Sintering behaviour and properties of zirconia ceramics prepared by pressureless sintering

Improvements in the sintering process and powder quality can lead to wider application of zirconia in ceramics. In this study, the effects of different temperatures on the stability, relative content of the tetragonal phase, and composition of Al₂O₃–ZrO₂ ceramic powders were explored using pressureless-assisted sintering. The crystallinity of the sintered Al₂O₃–ZrO₂ samples was significantly improved. The content of the tetragonal-phase ZrO₂ in sintered ceramic powders was 52.07%, 52.46%, 56.16%, 63.99%, and 64.90%, respectively, which was significantly higher than those of the raw materials. The average particle size of the sintered samples decreased from 1.07 μm to 0.17 μm with an increase in temperature, indicating that the ceramic powder particles were refined. The sample that was subjected to pressureless-assisted sintering at 1200 °C and held for 1 h exhibited the best stability and more uniform particle distribution compared to other samples. The particle size distribution data were closer to the standard line, satisfying the requirements of the normal distribution law. The results revealed that a high temperature was more favourable to the solid solution, and the formation of an Al₂O₃–ZrO₂ solid solution can diminish the influence of the volume expansion of ceramic powders on the sample properties during sintering. Therefore, the addition of the sintering aid Al₂O₃ significantly promotes the densification of the powders, and the pressureless sintering technique reduces the sintering temperature of the solid solution, thus imparting a crystalline structure and excellent mechanical properties to the material.     

Two-step sintering of Sm2O3 doped ceria stabilized zirconia

Effect of Sm₂O₃ addition and two-step sintering of Ceria Stabilized Zirconia (CSZ) on microstructure and mechanical properties were investigated in the present work. Samaria doped CSZ (SmCSZ) nanopowders were prepared by co-precipitation synthesis from their respective nitrate salts. Synthesized powders were calcined at 1000?°C for 2?h and then compacted to ?10?mm pellets using a uniaxial hydraulic press. Single step & two-step sintering methods were used to sinter the compacted pellets. Powders and sintered pellets were characterized for phase and microstructure using X-Ray Diffraction (XRD) and Scanning Electron Microscopy (SEM) technique. Rietveld method was used for quantification of obtained phases. The hardness of the sintered samples was evaluated by Vicker's hardness tester, and toughness was estimated by indentation fracture toughness method. Samples sintered using two-step sintering method shown optimum hardness and toughness (up to 1288 HV10 and 5.37?MPa?m^1/2) values compared to conventionally sintered samples because of reduced grain size.     

Preparation of high-quality transparent Al-rich spinel ceramics by reactive sintering

Transparent Al-rich spinel ceramics (MgO·nAl₂O₃, n = 1.05–2.5) were prepared by reactive sintering in air followed by the hot isostatic press (HIP). Commercial MgO and γ-Al₂O₃ powders were used as the raw materials, and the effects of composition and HIP temperature on the transmittance and microstructure of resulting samples were investigated. To obtain the high optical quality, extra alumina (n ≥ 1.1) was used to help eliminate residual pores and suppress abnormal grain growth during the sintering process. The appropriate HIP temperature was also critical to realize the single-phase formation and prevent the generation of second-phase precipitates. The resulting samples with n = 1.1 and 1.3 exhibited excellent optical quality and fine grains below 5 µm after HIPed at 1550 °C.     

Enhanced properties of pure alumina ceramics by oscillatory pressure sintering

A novel oscillatory pressure sintering (OPS) process to consolidate high-quality pure alumina ceramics is reported. The microstructure of the ceramics prepared by OPS develops into a higher final density, a smaller and a narrower distribution of grain sizes compared with those prepared by conventional pressureless sintering (PS) and hot-pressing (HP) processes. Enhanced mechanical properties of alumina ceramics were investigated by OPS process. The bending strength, hardness and elastic modulus of the OPS specimen reached about 546 MPa, 19.1 GPa and 374 GPa, respectively, i.e values significantly higher than that of the specimens by PS and HP. XRD analysis indicates the strengthening of atomic bonds aided by oscillatory pressure. The results suggest OPS to be an effective technique for preparing high-quality pure alumina ceramics.     

