Sintering Mechanisms and Kinetics for Reaction Hot‐Pressed ZrB2

Sintering mechanisms and kinetics were investigated for ZrB₂ ceramics produced using reaction hot pressing. Specimens were sintered at temperatures ranging from 1800°C to 2100°C for times up to 120 min. ZrB₂ was the primary phase, although trace amounts of ZrO₂ and C were also detected. Below 2000°C, the densification mechanism was grain‐boundary diffusion with an activation energy of 241 ± 41 kJ/mol. At higher temperatures, the densification mechanism was lattice diffusion with an activation energy of 695 ± 62 kJ/mol. Grain growth exponents were determined to be ~4.5, which indicated that a grain pinning mechanism was active in both temperature regimes. The diffusion coefficients for grain growth were 1.5 × 10^?16 cm⁴/s at 1900°C and 2.1 × 10^?15 cm⁴/s at 2100°C. This study revealed that dense ZrB₂ ceramics can be produced by reactive hot pressing in shorter times and at lower temperatures than conventional hot pressing of commercial powders.     

Insights into High‐Temperature Uniaxial Compression Deformation Behavior of Ti3AlC2

We report on strain‐rate‐dependent compression deformation behavior of Ti₃AlC₂ at 1000°C–1200°C. At 1000°C and high strain rate (10^?2 or 10^?3 s^?1), Ti₃AlC₂ deforms in a nonplastic manner. Upon increasing temperature and reducing strain rate, Ti₃AlC₂ exhibits a limited plasticity. For instance, the true plastic strain at 1200°C and 10^?4 s^?1 is only 3%, beyond which strain softening following a short hardening regime occurs. The softening results from the formation of localized microvoids and microcracks. Decreasing the strain rate further to 10^?5 s^?1 at 1200°C, strain hardening instead of softening is identified. Under such conditions, the plastic strain remarkably increases, reaching a value as high as 27%. Postdeformation microstructural analyses of the dislocation configurations explicitly evidence the dislocation reactions, formation of hexagonal dislocation networks and dislocation entanglements. These account for the strain hardening. The extraordinary plasticity at 1200°C and 10^?5 s^?1 benefits from the initiation of nonbasal slip systems. Finally, a complete high‐temperature deformation scenario for nanolaminated Ti₃AlC₂ is elaborated.     

High-Temperature Creep of Polycrystalline Magnesia: I,Effect of Simultaneous Grain Growth *

The creep of pure magnesia (99.9 +% MgO) was tested in transverse bending at temperatures from 1200° to 1500°C, strain rates near 10⁻²%/hr, and grain sizes of 4 to 50μ. In most cases, grain growth during the test affected the apparent creep behavior more than all the other variables combined. An analytical graphical method was used to separate the grain growth effect from other effects and to obtain more meaningful creep data. Creep occurred primarily by a viscous mechanism (Nabarro-Herring type, cation-lattice-diffusion controlling) with a minor amount of plastic creep (dislocation climb). The agreement with previous creep data was good.     

Fabrication,microstructure and high-temperature plastic deformation of three-phase Al2O3/Er3Al5O12/ZrO2 sintered ceramics

The fabrication, microstructure and high-temperature creep behavior of chemically compatible, three-phase alumina/erbium aluminum garnet (Er₃Al₅O₁₂, EAG)/erbia fully-stabilized cubic ZrO₂ (ESZ) particulate composites with the ternary eutectic composition is investigated. The composites were fabricated by a solid-state reaction route of α-Al₂O₃, Er₂O₃ and monoclinic ZrO₂ powders. The final phases α-Al₂O₃, EAG and ESZ were obtained after calcination of the powder mixtures at 1400 °C. High dense bulk composites were obtained after sintering at 1500 °C in air for 10 h, with a homogeneous microstructure formed by fine and equiaxed grains of the three phases with average sizes of 1 μm. The composites were tested in compression at temperatures between 1250 and 1450 °C in air at constant load and at constant strain rate. As the temperature increases, a gradual brittle-to-ductile transition was found. Extended steady states of deformation were attained without signs of creep damage in the ductile region, characterized by a stress exponent of nearly 2 and by the lack of dislocation activity and modifications in grain size and shape. The main deformation mechanism in steady state is grain boundary sliding, as found in superplastic metals and ceramics. In the semibrittle region, microcavities developed along grain boundaries; these flaws, however, did not grow and coalescence into macrocracks, resulting in a flaw-tolerant material. Alumina is the creep-controlling phase in the composite because of the grain boundary strengthening caused by the (unavoidable) Er³⁺- and Zr⁴⁺-doping provided by the other two phases.     

