Densification and mechanical properties of cBN–TiN–TiB2 composites prepared by spark plasma sintering of SiO2-coated cBN powder

cBN–TiN–TiB₂ composites were fabricated by spark plasma sintering at 1773–1973 K using cubic boron nitride (cBN) and SiO₂-coated cBN (cBN(SiO₂)) powders. The effect of SiO₂ coating, cBN content and sintering temperature on the phase composition, densification and mechanical properties of the composites was investigated. SiO₂ coating on cBN powder retarded the phase transformation of cBN in the composites up to 1873 K and facilitated viscous sintering that promoted the densification of the composites. Sintering at 1873 K, without the SiO₂ coating, caused the relative density and Vickers hardness of the composite to linearly decrease from 96.2% to 79.8% and from 25.3 to 4.4 GPa, respectively, whereas the cBN(SiO₂)–TiN–TiB₂ composites maintained high relative density (91.0–96.2%) and Vickers hardness (17.9–21.0 GPa) up to 50 vol% cBN. The cBN(SiO₂)–TiN–TiB₂ composites had high thermal conductivity (60 W m⁻¹ K⁻¹ at room temperature) comparable to the TiN–TiB₂ binary composite.     

Diffusion coefficient of carbon in Fe–Ni alloy during synthesis of diamond under high temperature and high pressure

Synthetic diamond particles were prepared under high temperature and high pressure using arrayed seeds. A dense Fe–Ni alloy shell covered each diamond seed during synthesis; the growth of diamond particles was controlled by the diffusion of carbon through the metallic shell. The diffusion coefficient of carbon through Fe–Ni melt at 1600 K and 5.5 GPa is about 5×10^?6 cm²/s, with an activation energy for diffusion of 336 kJ/mol.     

Spark plasma sintering of TiN–TiB2 composites

TiN–TiB₂ composites were fabricated by spark plasma sintering at 1773–2573 K. Effects of TiN and TiB₂ content on relative density, microstructure, and mechanical properties were investigated. Above 2373 K, TiN–TiB₂ composites exhibited relative densities over 95%. A high density of 99.7% was obtained at 2573 K with 20–30 vol% TiB₂. Shrinkage of the TiN–70 vol% TiB₂ composite was the highest at 1573–2473 K. For the TiN–70 vol% TiB₂ composite prepared at 1973–2373 K, TiN grains were small, while at 2573 K, TiB₂ became a continuous matrix, in which irregular-shaped TiN dispersed. hBN was formed in the TiN–TiB₂ composite containing 50–60 vol% TiB₂ above 2373 K. The maximum Vickers hardness and fracture toughness obtained for the TiN–80 vol% TiB₂ composite sintered at 2473 K was 26.3 GPa and 4.5 MPa m^1/2, respectively.     

Crystal growth of diamond from a phosphorus solvent under high pressure–high temperature conditions

Crystal growth of diamond in a phosphorus solvent was studied on a seed of natural octahedral diamond at high pressures and high temperatures of 6.2–6.5 GPa and 1600–1700°C for 5–23 h. Although new growth layers of diamond up to 30 μm in thickness were observed on {111} faces of a seed, growth almost stopped within the first 5 h caused by the following occurrence of spontaneous nucleation. The growth layer was usually gray or bluish gray in color and the surface became undulated with dense triangular growth hillocks and growth steps of 〈110〉 directions. On the grown surface were observed two other characteristic features: one is a circular depression with various size particularly observed in the beginning of the growth and the other is a peculiar growth step with the direction indexed as 〈321〉.     

In situ synthesis,physical and mechanical properties of ZrB2–ZrC–WB composites

In this study, two composition ZrB₂–ZrC–WB composites were synthesized by reactive hot-pressing of Zr + B₄C + WC powder mixtures at 1900 °C. The microstructure of the resulting composites was characterized by a combination of scanning electron microscopy and X-ray diffraction. It is seen that highly-dense ZrB₂–ZrC–WB composites with a homogenous fine-microstructure were obtained after the sintering. The mechanical behavior of the composites was evaluated using by testing under four-point bend testing at room and high temperatures. The results show that the high-temperature strength of the ZrB₂–ZrC–WB composites was substantially improved, compared to ZrB₂–ZrC-based composites without WB. In addition, the elastic properties, electrical conductivity, hardness and fracture toughness of the composites were measured at room temperature. The results reveal that these properties were comparable to those of ZrB₂–ZrC-based composites without WB.     

