented barium hexaferrite. Fe₂O₃ and BaCO₃ (precipitate grade) are wet mixed in a ball mill in stoichiometric proportion. The mixed slurry is then dried at 110° C for about 12h. The dried powder mixture containing moisture as a binder is uniaxially compacted at 5×10⁶–10×10⁶ kg m^–2 pressure. The green compacts are air sintered in the temperature range 1100–1300° C for 1 H. The best results of the sintered ferrite show maximum energy product (BH) _max in the range 7–10 kTAm^–1. The bulk of commercial requirements for toy magnets etc. may be met by this method of production which eliminates steps like calcination and cost intensive wet magnetic compaction.     

High temperature deformation of titanium diboride

Specimens of high purity polycrystalline titanium diboride, TiB₂, were tested in uniaxial compression under vacuum at a strain rate of 5 × 1O^–4sec^–1 to determine the plastic yield behaviour. Generally, plastic deformation was detected only above 170O° C. The apparatus was able to apply u stress of 900 MPa at a maximum temperature of 2000° C. The yield stress data fit an Arrhenius function, with an apparent activation energy of O.8 eV atom^–1. Dislocation glide over the Peierls barrier is thought to be the deformation mechanism, The dependence of the yield stress on the grain size obeyed the Hall-Petch relation within the bounds of experimental error. A TiB₂ single crystal containing TiC precipitates was also compression - tested at 2000° C, and its yield stress was approximately four times the stress predicted by the Hall-Petch expression for e pure TiB₂ single crystal, suggesting that the precipitate raises the yield stress but that the intrinsic lattice resistance is still significant. Submicrometre-sized graphite inclusions were observed in the polycrystalline specimens, but are thought not to have a direct effect on the yield stress in the temperature regime of the present study.