Final-stage densification kinetics of direct current–sintered ZrB2

Final-stage sintering was analyzed for nominally phase pure zirconium diboride synthesized by borothermal reduction of high-purity ZrO₂. Analysis was conducted on ZrB₂ ceramics with relative densities greater than 90% using the Nabarro–Herring stress–directed vacancy diffusion model. Temperatures of 1900°C or above and an applied uniaxial pressure of 50 MPa were required to fully densify ZrB₂ ceramics by direct current sintering. Ram travel data were collected and used to determine the relative density of the specimens during sintering. Specimens sintered between 1900 and 2100°C achieved relative densities greater than 97%, whereas specimens sintered below 1900°C failed to reach the final stage of sintering. The average grain size ranged from 1.0 to 14.7 μm. The activation energy was calculated from the slope of an Arrhenius plot that used the Kalish equation. The activation energy was 162 ± 34 kJ/mol, which is consistent with the activation energy for dislocation movement in ZrB₂. The diffusion coefficients for dislocation motion that controls densification were 5.1 × 10⁻⁶ cm²/s at 1900°C and 5.1 × 10⁻⁵ cm²/s at 2100°C, as calculated from activation energy and average grain sizes. This study provides evidence that the dominant mechanism for final-stage sintering of ZrB₂ ceramics is dislocation motion.     

Electrical Conductivity of Mullite Ceramics

The electrical conductivity of a lab‐produced homogeneous mullite ceramic sintered at 1625°C for 10 h with low porosity was measured by impedance spectroscopy in the 0.01 Hz to 1MHz frequency range at temperatures between 300°C and 1400°C in air. The electrical conductivity of the mullite ceramic is low at 300°C (≈0.5 × 10^?9 Scm^?1), typical for a ceramic insulator. Up to ≈ 800°C, the conductivity only slightly increases (≈0.5 × 10^?6 Scm^?1 at 800°C) corresponding to a relatively low activation energy (0.68eV) of the process. Above ≈ 800°C, the temperature‐dependent increase in the electrical conductivity is higher (≈10^?5 Scm^?1 at 1400°C), which goes along with a higher activation energy (1.14 eV). The electrical conductivity of the mullite ceramic and its temperature‐dependence are compared with prior studies. The conductivity of polycrystalline mullite is found to lie in‐between those of the strong insulator α‐alumina and the excellent ion conductor Y‐doped zirconia. The electrical conductivity of the mullite ceramic in the low‐temperature field (< ≈800°C) is approximately one order of magnitude higher than that of the mullite single crystals. This difference is essentially attributed to electronic grain‐boundary conductivity in the polycrystalline ceramic material. The electronic grain‐boundary conductivity may be triggered by defects at grain boundaries. At high temperatures, above ≈ 800°C, and up to 1400°C gradually increasing ionic oxygen conductivity dominates.     

Preliminary investigation of hydroxyapatite microstructures prepared by flash sintering

Flash sintering is a novel and emerging route for sintering ceramics within a few seconds, even under pressure-less conditions. In the current study, hydroxyapatite (HA) was fully densified by flash sintering at a furnace temperature of 1020°C. Flash sintering with constant electric fields of 750 and 1000?V?cm^?1 reduced the grain growth rate significantly compared to that sintered in the absence of an electric field at 1400°C. The microstructure of HA consolidated by flash sintering was compared with that of the without electric field sintered samples. The flash-sintered samples showed smaller grains (160?～?320?nm) than the without electric field sintered samples (～15?µm). The samples with a higher applied electric field showed slightly better densification than those with the lower field by flash sintering. Overall, the electric flash reduces the sintering temperature effectively and decreases the holding time to densify highly insulating ceramics, such as HA.     