In situ studies of oxidation of ZrB2 and ZrB2–SiC composites at high temperatures

High temperature oxidation of ZrB₂ and the effect of SiC on controlling the oxidation of ZrB₂ in ZrB₂–SiC composites were studied in situ, in air, using X-ray diffraction. Oxidation was studied by quantitatively analyzing the crystalline phase changes in the samples, both non-isothermally, as a function of temperature, up to ～1650 °C, as well as isothermally, as a function of time, at ～1300 °C. During the non-isothermal studies, the formation and transformation of intermediate crystalline phases of ZrO₂ were also observed. The change in SiC content, during isothermal oxidation studies of ZrB₂–SiC composites, was similar in the examined temperature range, regardless of sample microstructure and composition. Higher SiC content, however, markedly retarded the oxidation rate of the ZrB₂ phase in the composites. A novel approach to quantify the extent of oxidation by estimating the thickness of the oxidation layer formed during oxidation of ZrB₂ and ZrB₂–SiC composites, based on fractional conversion of ZrB₂ to ZrO₂ in situ, is presented.     

Microstructure and luminescence properties of the high pressure high temperature sintered AlN–TiN ceramics

Composite ceramics of titanium nitride grains incorporated in an aluminium nitride matrix have been synthesized by high pressure high temperature treatment of a mechanical mixture of AlN–TiN (3 mol % TiN) powders. The microstructure of the samples analysed by means of electron beam microanalysis and Raman spectroscopy shows that the formation of cubic AlN in the composite begins near titanium nitride grains. The areas of mixed chemical composition, which can be assigned to the formation of the solid solutions Al_1?xTi_xN, have been observed at the phase interfaces. The luminescence properties of AlN–TiN ceramics have been considered focusing on the choice of high pressure and high temperature treatment conditions. Three main components at 2.0 eV, 2.4 eV and 3.1 eV are revealed in the cathodoluminescence spectra analysed quantitatively. The observed emission originates from the radiative transitions with participation of valence band states, oxygen-vacancy centres (V_Al–O_N), nitrogen vacancies V_N, and shallow donors which form a complex system of energy levels in the bandgap of the wurtzite-type AlN.     

Synthesis and performance of TiB2–B4C composites by high pressure of TiC–B mixture

TiB₂–B₄C composites were in situ synthesized and consolidated by high pressure synthesis method from a mixture of TiC and B powders at the pressure and temperature of 5.0 GPa and 1500℃-1900℃. The phase composition, microstructure, density, hardness, thermal conductivity, and electrical resistivity of TiB₂–B₄C composites were analyzed. As the increase in the synthesis temperature, the products were TiB₂ and B₄C phases and that crystallinity improved. TiB₂–B₄C composites were dense without obvious pores. TiB₂–B₄C composites synthesized at 1800℃ obtained the optimized performance, including the relative density of 98.2%, the Vickers hardness of 31.7 ± 1.2 GPa with the load of 9.8 N, the thermal conductivity of 30.3 ± 0.7 W/(m K), and the electrical resistivity of 3.3 × 10⁻³ Ω cm, respectively. The grain size of the TiB₂–B₄C composites changed with the increase in synthesis temperature, leading to the changes in hardness, thermal conductivity, and electrical resistivity.     

β-SiAlON–BN composites by infiltration-mediated SHS under high pressure of nitrogen gas

Infiltration-mediated SHS of β-S_i6–z Al _z O _z N_8–z –BN composites was explored upon variation in applied nitrogen pressure, amount of combustible and low-melting components in green mixture, sample size, and BN content of resultant composites. Synthesized ceramic composites of different density and BN content were characterized by their strength parameters, tribological behavior, and thermal shock resistance.     

cBN–TiN,cBN–TiC composites: chemical equilibria,microstructure and hardness mechanical investigations

