Potential-current characteristics in SiC/ZrB2 composite ceramics

ZrB₂/SiC composite ceramics were fabricated to improve the electrical conductive properties of SiC matrix. The debinding and sintering temperatures were determined by computation of Gibbs free energy. As a result, all the samples have the relative density above 99%, and have excellent mechanical and electrical properties. The effects of ZrB₂ content on the microstructure, mechanical and electrical properties were systematically studied. With increasing ZrB₂ content, as-prepared composites show great improvement in their mechanical properties. Importantly, the introduction of ZrB₂ weakened varistor nonlinear characteristic of composite and reduced its resistivity. The reason is the evolution of grain boundary in conductive paths. The sharp decrease of resistivity indicates the formation of percolation paths. The percolation threshold at 1?mA?cm^?2 obtained via percolation model is 10.7963?vol% (19.7098?wt%) ZrB₂. This value is much less than conventional composites, because the percolation path originates from grain boundary breakdown other than continuous conductor chains.     

Combustion synthesis of high-temperature ZrB2-SiC ceramics

The work is dedicated to researching into combustion kinetics and mechanism as well as the stages of the chemical transformations during self-propagating high-temperature synthesis of ZrB₂-SiC based ceramics. Dependences of the combustion temperature and rate on the initial temperature (T₀) have been studied. It has been shown that the stages of the chemical reactions of ZrB₂ diboride and SiC carbide formation do not change within the range of T_0?=?298–700?К. The effective activation energy of the combustion process amounted to 170–270?kJ/mol, from which it has been concluded that chemical interaction through the melt plays a leading role. The stages of the chemical transformations in the combustion wave have been studied by dynamic X-ray diffraction. First, ZrB₂ phase forms from Zr-Si melt saturated with boron, and SiC phase is registered later. The SHS method has successfully been used in order to obtain ZrB₂-SiC composite powders and compact ceramics with a silicon carbide content of 25–75%. The ceramics are characterized by a residual porosity of 1.5%, hardness up to 25?GPa, the elastic modulus of 318?±?21?GPa, elastic recovery of 36% and thermal conductivity of 54.9?W/(m?×?K) at T_room.     

Mechanical properties of sintered ZrB2-SiC ceramics

ZrB₂ ceramics containing 10-30 vol% SiC were pressurelessly sintered to near full density (relative density >97%). The effects of carbon content, SiC volume fraction and SiC starting particle size on the mechanical properties were evaluated. Microstructure analysis indicated that higher levels of carbon additions (10 wt% based on SiC content) resulted in excess carbon at the grain boundaries, which decreased flexure strength. Elastic modulus, hardness, flexure strength and fracture toughness values all increased with increasing SiC content for compositions with 5 wt% carbon. Reducing the size of the starting SiC particles decreased the ZrB₂ grain size and changed the morphology of the final SiC grains from equiaxed to whisker-like, also affecting the flexure strength. The ceramics prepared from middle starting powder with an equiaxed SiC grain morphology had the highest flexure strength (600 MPa) compared with ceramics prepared from finer or coarser SiC powders.     

Influence of small amount of sintering additives on unlubricated sliding wear properties of SiC ceramics

Fully densified SiC ceramics were developed from commercially available β-SiC powders using small amount (3 wt%) of AlN-Sc₂O₃ or AlN-Y₂O₃ additives by hot pressing at 2050 °C for 6 h in nitrogen atmosphere, and their wear properties were investigated by subjecting to self-mated sliding at different loads (1, 6 and 13 N) under unlubricated conditions. SiC ceramics prepared with 3 wt% AlN-Y₂O₃ additives consisted of mostly large equi-axed grains with amorphous grain boundary phase of ∼1.2 nm thickness, whereas SiC ceramics sintered with 3 wt% AlN-Sc₂O₃ additives showed duplex microstructure of elongated and fine equi-axed grains with clean grain boundary. As the load was increased, the steady state coefficient of friction reduced from ∼0.6 to ∼0.2, and wear rate increased from 10⁻⁶ to 10⁻⁵ mm³/N·m. It was observed that the friction did not depend on the additive composition, while less wear was observed for the SiC ceramics sintered with 3 wt% AlN-Sc₂O₃ additives consisting of clean grain boundary. The material loss was increased with the increased amount of sintering additive to 10 wt%. The worn surface morphology revealed that the material was primarily removed via surface grooving and microcracking at 1 N load, while tribochemical wear dominated at 6 and 13 N loads.     