Transitions of polytetrafluoroethylene at about 90 and 130°C. studied by x-ray diffraction and infrared spectra

By means of x-ray diffraction, the lattice spacing of the (100) plane for molded polytetrafluoroethylene was measured at different temperatures from 25 to 190°C. In the crystalline region, the linear expansion coefficient, in the direction perpendicular to the molecular chain axis, was obtained as 1.1 × 10^?4°C.^?1 below 60°C., as 1.2 × 10^?4°C.^?1 above 90°C., and as a minimum value of some 0.2 × 10^?4°C.^?1 at about 80°C. As the linear expansion coefficient of the crystalline region in bulk was observed as some 0.6 × 10^?4°C.^?1, the expansion coefficient in the direction of molecular chain axis must be negative except in the transition region near 80°C. The variation of molecular chain axis separation with temperature showed an irregularity at about 80°C. but none near 130°C. in the crystalline region. Infrared absorbance of film samples of PTFE was measured at different temperatures of 25 to 150°C. range for 518, 627, and 639 cm.^?1 bands. On absorbance–temperature curves for those b?ands, irregularities were observed near 30, 50, 90, and 130°C. Particularly with 518 cm.^?1 band, a more crystalline sample gave more distinct irregularities near 50 and 90°C. than a less crystalline sample. The change at about 90°C. in infrared spectra may correspond to that obtained by x-ray measurements near 80°C., which was thought to occur in the crystalline region. The results obtained by x-ray and infrared measurements support the previous results by thermal, rheological, and dielectric methods: there exist first-order transitions in the crystalline region at about 90°C. and second-order transitions in the amorphous region at about 130°C.     

Solid‐State NMR Study of Mn2+ for Ca2+ Substitution in Thermally Processed Hydroxyapatites

In the present study calcium hydroxyapatites enriched at 0.08 wt% in Mn²⁺ ions (Mn–HA) and their unsubstituted forms (HA) were synthesized using the same standard wet chemical route. Mn‐HA and HA were both calcined at 800°C to give Mn‐HAc and HAc, respectively or sintered at 1250°C, to give Mn‐HAs and HAs, respectively. The influence of the heat treatment on physicochemical properties of Mn‐HA was investigated using powder X‐ray diffraction (PXRD), scanning, and transmission electron microscopy (SEM and TEM), and solid‐state nuclear magnetic resonance (ssNMR). Mn‐HAc and Mn‐HAs were compared to each other and to HAc and HAs, respectively. Assignment of the proton ssNMR peaks from high‐temperature‐treated apatites has been revised. It was found that Mn–HAc and HAc were nanocrystalline, while Mn‐HAs and HAs comprised micrometer sized, partially fused particles (SEM and TEM). PXRD and ssNMR demonstrated that the incorporation of Mn²⁺ into the crystal lattice of hydroxyapatite significantly facilitates its dehydroxylation and decomposition to oxyhydroxyapatite during calcination at 800°C, and induces its transformation to tetracalcium phosphate (TTCP) and alpha‐tricalcium phosphate (α‐TCP) at 1250°C. Contamination by CaO has also been detected. The ¹H→³¹P NMR cross‐polarization experiments have indicated that the Mn²⁺ ions preferentially occupied the Ca(I) position in the crystallographic unit cell of Mn‐HAc. In Mn‐HAs, the Mn²⁺ ions were evenly distributed between the Ca(I) and Ca(II) positions.     