This paper summarizes theoretical and experimental studies of cBN–TiN and cBN–TiC of cBN:TiN/TiC molar ratio 1:1 and 2:1. Theoretical calculations show that, at temperatures between 1000 and 1400°C, TiN reacts with BN forming one new phase, TiB₂, and that TiC reacts with cBN forming two new phases, TiB₂ and TiC_0.8N_0.2.. Experimental cBN–TiC/TiN composites were prepared by high pressure hot pressing and the samples were subsequently heat treated.After heat treatment, sinters of cBN–TiN/TiC were characterized using transmission electron microscopy and X-ray diffraction. The samples exhibited a dense polycrystalline structure, and a thin layer of fine TiB₂ was visible at the BN–binder interface. It was found that hardness decreased significantly after heat treatment.     

In situ synthesis of ZrB2–MoSi2 platelet composites: Reactive hot pressing process,microstructure and mechanical properties

Using elemental Zr, B, Mo and Si as raw materials, partially textured ZrB₂–MoSi₂ composites with in situ platelet ZrB₂ grains were fabricated by reactive hot pressing. Synthesized by a combustion reaction, the in situ formed ZrB₂ phase had unique characteristics to grow up to platelet grains, on the surroundings of Mo–Si–B ternary liquid phase at high temperature. Mechanical properties were dependent on grain size and aspect ratio of the ZrB₂ platelets. The rotation and realignment of the platelet ZrB₂ grains under hot pressing led to a partially textured microstructure, which showed anisotropic mechanical properties on different directions of the as-sintered samples. A roadmap of the reaction process, microstructure evolution and texture formation was given to describe the preparation of partially textured ZrB₂–MoSi₂ composites by reactive hot pressing.     

B deficiency in TiB2 and B solid solution in TiN in TiN–TiB2 composites prepared by spark plasma sintering

Dense TiN–TiB₂ composites were prepared by spark plasma sintering at 2573 K using TiN and TiB₂ powders. With increasing TiN content from 60 to 90 vol%, the c-axis length of TiB₂ in the TiN–TiB₂ composites decreased from the stoichiometric value (0.3230 nm) to 0.3227 nm because of B deficiency in TiB₂, whereas the a-axis length of TiB₂ was unchanged from the stoichiometric value of 0.3031 nm. The lattice parameter of TiN increased from the stoichiometric value (0.4243 nm) to 0.4250 nm with increasing TiB₂ content from 0 to 60 vol% because of B solid solution in TiN.     

High pressure synthesis of tungsten carbide–cubic boron nitride (WC–cBN) composites: Effect of thermodynamic condition and cBN volume fraction on their microstructure and properties

Tungsten carbide (WC) with different amounts of Cubic boron nitride (cBN) were synthesized by High Pressure-High Temperature (HPHT) method. The mapping correlation between thermodynamic condition, cBN addition, and microstructure, mechanical properties of WC–cBN composites was established and analyzed by response surface methodology. The main factors affecting the properties of composites were identified by ANOVA. The optimum thermodynamic condition was calculated. It was found that a minor phase transformation of cBN into the low-hardness hBN occurred at a temperature of 1300 °C and intensified at 1500 °C. The homogeneously dispersed cBN particles in the WC matrix promoted an improvement of hardness and fracture toughness, but the phase transition of cBN and its truss effect can dramatically reduce the mechanical properties. The Vickers hardness and fracture toughness of the well-sintered WC-cBN bulks reached a high value of 34 GPa and 13.6 MPa·m^1/2, which are improved by 17% and 52% respectively compared with the pure WC samples sintered under similar high-pressure level.     

Synthesis and characterization of novel Ti3SiC2–cBN composites

In this paper, synthesis of novel super hard and high performance composites of titanium silicon carbide–cubic boron nitride (Ti₃SiC₂–cBN) was evaluated at three different conditions: (a) high pressure synthesis at ~ 4.5 GPa, (b) hot pressing at ~ 35 MPa, and (c) sintering under ambient pressure (0.1 MPa) in a tube furnace. From the analysis of experimental results, the authors report that the novel Ti₃SiC₂–cBN composites can be successfully fabricated at 1050 °C under a pressure of ~ 4.5 GPa from the mixture of Ti₃SiC₂ powders and cBN powders. The subsequent analysis of the microstructure and hardness studies indicates that these composites are promising candidates for super hard materials.     