Pursuing enhanced oxidation resistance of ZrB2 ceramics by SiC and WC co-doping

The oxidative degradation of ZrB₂ ceramics is the main challenge for its extensive application under high temperature condition. Here, we report an effective method for co-doping suitable compounds into ZrB₂ in order to significantly improve its anti-oxidation performance. The incorporation of SiC and WC into ZrB₂ matrix is achieved using spark plasma sintering (SPS) at 1800?°C. The oxidation behavior of ZrB₂-based ceramics is investigated in the temperature range of 1000?°C–1600?°C. The oxidation resistance of single SiC-doped ZrB₂ ceramics is improved due to the formation of silica layer on the surface of the ceramics. As for the WC-doped ZrB₂, a dense ZrO₂ layer is formed which enhances the oxidation resistance. Notably, the SiC and WC co-doped ZrB₂ ceramics with relative density of almost 100% exhibit the lowest oxidation weight gain in the process of oxidation treatment. Consequently, the co-doped ZrB₂ ceramics have the highest oxidation resistance among all the samples.     

Influence of SiC on phase and microstructure of ZrB2 powders synthesized via carbothermal reduction at different temperatures

ZrB₂ powders were successfully prepared via carbothermal reduction of ZrO₂ with H₃BO₃ and carbon black under flowing argon. By introducing SiC species into reaction mixtures, the effects of SiC addition on phase composition and morphology of ZrB₂ powders thermally treated at different temperatures were investigated. The resultant samples were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), and energy dispersive spectrometer (EDS). The highly pure ZrB₂ with the mean size of 5?µm could be obtained at 1600?°C for 90?min and the grains presented columnar shapes. After addition of SiC, ZrB₂ revealed relatively better crystallinity and finer particle size. Regular columnar ZrB₂ grains ranging from 1 to 2?µm were seen existing after reaction at 1500?°C for 90?min.     

Reactive hot-pressing of ZrB2-ZrC-SiC ceramics via direct addition of SiC

A series of ZrB₂-ZrC-SiC composites with various SiC content from 0 to 20 vol% were prepared by reactive hot-pressing using Zr, B₄C and SiC as raw materials. Self-propagating high-temperature synthesis (SHS) occurred, and ZrC grains connected each other to form a layered structure when the SiC content is below 20 vol%. The evolution of microstructure has been discussed via reaction processes. The composite with 10 vol% SiC presents the most excellent mechanical properties (four-point bending strength: 828.6±49.9 MPa, Vickers hardness: 19.9±0.2 GPa) and finest grain size (ZrB₂: 1.52 µm, ZrC: 1.07 µm, SiC: 0.79 µm) among ZrB₂-ZrC-SiC composites with various SiC content from 0 to 20 vol%.     

粉体超微化对碳化硅陶瓷显微结构的影响

研究了粉体超微化后碳化硅陶瓷材料显微结构的变化特征 ,分析了超微化处理对碳化硅陶瓷烧结过程及显微结构的影响机理。经超微化处理后 ,粉体颗粒尺寸减小 ,分布范围变窄 ,硬团聚解聚 ,颗粒形状均匀分布 ;素坯均匀性提高 ,坯体烧结温度降低 ,促进了坯体烧结过程 ;陶瓷材料表面显微结构缺陷明显减少 ,获得了理想的显微结构和良好的力学性能     

Influence of cobalt and sintering temperature on structure and electrical properties of BaZr0.05Ti0.95O3 ceramics

Pure and Co-modified BaZr_0.05Ti_0.95O₃ ceramics were fabricated by the traditional solid state reaction technique. The influence of cobalt and sintering temperature on structure, dielectric, ferroelectric properties and diffuse phase transition of BZT ceramics were investigated systematically. 1300 °C was the optimal sintering temperature for BZT ceramics. The solid solubility limit of Co ions in BZT matrix was determined to be 0.4 mol%. The introduction of a moderate amount of Co ions was believed to benefit the microstructure development and make the grain size more uniform. Compared with undoped counterparts, 0.4 mol% Co-modified ceramics showed equivalent ferroelectric properties with a high remnant polarization (P_r=9.6 μC/cm²) and a low coercive field (E_c=0.21 kV/mm). Besides these, a relative high dielectric coefficient (ε_r=2030) and a low dielectric loss (tan δ=1.85%) were also obtained on this composition. The degree of diffuse phase transition was enhanced by the addition of Co ions. The related mechanism of the diffused phase transition behavior was discussed.     