Sintering highly dense ultra-high temperature ceramics with suppressed grain growth

Grain coarsening normally occurs at the final stage of sintering, resulting in trapped pores within grains, which deteriorates the density and the performance of ceramics, especially for ultra-high temperature ceramics (UHTCs). Here, we propose to sinter this class of ceramics in a specific temperature range and coupled with a relatively high pressure. The retarded grain boundary migration and pressure-enhanced diffusion ensure the proceeding of densification even at final stage. A highly dense TaC ceramic (98.6 %) with the average grain size of 1.48 μm was prepared under 250 MPa via high pressure spark plasma sintering using a C_f/C die at 1850 °C. It was suggested that the final-stage densification is mainly attributed to grain boundary plastic deformation-involved mechanisms. Compared to the usual sintering route using a high temperature (>2000 °C) and normal pressure (<100 MPa), this work provides a useful strategy to acquire highly dense and fine-grained UHTCs.     

Investigation of properties of ZnO ceramics sintered from ZnO-Zn nanopowders produced by pulsed electron beam evaporation

In this paper we have studied the properties of ZnO ceramics sintered from the ZnO-Zn nanopowders (NPs) produced by a pulsed electron beam evaporation of heterogeneous targets (oxide or metal) and to establish the influence of NPs prehistory on the luminescence and dilatometry properties of ceramics produced from them. Pressing was performed on uniaxial presses: static and the magnetic pulsed one. Sintering of ceramics was produced in air by heating to 1200 °C in 60 min. Maximal density of the ceramics did not exceed 81,25% of the theoretical density. The behavior of the shrinkage curves of ZnO-Zn NPs depends on their prehistory. Evolution of properties of ZnO-Zn nanoparticles (NPles) during annealing in air is studied by XRD and pulsed cathodoluminescence methods. The suppression of the ultraviolet emission in NP obtained by electron beam evaporation, and in ceramics sintered of them was established.     

Ultrastrong tough zirconia ceramics by defects-engineering

We report the preparation of a category of ultrastrong tough zirconia ceramics by engineering defects using an oscillatory pressure during pressure assisted sintering. The introduced oscillatory pressure enhances the dynamic grain rearrangement, plastic deformation, mass transportation, and pore removal, leading to the formation of pore-free ceramics characterized by the rich coherent grain boundaries among individual mesocrystalline grains with intragranular quasi-interfaces. As a proof of concept, the pressure required by oscillatory pressure sintering (OPS) for preparing fully dense 3Y-TZP ceramics is significantly reduced, which is just ∼1/5 of that required by hot isostatic pressing. The OPS-prepared 3Y-TZP ceramics reached a record-breaking high bending strength and fracture toughness, being up to 1.8 GPa and 16 MPa·m^1/2, respectively. This success illustrates a universal principle of engineering defects for making breakthrough in exploring other ultrastrong tough ceramics.     

Grain size effect on microwave dielectric properties of Na2WO4 ceramics prepared by cold sintering process

In this work, cold sintering was adopted to prepare Na₂WO₄ ceramics with different grain sizes ranging from 0.632 μm to 17.825 μm. Their microstructures, complex impedance, and microwave dielectric properties were studied in-depth. It was found that samples with relative densities higher than 92% can be successfully synthesized by cold sintering process at a low temperature of 240 °C. However, their electrical properties have strong dependence on the grain size. Specifically, the resistance of grain boundaries decreases dramatically with the increase of grain sizes, while the quality factor has a positive correlation with the grain sizes of Na₂WO₄ ceramics. Excellent microwave dielectric properties, including permittivity = 5.80, Q × f = 22,000 GHz, and TCF = −70 ppm/°C, are obtained for Na₂WO₄ ceramics with a grain size of 4.477 μm prepared by cold sintering process.     