Solvent-deficient synthesis of cerium oxide: Characterization and kinetics

The reaction mechanism and kinetics of CeO₂ synthesis using a solvent-deficient method are investigated by simultaneous thermogravimetric analysis (TGA)/differential scanning calorimetry (DSC), X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The decomposition process of the cerium(III) nitrate hexahydrate and ammonium bicarbonate precursor mixture with four observed stages is monitored using TGA/DSC measurements in a nonisothermal regime with heating rates of 5, 10, 15 and 20?°C min^?1. The proposed mechanism indicates a complex synthesis with several parallel reactions, some of which occur at room temperature. A detailed kinetic analysis is performed using isoconversional (expanded Friedman, modified Coats-Redfern and Kissinger) and model fitting (N^th order and nucleation and growth models) methods. The first three stages are best described by the N^th order model with activation energy values of 21, 53 and 90?kJ?mol^?1. The last stage, during which ammonium nitrate decomposition occurs, is best fit by the nucleation and growth model and has an activation energy of 129?kJ?mol^?1. The proposed mechanism, supported by the kinetic analysis in our study, indicates that CeO₂ has already formed before the reaction reaches 200?°C. The average crystallite size of CeO₂ synthesized at 300?°C, which was calculated from the XRD measurements and observed in the SEM and TEM data, is between 10 and 20?nm.     

The influence of impurity-doping on temperature dependence of dislocation-ribbon width in graphite

By means of an electron microscope, the width of dislocation ribbons in a stress-annealed pyrolytic graphite and doped with iodine chloride (ICl) and bromine was investigated as a function of temperature in the range 100°K to 300°K. The impurity content amounted to 1·1 at % for ICl and 1·6 at % for bromine. Through measurements of the ribbons widths W in steps of 20°K, the average temperature coefficients $\text{1}\text{W}\text{·}\text{dW}\text{?dT}$ were found to be 5 × 10^?4, 3 × 10^?4 and 1 × 10^?4°K^?1, for the original, ICl-doped and bromine-doped material respectively; this shows that the temperature dependence of the ribbon width in graphite is appreciably decreased by the presence of halogen impurities. The phenomenon is quantitatively analyzed in terms of the chemical interaction mechanism between stacking faults and impurities. A discussion of the viscous drag function of impurities for dislocations in relation to the internal friction is included.     

Temperature‐Dependent Deformation and Dislocation Density in SrTiO3 (001) Single Crystals

This study evaluates the change of flow stress as related to dislocation density in SrTiO₃ single crystals in order to provide guidance for later electrical studies. The key parameters varied are temperature and loading rate during the deformation. It is found that in <100>‐oriented SrTiO₃ single crystals, the dislocation density is enhanced by plastic deformation, more so at higher temperature as compared to room temperature. The experimental approach of quantifying the dislocation density through a determination of ex situ X‐ray diffraction rocking curves was successfully applied over the upper temperatures region of the lower temperature ductility zone for strontium titanate, i.e., in the so‐called “A‐regime”. For 1.0% deformed samples deformed at 300°C, a fourfold increase in dislocation density to 1.4 × 10¹³ m^?1 was found as compared to the nondeformed state (3.7 × 10¹² m^?1). Cross‐section techniques confirmed that the observed dislocation densities measured at the surfaces were identical to those seen in the core of the crystals. The use of rapid changes in loading rate provided an estimate for activation volume of the dislocation core for both 25°C and 300°C.     

A preliminary account of char structures produced from Liddell vitrinite pyrolysed at various heating rates

Liddell-seam vitrinite particles were heated to 1000 °C in nitrogen at uniform rates ranging from 10^?1 °C s^?1 to 10⁴ °C s^?1. Little melting or swelling was observed when the particles were heated at 10^?1 °C s^?1 even though the vitrinite is from a coking coal of high-volatile bituminous rank. Particle size (100 μm) and loose packing were probably major influences on the plasticity. Vitrinite particles heated at rates faster than 10^?1 °C s^?1 showed an increase in plasticity with heating rate but the effects related to plasticity and volatile evolution appeared to be approaching a limit. Simple cenospheres (primary vesicles) were formed and preserved at a heating rate of 1 °C s^?1. At a heating rate of 10 °C s^?1 secondary vesicles were produced and preserved in the walls of the primary vesicles. At faster heating rates only secondary and tertiary vesicles were preserved. At a heating rate of 10⁴ °C s^?1 the vesicles preserved were very small.     

