Effects of added diamond powder on the reaction sintering behaviour of diamond in the graphite-nickel system

Polycrystalline diamond sintered compact was prepared under high pressure and temperature conditions (7 GPa, 1700°C, 10 to 30min) from the starting material with the composition of the system 50 wt% carbon (diamond + graphitized pitch coke (GPC))-50 wt% Ni. The effects of added diamond powder on the microstructure of the sintered compact and reaction sintering behaviour were investigated. The grain size of diamond in the sintered compact decreased remarkably from 20 to 40m to 2 to 3m on addition of 10 to 20 wt% diamond powder (grain size: 1m) to the GPC-Ni system. The grain size can be controlled by that of the added diamond powder. A sufficient supply of carbon from GPC plays an important role in the formation of a covalently bonded compact of diamond. The grain growth of the formed diamond is depressed by the coexistence of diamond powder, which controls the solubility of carbon in the metal-carbon system and also the grain growth process by solution-reprecipitation.     

Effects of junction formation conditions on the photovoltaic properties of sintered CdS/CdTe solar cells

Microstructures and properties of sintered CdS films on glass substrates and sintered CdTe films on polycrystal CdS substrates have been investigated. The CdS films, which contained 9 wt % CdCl₂ as a sintering aid and were sintered at 650° C for 1 h in nitrogen, are transparent and have an average grain size of 15m and an electrical resistivity of 0.5cm. The CdTe films, which were coated on the sintered CdS substrate and were sintered above 610° C for 1 h in nitrogen, have a dense structure with an average grain size larger than 5m. All polycrystal CdS/CdTe solar cells were fabricated by this successive coating and sintering method. The sintering temperature of CdTe films on the sintered CdS films was varied from 585 to 700° C. Compositional interfaces and p-n juctions are formed during sintering. The highest solar efficiency (7.18%) was found in a solar cell made by sintering the composite layer of glass-CdS-CdTe at 625° C for 1 h. A fabrication temperature below 610° C resulted in poor solar cell efficiencies due to the porous structure of the CdTe films and above 650° C also resulted in poor efficiencies due to the formation of a CdS_1-x Te_x layer at the interface and a large p-n junction depth.     

The effect of silica characterization on the microstructure of BaFe12O19 ferrites

The anisotropically formed BaFe₁₂O₁₉ ferrites were prepared from the hot-rolled mill scale and silica was added to the ferrite during fine milling in the range 0.15 to 0.50 wt%. These ferrites were sintered at 1220° C for 2 h. The grain growth of the ferrites is dominantly influenced by the sizes of the silica added. Coarse-grain ( 1m) silica tends to promote discontinuous grain growth, which increases drastically with slightly increasing amounts of silica added, while fine-grain ( 0.013m) silica tends to retain fine grain microstructures with the same increasing amount of silica. The average grain size of the ferrite without silica addition was 8 to 10m. The size was increased to as large as 30m on addition of 0.15% coarse-grain silica and the microstructure was full of extremely large grains on the addition of 0.50% coarse-grain silica.     

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.     

The growth of non-stoichiometric apatites using the constant composition method

The kinetics of the crystal growth of calcium-deficient hydroxyapatites with different stoichiometry (Ca₅-(HPO₄)(PO₄)₃-(OH)₁-) have been investigated at 37°C using the constant composition method. The growth was performed in solutions supersaturated only with respect to Ca₅(PO₄)₃(OH) (HAp) by inoculating with well-characterized seed crystals. The stoichiometry of the grown apatites was consistent with values of 00.185. The deviation from HAp stoichiometry of the growing apatite increased with increasing supersaturation degree (S). The constant composition method also provides relevant information about the solubility behaviour of the growing phase with a definite composition. From the decrease of the normalized growth rate j with decreasing S, an estimate could be made of the composition of the solution for which the growth ceases. The determined solubility product of the grown apatite (4.28×10^-54 M⁹) was higher than the value obtained by the equilibration of the seed material. The results were interpreted on the basis of differences in crystal lattice perfection.This paper was accepted for publication after the 1995 Conference of the European Society of Biomaterials, Oporto, Portugal, 10–13 September.     

Hot dynamic consolidation of hard ceramics

Diamond and cubic boron nitride powders were shock compacted at high temperature (873 and 973 K) by using a planar impact system at 1.2 and 2.0 km s^–1. Silicon, graphite or a mixture of titanium and carbon powders were added to enhance the bonding of these superhard materials. Hot-consolidated specimens exhibited fewer surface cracks as compared with the specimens shock consolidated at room temperature. Diamond compacts having microhardness values over 55 GPa were obtained by subjecting porous mixtures of diamond crystals (4-8 m) plus 15 wt% graphite (325 mesh) to an impact velocity of 1.2 km s^–1 at 873 K. Well-consolidated c-BN samples, with microhardnesses (starting powders with 10–20 and 40–50 (m) over 53 GPa were obtained.     

