Effects of dopants with various valences on densification behavior and phase composition of a ZrO2–SiO2 nanocrystalline glass-ceramic

Effects of dopants with different valences on the densification behavior and phase composition of a ZrO₂–SiO₂ nanocrystalline glass-ceramic (NCGC) during pressureless sintering were investigated in this study. The raw powder of Ca²⁺, La³⁺, Ce⁴⁺ and Ta⁵⁺ ions doped ZrO₂–SiO₂ (referred to as Ca-ZS, La-ZS, Ce-ZS, Ta-ZS, respectively) and pure ZrO₂–SiO₂ (PZS) sample were synthesized by sol-gel method, followed by pressureless sintering. Compared with the PZS sample, doping of Ca²⁺ and La³⁺ ions significantly promoted the densification of the NCGCs. The “densification promotion” effect was attributed to the formation of oxygen vacancies and the decrease of SiO₂ viscosity due to doping of aliovalent cations. The dopants with various valences showed significant effects on the phase compositions of the NCGCs during sintering. Doping of Ca²⁺ ion accelerated the reaction kinetics between ZrO₂ nanocrystallites and amorphous SiO₂ to yield ZrSiO₄. The La³⁺ ion acted as destabilizer of t-ZrO₂, which resulted in a rapid tetragonal (t) to monoclinic (m) ZrO₂ phase transformation during sintering, while in the Ta⁵⁺ and Ce⁴⁺ ions doped sample, the phase transformation occurred gradually. All the doping ions increased the lattice parameters and the volume of t-ZrO₂ unit cell, while the effects of the doping ions on the lattice parameters of m-ZrO₂ unit cell were more complex.     

Sintering behavior of BaCe0.7Zr0.1Y0.2O3-δ electrolyte at 1150 °C with the utilization of CuO and Bi2O3 as sintering aids and its electrical performance

BaCe_0.7Zr_0.1Y_0.2O_3-δ (BCZY) is one of the promising electrolytic candidate for solid oxide fuel cell (SOFC) due to its good proton conductivity and better stability. Herein, the effect of dual sintering aids such as CuO-Bi₂O₃ upon the sinterability at low temperature, improved electrochemical properties, and thermo-chemical changes about proton-conducting BaCe_0.7Zr_0.1Y_0.2O_3-δ electrolyte were investigated in detail. FESEM micrographs and shrinkage curves revealed significant improvement in sinterability and densifications of BCZY electrolyte. The dense pellets were sintered with CuO-Bi₂O₃ (2–3 mol %) as sintering aids at a temperature of 1150 °C for 5 h. The perfectly uniform distribution of sintering aids increased the linear shrinkage of BCZY from 5% till 19–21%. The crystallite size and grain growth within the structure was enhanced due to the formation of the melting phase of Bi₂O₃ and Cu²⁺ incorporation in the perovskite structure. The elevated and improved electrochemical measurement for BCZY with 2 mol% of CuO-Bi₂O₃ as sintering aid categorized it well suited for solid oxide fuel cells.     

Effect of Nb content on the phase composition,densification, microstructure,and mechanical properties of high-entropy boride ceramics

Dense high-entropy (Hf,Zr,Ti,Ta,Nb)B₂ ceramics with Nb contents ranging from 0 to 20 at% were produced by a two-step spark plasma sintering process. X-ray diffraction indicated that a single-phase with hexagonal structure was detected in the composition without Nb. In contrast, two phases with the same hexagonal structure, but slightly different lattice parameters were present in compositions containing Nb. The addition of Nb resulted in the presence of a Nb-rich second phase and the amount of the second phase increased as the Nb content increased. The relative densities were all >99.5 %, but decreased from ～100 % to ～99.5 % as the Nb content increased from 0 to 20 at%. The average grain size decreased from 13.9 ± 5.5 μm for the composition without Nb additions to 5.2 ± 2.0 μm for the composition containing 20 at% Nb. The reduction of grain size with increasing Nb content was due to the suppression of grain growth by the Nb-rich second phase. The addition of Nb increased Young’s modulus and Vickers hardness, but decreased shear modulus. While some Nb dissolved into the main phase, a Nb-rich second phase was formed in all Nb-containing compositions.     

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.     

Densification effects on the fracture in fused silica under Vickers indentation

This study investigates the effects of densification on the deformation and fracture in fused silica under Vickers indentation by both the finite element analysis (FEA) and experimental tests. A refined elliptical constitutive model was used, which enables us to investigate the effects of the evolution of yield stress under pure shear and elastic properties with densification. The densification distribution was predicted and compared with experiments. The plastic deformation and indentation stress fields were used to analyze the initiation and morphology of various crack types. The formation mechanism of borderline cracks was revealed for the first time. This study reveals that the asymmetry of the densification distribution and elastic-plastic boundary significantly influences the cracking behavior. Under the Vickers indentation, conical cracks have the largest penetration depth. When these cracks emerge from a region far from the impression, they extend with constant radii to form circles on the sample surface. Otherwise, they tend to be initiated at the centers of the indenter-material contact edges before propagating towards the impression corners with increasing radii. Therefore, the borderline cracks consisting of successive partial conical cracks can form at a low load and makes them the first type of crack to appear.     