Diametral strength testing of hydroxyapatites doped with yttrium and fluoride

Abstract

Abstract

This study aimed to investigate the diametral strength testing of hydroxyapatite (HA) doped with Y and fluoride with different compositions. Hydroxyapatites were synthesised by precipitation method and sintered at 900, 1100 and 1300°C for 1?h. High amounts of doping caused a decrease in relative densities of HAs. Higher sintering temperatures helped in increasing the relative densities. No second phases were observed by X-ray diffraction spectra of 2·5?mol.-%Y and 2·5?mol.-%F doped HA after the sintering at all temperatures. Trace amounts of β-tricalcium phosphate was found in 7·5?mol.-%Y and 2·5?mol.-%F doped HA sintered at 1100 and 1300°C. Diametral strength of doped HAs mostly enhanced with the addition of Y³⁺ and F^?. 2·5YFHA sintered at 1300°C had the highest diametral strength of 11·6?MPa with a relative density of 94·3% of theoretical density.     

Use of ultrasound in petroleum residue upgradation

Conventional processes for the upgradation of residual feedstocks, viz., thermal cracking and catalytic cracking are carried out in the temperature range of 400–520°C. Such high temperatures can in principle be substituted by acoustic cavitation. In the present work, two vacuum residues, namely, Arabian mix vacuum residue (AMVR) and Bombay high vacuum residue (BHVR) and one asphalt, viz., Haldia asphalt (HA) were subjected to acoustic cavitation for different reaction times from 15 min to 120 min at ambient temperature and pressure. An attempt has been made to seek a performance comparison of two devices of acoustic cavitation, namely, ultrasonic bath and ultrasonic horn with regard to their ability to upgrade the petroleum residues to lighter, more value‐added products mainly the hydrocarbons boiling in the range of gas oil fraction. Another attempt has been made to study the effect of ultrasound on the upgradation of the residue when it is emulsified in water with the help of different surfactants. For all the cases, a kinetic model has been developed based on the constituents of the residue so as to get an insight into the reaction mechanism. The study revealed that ultrasonic horn is more effective in bringing about the upgradation than ultrasonic bath and that the acoustic cavitation of the aqueous emulsified hydrocarbon mixture could reduce the asphaltenes content to a greater extent than the acoustic cavitation of non‐emulsified hydrocarbon mixture. The reduction in asphaltenes content of BHVR was found to be more followed by AMVR followed by HA. The variation in the rate constants was found to be feed specific and the rate constants for the conditions of maximum conversion of asphaltenes to gas oil for AMVR, BHVR and HA were found to be 0.29 × 10^?4 s^?1, 1.4 × 10^?4 s^?1 and 0.23 × 10^?4 s^?1, respectively.     

Wet chemistry approach to the preparation of tantalum-doped hydroxyapatite: Dopant content effects

Tantalum-doped hydroxyapatite (Ta-doped HA) nanopowders with different Ta contents were synthesized by a wet-chemical precipitation route. The structure modification and charge compensation mechanism were investigated by various characterization techniques. Due to the smaller size of tantalum ions compared to the Ca²⁺ size, it was assumed that the tantalum ions occupy either the Ca²⁺ and/or the interstitial positions in the HA lattice, where the charge imbalance from to this substitution was compensated by the Ca²⁺ vacancies. From the XRD patterns, the as-synthesized nanopowders were poorly crystalline apatite in the absence and presence of different dopant contents. The hexagonal HA and tricalcium phosphate (β-TCP) phases as biphasic calcium phosphate mixtures were formed after heating at 900 °C. In addition to the β-TCP phase, minor extra phases such as calcium oxide (CaO) and calcium pyrophosphate (Ca₂P₂O₇) were identified from the HA decomposition. The FTIR results indicated that the decrease of structural hydroxyl groups depended on both tantalum oxyanions and carbonate contents. In the XPS profile, the Ta 4 f peak of the doped sample could be decomposed into four main components, which showed different oxidation states for tantalum (TaO₂ oxide). According to the TEM observations, the doped calcined powder at 900 °C was composed of uniform nanoneedles with an average length and width of 120 ± 50 and 10 ± 5 nm, respectively.     

