Sintering kinetics and properties of NiFe2O4-based ceramics inert anodes doped with TiN nanoparticles

Sintering kinetics of NiFe₂O₄-based ceramics inert anodes for aluminum electrolysis doped 7 wt% TiN nanoparticles were conducted to investigate densification and grain growth behaviors. The linear shrinkage increased gradually with the increasing sintering temperature between 1000 and 1450°C, whereas the linear shrinkage rate exhibited a broad peak. The maximum linear shrinkage rate was obtained at 1189.4°C, and the highest densification rate was achieved at the relative density of 75.20%. Based on the pressureless sintering kinetics window, the sintering process was divided into the initial stage, the intermediate stage, and the final stage. The grain growth exponent reduced with increased sintering temperature, whereas the grain growth activation energy decreased by increasing sintering temperature and shortening dwelling time. The grain growth was mainly controlled by atomic diffusion. NiFe₂O₄-based ceramics possessed high-temperature semiconductor essential characteristics. The electrical conductivity of NiFe₂O₄-based ceramics first increased and then decreased with increasing sintering temperature, reached their maximum value (960°C) of 33.45 S/cm under 1300°C, mainly attributed to the relatively dense and uniform microstructure. The thermal shock resistance of NiFe₂O₄-based ceramic was improved by a stronger grain boundary bonding strength and lower coefficient of linear thermal expansion.     

Role of oxygen on the phase stability and microstructure evolution of CaCu3Ti4O12 ceramics

Phase stability and microstructure evolution of polycrystalline CaCu₃Ti₄O₁₂ (CCTO) ceramics were studied by controlling the partial pressure of oxygen (from a poor to an oxygen rich atmosphere) during the sintering process at high temperatures. The samples were analyzed by X-ray powder diffraction, scanning electron microscopy and X-ray energy dispersive spectroscopy. Our results show that the oxygen partial pressure during the sintering process is an important parameter that controls the phase stability, non-stoichiometry, and decomposition process of the CCTO phase as well as the densification and grain growth mechanisms on these polycrystalline ceramics. These results provided us further insight into the important role of copper reduction and copper/oxygen diffusion on the crystalline structure and morphological characteristics of polycrystalline CCTO ceramics.     

Fabrication of high-density NiFe2O4 ceramics by slip casting and pressureless sintering

High-density NiFe₂O₄ ceramics with homogeneous microstructure were produced by slip casting and pressureless sintering. The slurry stability, sintering behavior, and microstructure of NiFe₂O₄ ceramics were investigated. A stable slurry can be obtained by adding 12.5 wt% NiFe₂O₄ nanoparticle and 5 wt% nano-binder at a slurry pH around 11.0. The linear shrinkage and linear shrinkage rate for both NiFe₂O₄ ceramic green bodies shaped by cold press molding and slip casting showed nearly the same trends. The temperature associated with the maximum linear shrinkage rate of slip casted green body was 1263.5°C, which was lower than that of cold press molded sample (1272.0°C). The sintering activation energy of slip casted green body was also lower than that of cold press molded sample (279.18 vs 288.47 kJ mol⁻¹), owing to high density and homogeneity of slip-casted green compact. A high-density NiFe₂O₄ ceramics with uniform grain size distribution can be produced by slip casting and pressureless sintering at 1350°C for 6 hours, attributed to the ability of slip casting to minimize agglomerates and micropores. It demonstrated that slip casting was more suitable to prepare high-density NiFe₂O₄ ceramics with good homogeneity.     

Ultrafast high-temperature sintering of dense and textured alumina

Crystallographic texture engineering in ceramics is essential to achieve direction-specific properties. Current texture engineering methods are time-consuming, energy extensive, or can lead to unnecessary diffusion of added dopants. Herein, we explore ultrafast high-temperature sintering (UHS) to prepare dense and textured alumina using templated grain growth (TGG). From a slurry containing alumina microplatelets coated with Fe₃O₄ nanoparticles dispersed in a matrix of alumina nanoparticles, green bodies with oriented microplatelets were prepared using magnetic assisted slip casting (MASC). The effects of the sintering temperature, time and heating rate on the density and microstructure of the obtained ceramics were then studied. We found that TGG occurs for a temperature range between 1640 and 1780 °C and 10 s sintering time. Sintering at 1700 °C for 10 s led to dense and textured alumina with anisotropic grains thanks to the Fe₃O₄ coating, which did not have the time to diffuse. The highest texture and relative density were obtained with a heating rate of ~5500 °C/min, leading to texture-dependent anisotropic mechanical properties. This study opens new avenues for fabricating textured ceramics in ultra-short times.     