Grain growth kinetics of 3 mol. % yttria-stabilized zirconia during flash sintering

Grain growth kinetics of dense 3 mol. % yttria-stabilized zirconia (3YSZ) ceramics during both DC flash sintering and conventional annealing were investigated using the grain size as a marker of microstructure evolution. The results indicated faster grain growth under greater current density. In contrast to conventionally annealed specimen, the grain boundary mobility was enhanced by almost two orders of magnitude with the applied electric current, revealing that joule heating alone was not sufficient to account for the experimental results. Instead, activation energy for grain growth decreased significantly due to electro-sintering. Systematic characterization of graded microstructure further indicated that local oxygen vacancies and specimen temperature were responsible for a grain size transition. Based on electrochemical reaction involved in flash sintering, grain size reduction at the cathode was proposed to be attributed to the local rearrangement of lattice cations and generated oxygen ions.     

Field assisted sintering of ceramic constituted by alumina and yttria stabilized zirconia

We show that a two-phase 50 vol% 3YSZ-alumina ceramic flash-sinters at a furnace temperature of 1060 °C under an electrical field of 150 V cm⁻¹. In contrast undoped, single-phase alumina remains immune to field assisted sintering at fields up to 1000 V cm⁻¹, although single-phase 3YSZ flash sinters at 750 °C (furnace temperature). The mechanisms of field assisted sintering are divided into two regimes. At low fields the sintering rate increases gradually (FAST), while at high fields sintering occurs abruptly (FLASH). Interestingly, alumina/zirconia composites show a hybrid behavior such that early sintering occurs in FAST mode, which is then followed by flash-sintering. The specimens held in the flashed state, after they had sintered to near full density, show much higher rate of grain growth than in conventional experiments. These results are in contrast to earlier work where the rate of grain growth had been shown to be slower under weak electrical fields.     

Sintering of Confined Silica in Oxidized Silicon Particles

We observed electron-beam-induced sintering of amorphous silica in oxidized submicrometer silicon particles and analyzed the nature of mass transport in linear and triangular particle assemblies. The movement of silica around the rigid crystalline cores occurs rapidly and fills the necks, but the relative core positions in the sintered product depends on the initial geometry of the confined oxide. However, a thin layer of silica remains stable against the flow.     

Tailoring the grain size of zirconia polycrystalline fibers by cetyltrimethyl ammonium bromide

In the study, cetyltrimethyl ammonium bromide (CTAB) has been found to have a significant effect on the grain size of zirconia (ZrO₂) polycrystalline fibers from a precursor of polyacetylacetonatozirconium (PAZ). A relation between the variation in the grain size of the fibers sintered at 1000 °C for 1 h and CTAB addition has been established by scanning electron microscopy (SEM) and matching the results by a Gaussian Function. The grain size increased firstly and then decreased at an elevated weight percent of CTAB with respect to PAZ. ZrO₂ nucleation at 500 °C and grain growth during thermal treatment between 500 and 1000 °C were investigated by thermal analysis (TG-DTA), X-ray photoelectron spectroscopy (XPS), high resolution transmission electron microscopy (HRTEM) and X-ray diffraction (XRD). The results indicate that the addition of CTAB accelerated the decomposition of PAZ. The enhanced decomposition promoted ZrO₂ nucleation and the removal of residual carbon. While excess CTAB resulted in the increase of residual carbon on grain surface. The general kinetics of the grain growth was evaluated by Arrhenius equation and the results did matched well with the variation in grain size.     