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.     

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.     

Shock compaction of cubic boron nitride powders

C-BN powders with different grain sizes were dynamically compacted by explosive shock loading using approximate peak pressures from 33 to 77G Pa. The density and the microhardness of the resulting c-BN compacts were strongly dependent upon the grain size of the c-BN powders used as the starting materials. The best c-BN compacts, with 98% of the theoretical density and microhardness of 51.3G Pa, were obtained from the coarse c-BN powder (40 to 60m). In the compacted fine c-BN powder (2 to 4m) conversion of the c-BN to low density forms of BN at a residual temperature degraded the interparticle bonding significantly. X-ray line-broadening analysis of the compacted c-BN powders indicated that the residual lattice strain increased with the increase in grain size of the starting powder, while the crystallite size was independent of the grain size.     

Duplex spinel-ZrO2 ceramics

Duplex spinel-ZrO₂ ceramic composites were produced by an emulsion-hot kerosene drying technique. The sintered duplex spinel-ZrO₂ ceramics which had the composition of 55 wt% Al₂O₃-20 wt% ZrO₂-25 wt% MgO, consisted of a spinel matrix, whose grain size was in the range of 1.5 to 2.0 m, and uniformly dispersed zirconia agglomerates having grain sizes ranging from 1.0 to 2.0 m. Zirconia agglomerates began to appear at a temperature of 1500 °C and the duplex spinel-ZrO₂ structure was formed with the weight ratio of Al₂O₃/MgO being within 1.67 to 2.20 and the amount of ZrO₂ addition being within 5 to 25 wt %. The relative density, fracture toughness, flexural strength, and critical temperature difference of the spinel-ZrO₂ composite were 97.8%, 1.98 MPam^0.5, 390 MPa, and 275 °C, respectively.     

Manufacturing and friction welding properties of particulate reinforced 7005 Al

This study has successfully incorporated Al₂O₃, SiC particulates into the 7005Al alloy matrix by using a drag-push method. The reinforced particulates are uniformly distributed in the matrix. This study also discusses the influence of aging treatment on the friction welding properties of 7005Al/10 wt%, 15 m and 6 m SiC_(p) composites and 7005Al/10 wt%, 15 m Al₂O_3(p) composites joint system. Experimental results show that after peak aging treatment was performed, if SiC particulates were used in the strengthening phase, the heat-affected zone (HAZ) had higher density of strengthening particulate, this resulted an increase in the hardness and stress concentration at the fully plasticized zone (Zpl) of the HAZ region, but a decrease in the width of the Zpl zone and the welding strength. And the welded fracture surface morphology had a low-ductile fracture.     

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.     

On the preparation and electrical properties of PtSb2

The preparation and the Czochralski growth of single crystals of PtSb₂ by a liquid encapsulation technique is described. Conductivity and Hall effect measurements have been made in the temperature range 20 to 300° K. It is found that the material is n-type, with a carrier concentration of about 6 × 10¹⁶/cm³, the ratio of electron to hole mobility, _e/ _h, is 0.57 at 110° K, and the electron mobility has a maximum value of 2100 cm²/V sec at 50° K. The thermal energy gap is 0.112 eV.     

Study of the lattice strain relaxation in the Ga1-X Al X Sb/GaSb system by x-ray topography and high resolution diffraction

High resolution x-ray diffraction and topographic methods have been used to study lattice strain relaxation in the Ga_1-X Al _X Sb/GaSb system. Samples with layer thickness ranging between 0.1 and 6 m and with Al concentration x=0.402±0.005 have been grown by molecular beam epitaxy at 550 °C on (0 0 1) oriented undoped GaSb LEC substrates. A first critical thickness (t _C1), related to the misfit dislocation generation, has been found to be between 0.16 < t _C1 < 0.20 m. Due to the weak sensitivity of the rocking curve to the onset of relaxation, this result has been obtained by means of a double crystal topographic technique. A plateau region in the curve of the residual strain versus thickness has been observed for t ranging between 0.2 and 0.5 m. The residual strain _res shows a dependence close to t^–0.5 above a second critical thickness value t _C2 slightly larger than 0.5 m. Finally, in the last region above a layer thickness of 3 m, strong dislocation interaction effects seem to affect the relaxation. A comparison with theoretical models has been made.     

Pressureless sintering of β-SiC with Al2O3 additions

-SiC was pressureless sintered to 98% theoretical density using Al₂O₃ as a liquid-phase forming additive. The reaction between SiC and Al₂O₃ which results in gaseous products, was inhibited by using a pressurized CO gas or, alternatively, a sealed crucible. The densification behaviour and microstructural development of this material are described. The microstructure consists of fine elongated -SiC grains (maximum length 10 m and width 2–3 m) in a matrix of fine equi-axed grains (2–3 m) and plate-like grains (2–5m). The densification behaviour, composition and phases in the sintered product were studied as a function of the sintering parameters and the initial composition. Typically, 50% of the -phase was transformed to the -phase.     