Mechanisms of TiB2 and graphite nucleation during TiC–B4C high temperature interaction

Reactive hot pressing of TiC–B₄C precursors was undertaken at 1800 °C to produce TiB₂ with carbon inclusions. Atomic mechanisms of titanium diboride nucleation, as well as sponge-like carbon inclusions and submicron platelets of graphite precipitation have been investigated. Precursor grain size, green body composition and synthesis time were varied to analyze phase transformation. The carbon left after B₄C high temperature decomposition is shown remaining as graphite sponge-like inclusions. Ab-initio calculations confirm that the boron atoms accumulation on (111) TiC plains leads to tensile stress. The developed stress cleaves TiC grains and enhances further reaction. Most of carbon expelled from TiC during its transformation into TiB₂ forms graphite submicron platelets.     

The high temperature–high pressure sintering of diamond–Cu–Si–B composite

Such elements like Si, B and Cu have been utilized as components of binder aiming at acquiring high adhesion of the binder with the diamond grains, thermal stability of the composite and, relatively low fusion temperature of the binder. The present work has as its main objective the study of the interaction between components during sintering of polycrystalline diamonds with addition of binders under high pressures, in the range from 5.0 to 6.0 GPa and high temperatures, in the range from 1473 to 1773 K with process time between 15 and 30 s. After sintering the compacts were subjected to investigations concerning the influence of the mixture composition and of the process parameters on the density and wear resistance of the compacts. The method of factorial planning was utilized in order to obtain model which describes influence of sintering parameters on the properties of compacts.     

Synthesis of Si3N4–TiN–SiC composites by combustion reaction under high nitrogen pressures

Si₃N₄–TiN–SiC composites were synthesized from TiSi₂ and SiC mixtures via the combustion reaction under high nitrogen pressure. The nitridation mechanism of TiSi₂ was analyzed. The results show that the nitridation of TiSi₂ produced TiN and Si firstly, and Si₃N₄ phase was formed by the further nitriding of Si. The molten eutectic phase and its agglomeration between Si and TiSi₂ formed one core-shell structure and affected the nitridation process. Under higher nitrogen pressure, the nitridation reaction was complete and the relatively dense Si₃N₄–TiN–SiC composites obtained. TEM observation revealed inhomogeneous Si₃N₄ grain size, amorphous phase, cavities, microcracks and dislocations, and graphite from the nitridation of SiC in the microstructure.     

Densification of SiO2–cBN composites by using Ni nanoparticle and SiO2 nanolayer coated cBN powder

Cubic boron nitride (cBN) powder was coated with Ni nanoparticle and SiO₂ nanolayer (abbreviated as cBN/Ni and cBN/SiO₂, respectively) by rotary chemical vapor deposition (RCVD), and compacted with SiO₂ powder by spark plasma sintering at 1473–1973 K for 0.6 ks. The effects of Ni and SiO₂ coatings on the densification, phase transformation of cBN and hardness of SiO₂–cBN composites were compared. The phase transformation of cBN to hBN was identified at 1973 K in SiO₂–cBN/SiO₂ composites, 300 K higher than that in SiO₂–cBN/Ni composites, indicating that SiO₂ retarded the transformation of cBN. The relative density of SiO₂–cBN/SiO₂ with 50 vol% cBN sintered at 1873 K was 99% with a hardness of 14.5 GPa.     

In situ synthesis of Ba0.5Sr0.5TiO3–Mg3B2O6 composites and their dielectric response

Ba_0.5Sr_0.5TiO₃–Mg₃B₂O₆ (BST–MB) composites have been prepared in situ by a citrate gel process, and their structure and effective dielectric response have been investigated. The precursor with pH≥7 is suitable for in situ formation of the diphase structure consisting of BST and MB. Accordingly, MB particles homogeneously disperse in BST particles, accompanied by the formation of boron-rich grain boundary resulting from liquid phases sintering of B₂O₃. Related with the existence of boron-rich grain boundary and the incorporation of Mg²⁺ into BST lattice, permittivity decreases rapidly with increasing volume fraction of MB from 0.0 to 0.2 and then decreases slowly with further increasing, which coincides with theoretical prediction of the layered model.