A novel economical grain boundary engineered ultra-high performance ZnO varistor with lesser dopants

A varistor having ultra-high performance was developed from doped ZnO nanopowders using a novel composition consisting of only three (Bi, Ca and Co oxides) dopants. Improved varistor properties were obtained (breakdown field (E_b) 27.5?±?5?kVcm^?1, coefficient of nonlinearity (α) 72?±?3 and leakage current density (L_c) 1.5?±?0.06?μAcm^?2) which are attributed to the small grain size and grain boundary engineering by phases such as Ca₄Bi₆O₁₃ and Ca_0.89Bi_3.11O_5.56 along with Co⁺² doping in the ZnO lattice. Complex impedance data indicated three relaxations at 25?°C and two relaxations at high temperature (>100?°C). The complex impedance data were fitted into two parallel RC model to extract electrical properties. Two stages of activation energy for DC conductivity were observed in these varistor samples where region I (<150?°C) is found to be due to shallow traps and region II (<225?°C) is due to deep traps. The novel composition is useful for commercial exploitation in wide range of surge protection applications.     

Creep of Nextel™ 610 Fiber at 1100°C in Air and in Steam

Creep of Nextel^?610 fibers was investigated at 1100°C and 100–500 MPa in air and in steam. The effect of loading rate on fiber tensile strength was also explored. The presence of steam accelerated creep and reduced fiber lifetimes. Loading rate had a considerable effect on tensile strength in steam, but not in air. A linear elastic crack growth model was used to predict the creep lifetimes from the constant loading rate data. The dependence of tensile strength on loading rate and the predictability of creep lifetimes suggest that the failure mechanism in steam was environmentally assisted subcritical crack growth. The creep‐rupture data were analyzed in terms of a Monkman‐Grant (MG) relationship. Monkman‐Grant parameters for creep‐rupture data were the same in steam and air, and predicted creep‐rupture at 1100°C in both environments. A grain‐size increase of about 25% was observed by TEM after 100 h at 1100°C in steam, which was about two times that observed in air.     

Studies on polycrystalline layered ceramic oxide: LiFeVO4

Abstract

A new polycrystalline layered ceramic oxide, LiFeVO₄, has been prepared by a standard solid state reaction technique. The preparation conditions were optimised using thermogravimmetric analysis (TGA) technique. Material formation under the reported conditions was confirmed by X-ray diffraction studies. A preliminary structural analysis indicated that the crystal structure was orthorhombic with lattice parameters: a=4·3368 Å, b=13·1119 Å and c=16·3426 Å. The phase morphology and surface property were studied by scanning electron microscopy. Complex impedance analysis of the sample indicated bulk contribution to electrical properties at T≤125°C, grain boundary effects at the temperatures ≥125°C, negative temperature coefficient of resistance (NTCR) effect and evidence of temperature dependent electrical relaxation phenomena in the sample. The dc conductivity σ_dc shows typical Arrhenius behaviour when observed as a function of temperature. The activation energy value was estimated to be 0·24 eV. The value of σ_dc, evaluated from complex impedance spectrum, shows a jump of nearly two orders of magnitude at higher temperature (～1·24 × 10^?5 S cm^?1 at 350°C) when compared with that of σ_dc (1·14 × 10^?6 S cm^?1 at 50°C). Alternating current conductivity spectrum obeys Jonscher's universal power law. The results of σ_ac v. temperature are also discussed.     

Sn-containing Si3N4-based composites for adaptive excellent friction and wear in a wide temperature range

Ceramic design based on reducing friction and wear-related failures in moving mechanical systems has gained tremendous attention due to increased demands for durability, reliability and energy conservation. However, only few materials can meet these requirements at high temperatures. Here, we designed and prepared a Sn-containing Si₃N₄-based composite, which displayed excellent tribological properties at high temperatures. The results showed that the friction coefficient and wear rate of the composites were reduced to 0.27 and 4.88 × 10^?6 mm³ N^?1 m^?1 in air at 800 °C. The wear mechanism of the sliding pairs at different temperatures was revealed via detailed analyses of the worn surfaces. In addition, the tribo-driven graphitization was detected on the wear surfaces and in the wear debris, and the carbon phase was identified by SEM, TEM, and Raman spectrum.