Conventional HP sintering of asymmetric hexagonal structure Yb3+-doped Sr5(PO4)3F transparent ceramic without additives

The 2 at.% Yb³⁺:Sr₅(PO₄)₃F (S-FAP) polycrystalline transparent ceramic with asymmetric hexagonal structures has been synthesized by vacuum hot-pressing the nanoparticles prepared via coprecipitation method. X-ray diffraction results of powder and ceramic indicate that their phase peaks are well matched to the crystal structure of S-FAP. The average particle size of 35.5 nm has been exhibited by powder scanning electron microscopy images, and subsequent images of the ceramic cross section and surface morphology revealed a homogenous and compact microstructure with an average grain size of around 220 nm. The relationship between the optical loss caused by the scattering of anisotropic ceramic grains and the optical transmittance of ceramics was revealed in the hexagonal S-FAP transparent ceramics with different thicknesses. The in-line transmittance of hot-pressed ceramics with 1.5-mm thickness achieved 79.95% at 1100-nm wavelength, and the room-temperature absorption and emission spectra of Yb³⁺ in S-FAP polycrystalline ceramic matrix were measured using a spectrofluorometer.     

Numerical Simulation of Anisotropic Shrinkage in a 2D Compact of Elongated Particles

Microstructural evolution during simple solid-state sintering of two-dimensional compacts of elongated particles packed in different arrangements was simulated using a kinetic, Monte Carlo model. The model used simulates curvature-driven grain growth, pore migration by surface diffusion, vacancy formation, diffusion along grain boundaries, and annihilation. Only the shape of the particles was anisotropic; all other extensive thermodynamic and kinetic properties such as surface energies and diffusivities were isotropic. We verified our model by simulating sintering in the analytically tractable cases of simple-packed and close-packed, elongated particles and comparing the shrinkage rate anisotropies with those predicted analytically. Once our model was verified, we used it to simulate sintering in a powder compact of aligned, elongated particles of arbitrary size and shape to gain an understanding of differential shrinkage. Anisotropic shrinkage occurred in all compacts with aligned, elongated particles. However, the direction of higher shrinkage was in some cases along the direction of elongation and in other cases in the perpendicular direction, depending on the details of the powder compact. In compacts of simple-packed, mono-sized, elongated particles, shrinkage was higher in the direction of elongation. In compacts of close-packed, mono-sized, elongated particles and of elongated particles with a size and shape distribution, the shrinkage was lower in the direction of elongation. The results of these simulations are analyzed, and the implication of these results is discussed.     

A strategy for fabricating anisotropic SI3N4 ceramics with controllable mechanical and thermal properties

Heat dissipation material with programmable anisotropic property is very challenging, yet can realize the controllable thermal diffusion for heating device. In this work, anisotropic Si₃N₄ ceramics with oriented grains are prepared to adjust and improve the mechanical and thermal properties under the applied stress field by rolling film forming technology. Through the design of the sintering aids in the process of liquid-phase sintering, the orientation degree of the Si₃N₄ grains is programmable as well as the mechanical property and the thermal property of the Si₃N₄ ceramics. As a consequence, the obtained Si₃N₄ ceramics show significant anisotropy in mechanical properties and thermal conductivity. The typical fracture toughness and thermal conductivity along the grain orientation direction are 10.6 MPa⋅m^1/2 and 45.45 W/(m⋅K) while they are 4.5 MPa⋅m^1/2 and 66.42 W/(m⋅K) in the direction perpendicular to the oriented grain, respectively. This grain orientation method paves the way for the thermal performance design and the production of programmable heat dissipation material.     

Grain growth behavior in bismuth titanate-based ceramics

Bismuth titanate and lanthanum-doped bismuth titanate ceramics were prepared from freeze-dried powders employing conventional solid state reaction and sintering procedures. The sintering process was carried out at 1150 °C from 4 up to 48 h. X-ray diffraction analysis showed that preferred orientation was reduced in bismuth titanate ceramic as sintering time increased while lanthanum-doped sample showed much less degree of preferred orientation and was independent of sintering time. Grain growth studies also showed that initial anisotropic grain growth rate was the main factor controlling the grain morphology, rendering the plate-shaped grain in both pure and lanthanum-doped bismuth titanate ceramics. Based on established grain growth law, pore-controlled diffusion could be the major mechanism determining the observed microstructure in these layered compounds.     