助烧剂和造孔剂对真空烧结SiC多孔陶瓷性能的影响

以粒度≤0.063mm的SiC为主要原料,分别加入30%(质量分数)的Al2O3-Y2O3与10%的Al2O3-高岭土复合助烧剂,并外加不同量(分别为12.8%、26.3%、30.0%和36.4%)的造孔剂羧甲基纤维素钠(CMC),制样后首先在空气炉中经过300℃2h或1100℃4h的预烧,然后在真空炉中于1550℃4h真空烧结而制备成SiC多孔陶瓷,并研究了助烧剂种类以及造孔剂CMC外加量对SiC多孔陶瓷显微组织、显气孔率及抗折强度的影响。结果显示:采用Al2O3-Y2O3作为助烧剂的SiC多孔陶瓷比Al2O3-高岭土作助烧剂的具有较高的抗折强度,显气孔率稍有减小;随着羧甲基纤维素钠量的增加,加入两种助烧剂的SiC多孔陶瓷均表现为显气孔率增加,抗折强度降低。     

ZrB2-MoSi2 ceramics: A comprehensive overview of microstructure and properties relationships. Part II: Mechanical properties

The mechanical behavior of ZrB₂-MoSi₂ ceramics made of ZrB₂ powder with three different particle sizes and MoSi₂ additions from 5 to 70 vol% was characterized up to 1500 °C. Microhardness (12–17 GPa), Young’s modulus (450–540 GPa) and shear modulus (190–240 GPa) decreased with both increasing MoSi₂ content and with decreasing ZrB₂ grain size. Room temperature fracture toughness was unaffected by grain size or silicide content, whilst at 1500 °C in air it increased with MoSi₂ and ZrB₂ grain size, from 4.1 to 8.7 MPa m^½. Room temperature strength did not trend with MoSi₂ content, but increased with decreasing ZrB₂ grain size from 440 to 590 MPa for the largest starting particle size to 700–800 MPa for the finest due to the decreasing size of surface grain pullout. At 1500 °C, flexure strength for ZrB₂ with MoSi₂ contents above 25 vol% were roughly constant, 400–450 MPa, whilst for lower content strength was controlled by oxidation damages. Strength for compositions made using fine and medium ZrB₂ powders increased with increasing MoSi₂ content, 250–450 MPa. Ceramics made with coarse ZrB₂ displayed the highest strengths, which decreased with increasing MoSi₂ content from 600 to 450 MPa.     

Synthesis of ZrB2-SiC powders in one-step reduction process

ZrB₂-SiC composite powders were synthesized through one-step reduction process of ZrO₂, B₄C, carbon black, silicon or silica under flowing argon. Effects of B₄C contents, calcination temperatures and different silicon sources on the phase composition and morphology were investigated. Combining the X-ray diffraction (XRD) results and scanning electron microscope (SEM) images, the spherical ZrB₂-SiC powders ranging from 100?nm to 300?nm would be prepared with silicon at 1500?°C for 60?min when n(B)/n(Zr) was at 2.4. As using silica as the raw material, the obtained ZrB₂ and SiC particles in the powders exhibited different shapes and sizes. The SiC grains were uniformly formed among the ZrB₂ grains.     

Effect of silicon carbide additive on microstructure and properties of porcelain ceramics

Porcelain green bodies with various silicon carbide contents (0-3 wt.%) were prepared from a porcelain tile powder as a major raw material and SiC particle as an additive, and were sintered at 1000-1240 °C. The samples were systematically characterized by the X-ray diffraction (XRD), scanning electron microscope (SEM) and metallurgical microscope. Effects of the SiC content and sintering temperature on the pore size, SiC particle size and sintered density were investigated in detail, and the correlative mechanism was also discussed. The SiC particle size decreased and the pore size augmented with increasing the sintering temperature. The sintered density decreased and the pore size enlarged with increasing the SiC content. The experimental results indicate that a small amount of SiC can cause porcelain ceramics to foam during sintering, and a foaming origin of the polishing porcelain waste during sintering could be attributed to the oxidation reaction of SiC particles under high temperature and alkaline molten salt conditions.     

Spark plasma sintering and characterization of ZrC-TiB2 composites

ZrC-based composites were consolidated from ZrC and TiB₂ powders by the Spark Plasma Sintering (SPS) technique at 1685 °C and 1700 °C for 300 s under 40-50-60 MPa. Densification, crystalline phases, microstructure, mechanical properties and oxidation behavior of the composites were investigated. The sintered bodies were composed of a (Zr,Ti)C solid solution and a ZrB phase. The densification behaviors of the composites were improved by increasing the TiB₂ content and applied pressure. The highest value of hardness, 21.64 GPa, was attained with the addition of 30 vol% TiB₂. Oxidation tests were performed at 900 °C for 2 h and the formation of ZrO₂, TiO₂ and B₂O₃ phases were identified by using XRD.     