Stimulation of densification during the reduction of U3O8 to UO2 by atmosphere control

A reduction process in the head-end for pyroprocessing has been adopted to avoid oxidation attack on the molybdenum crucible during sintering. The reduction process is employed to reduce U₃O₈ pellets to UO₂ prior to sintering. This allows elimination of the oxygen source, which causes oxidation attack during sintering, thereby permitting the use of a metallic crucible. However, little densification occurs due to the low reduction temperature limited by the INCONEL crucible. Consequently, the amount of material scraps from the pellets increases, thus creating an additional processing burden due to its high radioactivity. To reduce the amount of scraps, densification should be enhanced. This study suggests a simple atmospheric control strategy and clarifies its effects. With the atmospheric control, a higher bulk density and better attrition resistance were obtained in comparison to without this strategy. This can be explained in terms of O/U ratio dependent diffusion kinetics during the reduction of U₃O₈ to UO₂.     

Influence of ZrB2 hard ceramic reinforcement on mechanical and wear properties of aluminum

In this work, the effect of ZrB₂ (0, 5, 10 and 20?vol%) ceramic reinforcement on densification, structure, and properties of mechanically alloyed Al was investigated. The milling of Al-ZrB₂ powder compositions resulted in formation of agglomerates with varied size. In particular, the size of agglomerates was reduced considerably with increased addition of ZrB₂ to Al. Interestingly, the densification of hot pressed Al increased from 96.06% to 99.22% with ZrB₂ addition. The reduction of agglomerates size was attributed to the enhanced densification of Al-ZrB₂ composites. Pure Al showed relatively low hardness (0.94?GPa) and it was improved to 1.78?GPa with the addition of 20?vol% ZrB₂. The mechanical properties have significantly been improved for Al-ZrB₂ composites. Especially Al - 20?vol% ZrB₂ possessed a very high yield strength (529?MPa), compressive strength (630?MPa) and compressive strain of 19.25%. Realization of such a good combination of mechanical properties is the highest ever reported for Al composites so far in the literature. The coefficient of friction (COF) of Al-ZrB₂ varied narrowly between 0.33 and 0.40 after dry sliding wear against steel disc. The wear rate of Al-ZrB₂ composites was within mild wear regime and varied between 98.88?×?10^?6 and 34.66?×?10^?6 mm³/Nm. Among all the compositions, Al - 20?vol% ZrB₂ composite exhibited the lowest wear rate and high wear rate was noted for pure Al. Mild abrasion, tribo-oxidation, third body wear (wear debris) and delamination were the major material removal mechanisms for Al-ZrB₂ composites. Overall the hardness, strength and wear resistance of Al - 20?vol% ZrB₂ composite was improved by 84.3%, 84.3% and 64.2%, respectively when compared to pure Al.     

Influence of TiN dopant on microstructure of TiB2 ceramic sintered by spark plasma

In this study, the impact of TiN as a sintering aid on the relative density and microstructure of TiB₂ ceramic was investigated. Monolithic TiB₂ and TiB₂ doped with 5?wt% TiN were sintered at 1900?°C for 7?min dwell time under the pressure of 40?MPa by spark plasma. The addition of TiN affected the microstructure of TiB₂-based sample considerably depicting the finer grains in the as-sintered ceramic. X-ray diffraction evaluation indicated that no interaction occurred between the initial materials. However, detail investigation by the map analysis and energy dispersive spectroscopy results revealed the formation of in-situ nano-sized hBN secondary phase in the TiN-doped TiB₂. In addition, TiN played a remarkable role on increasing the relative density of TiN-doped TiB₂ ceramic producing a nearly fully dense ceramic with relative density of 99.9% in comparison with the monolithic ceramic having 96.7% relative density.     

Densification and anticorrosion performances of vacuum evaporated aluminium coatings on NdFeB magnets

Al coated NdFeB magnets obtained by vacuum evaporation technique were densified by high energy ball milling method.The surface morphology,metal composition and micro structure of the coatings were characterized by scanning electron microscopy,X-ray diffraction and X-ray photoelectron spectroscopy,respectively.The anticorrosive properties were investigated by potentiodynamic polarization curves and neutral salt spray test.The pores in the Al coatings of columnar crystals(Al) induced by the evaporation technique,were apparently filled in the following ball milling process,leading to the densification of Al coatings and the evident improvement of the anticorrosive performances.When treated with ball milling for 30 min,the sample achieves the best anticorrosive performances with the self-corrosion potential of-0.87 V,self-corrosion current density of 1.65 μA/cm~2 and the neutral salt spray(NSS) time of 144 h(red rust).The improvement of the anticorro sive performances of vacuum evaporated Al coating mainly lies in the densification effect of the coating,which depends on different loading conditions of ball milling process.     

Effect of oscillatory pressure on the sintering behavior of ZrO2 ceramic

Zirconia ceramics were prepared by oscillatory pressure sintering (OPS) and hot pressing (HP). The result revealed that OPS could enhance densification compared to HP when sintering temperature was higher than a critical value. The onset temperature for rapid grain growth was found to be same for both techniques. However, rate of grain growth in OPS was lower than that in HP. Furthermore, the result also showed that samples prepared by OPS exhibited higher hardness than those prepared by HP when sintering temperature was higher than the critical value. The improved hardness was solely due to the higher density of the samples prepared by OPS.