Anisotropic kinetic of the kaolinite to mullite reaction sequence in multilayer ceramics

Multilayer ceramics with a composite and organized microstructure were realized from kaolin and alumina fibers to improve strength and fracture toughness. Dilatometry experiments along 3 directions reveal anisotropic shrinkages, which are in correlation with different activation energy for sintering. Mullite growth is strongly anisotropic, inducing the formation of an organized microstructure, where larger mullite crystals are mainly oriented in plane of layer and perpendicular to alumina fibers. Kinetic data from thermal transformations show that the starting reaction mechanism is mullite nucleation, and it is continued by a strongly anisotropic grain growth. It is explained by topotactic transformations at phyllosilicate faces and along alumina arrangements. Mullite growth kinetics is also favored perpendicularly to fiber main dimension by the anisotropy of alumina diffusion coefficient. It shows the limited importance of mullite crystallization in microstructural transformation, but it also shows that controlled mullite growth is central in microstructural arrangement.     

Grain-Oriented Microstructure of Alumina Ceramics Made through the Injection Molding Process

The relevance of powder packing structure and microstructure in alumina ceramics made through the injection molding process was investigated in the present study. The packing structure of oriented powder particles was retained in the present ceramics after sintering. Even after significant growth, the orientation of the grains was similar to that of the particles in the green body. Anisotropic shrinkage during sintering was attributed to the packing structure. A density distribution also was found, but its origin remains to be clarified.     

Two-step sintering of 0.93Bi0.5Na0.5TiO3-0.07BaTiO3 lead-free piezoelectric material

Two-step sintering (TSS) as an efficient sintering method for obtaining dense microstructure while preventing excess grain growth was used for sintering 0.93Bi_0.5Na_0.5TiO₃-0.07BaTiO₃ composition which is located near the morphotropic phase boundary of this binary system. In order to compare the obtained microstructure and piezoelectric properties, conventional single step sintering (SSS) was also examined. Microstructure evolution during sintering at different temperatures was investigated to find the optimum sintering temperature. Ferroelectric hysteresis loop as well as unipolar strain behavior of optimally sintered ceramics was studied. According to density measurement and microstructure studies of the prepared ceramics, TSS resulted in finer and more dense and uniform microstructure compared to SSS method. As a result remnant polarization of TSSed ceramic was increased by 35% and its coercive field was decreased by 16%. The inverse piezoelectric coefficient of the SSSed and TSSed was obtained 220 and 300 p.m./V, respectively. These values are high enough for practical applications such as actuators. The obtained results clearly showed that TSS is capable of sintering 0.93Bi_0.5Na_0.5TiO₃-0.07BaTiO₃ at temperatures lower than which is required for SSS method. Therefore the composition stoichiometry is maintained after sintering and denser microstructure without abnormal grain growth is obtained which is responsible for improved electrical properties of the piezoceramics.     

High-strength Ti2AlN ceramics prepared by pulse electric current sintering based on powders synthesized by molten salt method

Ti₂AlN powders were synthesized through molten salt method and re-calcination process using TiH₂, Al and TiN powders as raw materials at 1100 ℃. The composition of final composite was directly influenced by the initial Al and TiH₂ content in the starting mixture. The purity of the synthesized Ti₂AlN powder could reach 97.1 wt% when the Al molar ratio was 1.05. Then high strength Ti₂AlN ceramics were successfully prepared in different modes, including two forms of pulse electric current sintering (PECS/SPS) and hot-pressing sintering (HP). A record-high flexural strength of 719 MPa was obtained for the PECS/SPS with an electrical insulating die (PECS/SPS II) sintered sample, based on the synthesized powder in which the initial molar ratio of Al was 1.1. The sintering behaviors in various modes were analyzed, confirming the shrinkage of particles starting at lower temperature in PECS/SPS II. The density, microstructure, Vickers hardness and elastic modulus of sintered ceramics were also investigated. Therefore, the present work provided the new methods about powder preparation and ceramic sintering of Ti₂AlN, making it possible to be used as high strength structural ceramics.     

Spark plasma sintering of TiN ceramics codoped with SiC and CNT

In this research, we investigated the effects of SiC and multi-walled carbon nanotube (MWCNTs) addition on the densification and microstructure of titanium nitride (TiN) ceramics. Four samples including monolithic TiN, TiN-5?wt% MWCNTs, TiN-20?vol% SiC and TiN-20?vol% SiC-5?wt% MWCNTs were prepared by spark plasma sintering at 1900?°C for 7?min under 40?MPa pressure. X-ray powder diffraction patterns and scanning electron microscope (SEM) micrographs of the prepared ceramics showed that no new phase was formed during the sintering process. The highest calculated relative density was related to the TiN ceramic doped with 20?vol% SiC, while the sample doped with 5?wt% MWCNTs presented the lowest density. In addition, the SEM investigations revealed that the addition of sintering aids e.g. SiC and MWCNTs leads to a finer microstructure ceramic. These additives generally remain within the spaces among the TiN particles and prohibit extensive grain growth in the fabricated ceramics.     