Effect of composition fluctuation on structural and electrical properties of BZT-xBCT ceramics prepared by Plasma Activated Sintering

Lead-free [Ba(Zr_0.2Ti_0.8)O₃-x(Ba_0.7Ca_0.3)TiO₃, BZT-xBCT] ceramics were prepared by Plasma Activated Sintering (PAS). The effect of composition fluctuation on structural and electrical properties of BZT-xBCT ceramics was investigated. It was found PAS can obtain compact BZT-xBCT ceramics and BZT-0.50BCT ceramic possessed a MPB structure consisting of rhombohedral and tetragonal phases. Impedance spectroscopy confirmed two contributions from grains and grain boundaries, and the ceramics showed typical characteristic of diffuse phase transition. As compared with the BZT-xBCT ceramics with the pseudo-cubic phase, PAS-ed BZT-0.50BCT ceramic exhibited better properties of d₃₃ = 127 pC/N, k_p = 25.1%, ε_r = 2614, ε_m = 6655, and 2P_r = 25.2 μC/cm² due to the existence of the MPB structure.     

Enhanced oxidation resistance of ZrB2/SiC composite through in situ reaction of gadolinium oxide in patterned surface cavities

Micro-cavities on the surface of dense ZrB₂/20 vol.% SiC composites, machined by ultra-fast laser ablation, were filled with Gd₂O₃ nanopowder and oxidized in static air at 1600 °C. Optimized rectangular pattern of cavities, 10 μm diameter and deep, 20 μm apart conferred improved oxidation resistance compared to the untreated ZrB₂/20 vol.% SiC due to the formation of glasses of higher viscosity with lower oxygen diffusivities. Reduction of the oxidized depth was revealed by a significant decrease of 10 μm (60%) in the extent of the protective layer. The filled-cavity strategy leads to better protection against oxygen diffusivity into the composite without altering the bulk properties.     

Spark plasma sintering and mechanical properties of compounds in TiB2-SiC pseudo-diagram

The influence of spark plasma sintering (SPS) parameters (temperature, time, pressure) and the role of particle size on densification, microstructure and mechanical properties of commercial additive-free TiB₂, SiC and composites thereof were studied by X-ray diffraction, scanning electron microscopy, the ultrasonic method and indentation. Three particle sizes of SiC and 2 of TiB₂ were processed. An optimal cycle was found for TiB₂ and SiC: 2000?°C, 3?min dwell time, and 100?MPa applied at 600?°C. The relative density of pure SiC increases linearly from 70% to 90% when the initial particle size decreases from 1.75?µm to 0.5?µm. Pure TiB₂ was densified up to 87%. Using 2.5?wt% SiC in TiB₂, the relative density increases to 97%. Young's modulus and the hardness of all samples were measured, with results discussed. The higher properties were obtained for additive-free TiB₂–5%SiC with a relative density of 97% and with the Young's modulus and Vickers hardness values being close to 378?GPa and 23?GPa, respectively.     

Dopant effects on high temperature mechanical properties of zirconium carbide ceramics

Combining theoretical and experimental methods, the effects of 5?vol.-% WC dopant on the microstructure evolution, sintering behaviour and mechanical properties of ZrC ceramics were investigated. WC dopant was found to improve the high temperature elastic modulus and bending strength of ZrC ceramics. Both calculations and experimental results showed that the formation of (Zr, W)C solid solution promote dissolution of the impurity oxygen from the starting powder into the lattice sites, resulting in less oxygen defects in grain boundaries. Internal friction curve can also conform that the ZrC ceramics doped with WC have cleaner grain boundaries, which improved higher elastic modulus and bending strength in WC doped ZrC ceramics at elevated temperature.     

Effect of tantalum solid solution additions on the mechanical behavior of ZrB2

Mechanical properties and microstructure were compared for zirconium diboride and two zirconium diboride solid solutions containing 3 and 6 at% tantalum diboride. X-ray diffraction indicated that the ceramics were nearly phase-pure and that tantalum dissolved into the ZrB₂ lattice to form (Zr,Ta)B₂ solid solutions. Microstructural analysis indicated that samples achieved nearly full relative density with average grain sizes that ranged from 3?5 μm. The three compositions had similar values of Young’s modulus (510?531 GPa), shear modulus (225?228 GPa), Vickers hardness (15.2–16.4 GPa), and flexural strength (391?452 MPa). Fracture toughness ranged from 2.6 to 3.7 MPa m^1/2 and with increasing tantalum content, the fracture mode changed from predominantly intergranular to predominantly transgranular. Diboride solid solution materials had comparable properties to the single metal diboride, but differences in microstructure, secondary phases, and strain state among the three ceramics partially obscured the actual effects of the solid solution on fracture behavior.