Observations on whiskers and skeletal crystals in PbSe layers by scanning electron microscopy

Whiskers and skeletal crystals of PbSe are obtained on substrates of (100) germanium. The production conditions and peculiarities of their structures are discussed. SEM observations show that the whiskers are prism-shaped possessing rectangular or square cross-sections with lengths up to 190m and widths of the surrounding walls up to 26m. Hollow pyramidal crystals with their apexes connected to the layer surface by a whisker are described, as well as hollow crystals with an open or a closed surrounding surface. Certain aspects of the growth mechanism of skeletal crystals and whiskers are discussed.     

Improved thermal shock resistant refractories from plasma-dissociated zircon

Dissociated zircon (DZ), produced in a plasma furnace recombined and sintered to about 92% of the theoretical density in the range 1300 to 1500° C The work-of-fracture of DZ increased from 20J m^–2 to 73 J m^–2 with additions of 10 wt% monoclinic zirconia particles which had a mean diameter of about 13m. Thermal shock data showed that crack propagation in DZ/ZrO₂ composites was stable.     

State of Radiorhodium in High-Level Liquid Waste from Regeneration of Spent Nuclear Fuel

The state of radiorhodium in liquid waste from processing of spent nuclear fuel was analyzed in detail by ESR and NMR spectroscopy on several nuclei. The most probable oxidation state of rhodium in nitric acid solutions is +3. Three procedures for preparing nitric acid solutions of rhodium were studied. The composition of Rh(III) complexes in these solutions is similar but not identical. The method for identifying the ionic composition of similar objects was proposed. The speciation of rhodium in nitric acid solutions with the acid concentration ranging from 2×10^{- 2} to 15 M was studied. Polynuclear oligomers with (-ONO₂)₂ bridges, mainly tetramers, are formed in solutions with CRh > 2 M, [NO₃ ^-] 8 M, and [H⁺] 0.7 M. At CRh = (1-2)×10^{- 2}, [NO₃ ^-] = 1-4 M, and [H⁺] = 0.4-4 M, the (-OH, -ONO₂) dimer and trimer prevail; at [NO₃ ^-] < 1 M and [H⁺] < 0.2 M, the (-OH, -ONO₂) dimer dominates. No Rh(III) aqua ion and no monomeric nitrate complexes were detected in the quasiequilibrium system at any concentrations of the components. In nitrate-nitrite solutions, both subnitrated (-OH, -ONO₂) Rh(III) oligomers and mononuclear Rh(III) nitroaqua complexes exist. The equilibrium between these species is attained very slowly and depends on the equilibrium concentration of nitrite anion. Forecast was given on isolation of rhodium from nitric acid solutions of SNF by extraction, ion-exchange, electrolytic, and precipitation procedures.     

Microstructure and properties of an infra-red transmitting chalcogenide glass-ceramic

A chalcogenide glass-ceramic (0.3 PbSe-0.7 Ge_1.5 As_0.5 Se₃) which transmits in the infra-red region between 8 and 12 m was produced from a phase separated parent glass. The glass transition temperature (T _g) was increased from 280 to 340°C by crystallizing the phase with the lowerT _g. Further heat-treatment produced a glass-ceramic that was up to 60% crystalline and contained PbSe, PbSe₂ and GeSe₂ crystals with a gran size of 0.5 m. The infra-red transmission of the glass-ceramic decreased with increased crystallinity. The glass-ceramic modulus of rupture (38 MN m^–2) was increased to as much as twice that of the glass and the Vickers hardness increased by 30% to 280 kg mm^–2.     

Dislocation generation at surfaces of tin single crystals

Single crystals of 99.999% purity-tin grown from the melt were shown by X-ray topography to contain dislocations with Burgers vectors of [001] type and of 1/2111 type. Specimen plates cut roughly parallel to (311) were chemically thinned from 1.25 mm to 100m thickness and in two cases characteristic dislocation structures were generated at their surfaces. A specimen thinned in concentrated HCl possessed stress-producing centres distributed on its surfaces with a density of about 75 mm^–2 from which regular helices and coaxial prismatic loops with [001] Burgers vector were generated together with irregular loops of 1/2111 Burgers vector dislocations. In one specimen thinned in a H₃PO₄, CH₃COOH, HF and HNO₃ mixture large arrays of pure edge dislocations grew parallel to the surface at a depth of 2 to 4m below it, the individual dislocations extending at about 1m h^–1 during several weeks. These edge arrays all had that one of the four 1/2111-type Burgers vectors which made the smallest angle (5°) with the surface. The Burgers vector sense, determined by X-ray diffraction contrast, corresponded to a sheet of vacancies lying between the dislocation line and the surface.Visitor to H. H. Wills Physics Laboratory under Royal Society-SSR Cultural Agreement.