Effect of starting Si3N4 powder type and sintering conditions on grain morphology of α-SiAlON ceramics

Abstract

Nitrogen rich multication α-SiAlON ceramics doped with Y-Ce have been densified by gas pressure sintering using α-Si₃N₄ or mixed β/α-Si₃N₄ starting powder. The effects of α-SiAlON nucleation and growth mechanisms were investigated by using di fferent sintering cycles. X-ray diffraction studies after sintering revealed that 21R polytype phase was present in addition to α -SiAlON matrix phase. Microstructural characterisation of sintered materials prepared using α-Si₃N₄ powder in the starting composition revealed a typical equiaxed grain morphology, as expected if the α-SiAlON nucleation step was not applied before grain growth. However, needlelike α-SiAlON grains were observed if a nucleation step was carried out before final sintering. In starting powders containing mixed β/α-Si₃N₄, needlelike grain morphology was also observed. The effects of different Si₃N4 starting powders and sintering conditions on the grain morphology and mechanical properties are discussed.     

Enhancement of mechanical properties of Os0.9Re0.1B2 ceramics via buried boron powder assisted sintering

As a new type of hard/super-hard materials, the consolidation of transition metal borides is very critical for obtaining bulk ceramics with excellent properties. In the present work, buried boron powder assisted pressures-less sintering was applied for preparation of Os_0.9Re_0.1B₂ ceramics with the aim for mechanical properties improvement. Os_0.9Re_0.1B₂ powders were firstly synthesized via mechanochemical technique with moral ratios of (Os + Re):B = 1:2.5 and 1:2.25, respectively. Bulk samples were then consolidated using buried powder sintering and exposed sintering, respectively, for comparison. The influence of buried boron powder sintering on the phase composition, microstructure, and mechanical properties (micro-hardness, nano-hardness, and Young's modulus) of Os_0.9Re_0.1B₂ ceramic samples were investigated. The results show that by employing buried powder sintering, B powders surrounded the sample during the sintering process, which on the one hand, inhibited decomposition of Os_0.9Re_0.1B₂ to (Os_0.9Re_0.1)₂B₃, while on the other hand, decreased the grain size of the sample. Further, a columnar to equiaxial transition for the grains was found with grain size decreased when (Os + Re):B = 1:2.25. The samples prepared with buried powder sintering have higher mechanical properties as compared with those prepared with exposed sintering. The sample prepared from (Os + Re): B = 1:2.25 by buried powder sintering had the best mechanical properties among the four studied samples, along with the smallest grain size. The mechanical properties of the samples were greatly influenced by the grain size and relative density.     

Fabrication of transparent crystal-oriented polycrystalline strontium barium niobate ceramics for electro-optical application

The transparent polycrystalline ceramics with anisotropic crystal system was successfully fabricated by colloidal processing in a high magnetic field and subsequent vacuum sintering and hot isostatic pressing sintering. In this study, we report the fabrication of the transparent c-axis-oriented Sr_0.6Ba_0.4Nb₂O₆ (SBN60) ceramics. The degree of orientation of SBN60 expressed as the Lotgering factor was ∼1.0 and its relative density was over 99.9%. The transmittance of the crystal-oriented SBN60 was 50% at 1500 nm. Optical phase modulation of SBN60 was successfully observed through the measurement of its phase modulation, which confirms the presence of an electro-optical effect.     

Grain coalescence in (Ti0.2Zr0.2Hf0.2Nb0.2Ta0.2)C during spark plasma sintering

High-entropy (Ti_0.2Zr_0.2Hf_0.2Nb_0.2Ta_0.2)C ceramics (HEC) are fabricated via spark plasma sintering using different die configurations, including the conductive and insulating dies. Compared to the conductive die, the grain sizes of samples sintered in the insulating die are significantly larger, which is attributed to the higher local temperature as a result of the higher current density in the sample. Furthermore, the microstructure evolution and grain growth mechanism of HEC are investigated for the first time. We find that at moderate temperatures (∼1600°C), the grain growth of HEC can occur by a grain coalescence mechanism, forming numerous irregular grains in the porous sample. Three factors are crucial to induce grain coalescence, including the formation of partial melting layers on particle surfaces, nanograin rearrangement via rotation and sliding, and the formation of low-angle grain boundaries. During the final sintering stage, the irregular grains will change into polyhedral shapes by grain boundary migration. These findings are of assistance to better understand and control the microstructure evolution of HEC and other ultrahigh-temperature carbide ceramics.     

Sintering behavior and mechanical properties of spark plasma sintering SiO2-MgO ceramics

SiO₂-MgO ceramics containing different weight fractions (0, 0.5, 1, 2, and 4 wt%) of SiO₂ powder were prepared by mixing nano MgO powder, and the powder mixtures were densified by spark plasma sintering (SPS). The effect of SiO₂ addition and SPS method on the sintering behavior, microstructure and mechanical properties were investigated. Results were compared to specimens obtained by conventional hot pressing (HP) under a similar sintering schedule. The highest relative density, flexural strength and hardness of 2 wt% SiO₂-MgO ceramics reached 99.98%, 253.99 ± 7.47 MPa and 7.56 ± 0.21 GPa when sintered at 1400 °C by SPS, respectively. The observed improvement in the sintering behavior and mechanical properties are mainly attributed to grain boundary "strengthening" and intragranular "weakening" of the MgO matrix. Furthermore, the spark plasma sintering temperature could be decreased by more than 100 °C as compared with the HP method, SPS favouring enhanced grain boundary sliding, plastic deformation and diffusion in the sintering process.     

Thermal conductivity of spark plasma sintered SiC ceramics with Alumina and Yttria

In this study, dense SiC ceramics were fabricated at 1650?1750 °C for 10?60 min by spark plasma sintering (SPS) using 3?10 wt.% Al₂O₃-Y₂O₃ as sintering additives. Effects of sintering temperature, sintering additive content and holding time on microstructure as well as correlations between microstructure and thermal conductivity were investigated. An increase in the sintering temperature promotes grain growth. Extending holding time has little influence on grain size but results in formation of continuous network of sintering additive, which increases interfacial thermal resistance and thus decreases thermal conductivity. For SiC ceramics composed of continuous SiC matrix and discrete secondary phase (yttrium aluminum garnet, YAG), an increase in the sintering additive content results in smaller grain size and lower thermal conductivity. The lower thermal conductivity of the SiC ceramic with higher sintering additive content is mainly due to the smaller grain size rather than the low intrinsic thermal conductivity of YAG.     

Densification mechanism and microstructure characteristics of nano- and micro- crystalline alumina by high-pressure and low temperature sintering

Fully dense ceramics with retarded grain growth can be attained effectively at relatively low temperatures using a high-pressure sintering method. However, there is a paucity of in-depth research on the densification mechanism, grain growth process, grain boundary characterization, and residual stress. Using a strong, reliable die made from a carbon-fiber-reinforced carbon (C_f/C) composite for spark plasma sintering, two kinds of commercially pure α-Al₂O₃ powders, with average particle sizes of 220 nm and 3 μm, were sintered at relatively low temperatures and under high pressures of up to 200 MPa. The sintering densification temperature and the starting threshold temperature of grain growth (T_sg) were determined by the applied pressure and the surface energy relative to grain size, as they were both observed to increase with grain size and to decrease with applied pressure. Densification with limited grain coarsening occurred under an applied pressure of 200 MPa at 1050 °C for the 220 nm Al₂O₃ powder and 1400 °C for the 3 μm Al₂O₃ powder. The grain boundary energy, residual stress, and dislocation density of the ceramics sintered under high pressure and low temperature were higher than those of the samples sintered without additional pressure. Plastic deformation occurring at the contact area of the adjacent particles was proved to be the dominant mechanism for sintering under high pressure, and a mathematical model based on the plasticity mechanics and close packing of equal spheres was established. Based on the mathematical model, the predicted relative density of an Al₂O₃ compact can reach ～80 % via the plastic deformation mechanism, which fits well with experimental observations. The densification kinetics were investigated from the sintering parameters, i.e., the holding temperature, dwell time, and applied pressure. Diffusion, grain boundary sliding, and dislocation motion were assistant mechanisms in the final stage of sintering, as indicated by the stress exponent and the microstructural evolution. During the sintering of the 220 nm alumina at 1125 °C and 100 MPa, the deformation tends to increase defects and vacancies generation, both of which accelerate lattice diffusion and thus enhance grain growth.