Densification and properties of zirconia prepared by three different sintering techniques

Densification of nanocrystalline yttria stabilized zirconia (YSZ) powder with 8 mol% Y₂O₃, prepared by a glycine/nitrate smoldering combustion method, was investigated by spark plasma sintering, hot pressing and conventional sintering. The spark plasma sintering technique was shown to be superior to the other methods giving dense materials (≥96%) with uniform morphology at lower temperatures and shorter sintering time. The grain size of the materials was 0.21, 0.37 and 12 μm after spark plasma sintering, hot pressing and conventional sintering, respectively. Total electrical conductivity of the materials showed no clear correlation with the grain size, but the activation energy for spark plasma sintered materials was slightly higher than for materials prepared by the two other densification methods. The hardness, measured by the Vickers indentation method, was found to be independent on grain size while fracture toughness, derived by the indentation method, was slightly decreasing with increasing grain size.     

Crystal defects and phase transitions of nanocrystalline yttria-stabilised zirconia induced by high-energy ball milling

Yttria-stabilised zirconia (YSZ) is a promising electrolyte for SOFCs and gas sensors. In this study, the particle size of a co-precipitated 5 mol% yttria-stabilised zirconia (5 YSZ) powder was refined from 10.47 μm to 130 nm via high-energy ball milling to improve its sinterability and ionic conductivity. The ball milling process increased the specific surface area of the 5 YSZ powder from approximately 11 to 22 m² g^?1. The transmission electron microscopy (TEM) and high-resolution TEM (HRTEM) results indicated that the 5 YSZ crystallites decomposed into irregular shapes with the evolution of point, linear, and planar defects. An increase in the milling duration increased the number of oxygen defects in the 5 YSZ powder, as revealed by the X-ray photoelectron spectroscopy results. The tetragonal-to-monoclinic phase transformation occurring in the powder was investigated by X-ray diffraction, Raman spectroscopy, HRTEM, and selected-area electron diffraction pattern analyses. The ball-milled powders could be easily densified, but the presence of too many crystal defects and the large fraction of the m-ZrO₂ phase were detrimental to the further densification of the 5 YSZ powders. In spite of the high sintering temperature (1500 °C) used in this study, the maximum relative density of 99.67% could be achieved for the powder ball-milled for 60 min at the rotor speed of 1500 rpm. Moreover, the ionic conductivity of 5 YSZ was improved significantly from 20.6 to 36.2 mS cm^?1 (850 °C) after the high-energy ball milling process.     

Phase transformation kinetics of 3 mol% yttria partially stabilized zirconia (3Y-PSZ) nanopowders prepared by a non-isothermal process

A crystalline nanopowder of 3 mol% yttria-partially stabilized zirconia (3Y-PSZ) has been synthesized using ZrOCl₂ and Y(NO₃)₃ as raw materials throughout a co-precipitation process in an alcohol-water solution. The phase transformation kinetics of the 3Y-PSZ freeze dried precursor powders have been investigated by nonisothermal methods. Differential thermal and thermogravimetric analyses (DTA/TG), X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and high resolution TEM (HRTEM) have been utilized to characterize the 3Y-PSZ nanocrystallites. When the 3Y-PSZ freeze dried powders are calcined in the range of 703-1073 K for 2 h, the crystal structure is composed of tetragonal and monoclinic ZrO₂. The BET specific surface area of the 3Y-PSZ freeze dried precursor powders calcined at 703 K for 2 h is 118.42 m²/g, which is equivalent to a crystallite size of 8.14 nm. The activation energy from tetragonal ZrO₂ converted to monoclinic ZrO₂ in the 3Y-PSZ freeze dried precursor powders was determined as 401.89 kJ/mol. The tetragonal (T) and monoclinic (M) ZrO₂ phases coexist with a spherical morphology, and based on TEM examination have a size distribution between 10 and 20 nm. When sintering green compacts of the 3Y-PSZ, a significant linear shrinkage of 8% is observed at about 1283 K. On sintering the densification cycle is complete at approximately 1623 K when a total shrinkage of 32% is observed and a final density above 99% of theoretical was achieved.     

电子束辐照法在水处理中的应用

在介绍电子束辐照机理的基础上，概述了其在环境保护中的应用，并着重从降解有毒有害和难降解的有机污染物、重金属离子的去除等方面对国外就电子束辐照在水处理中的研究和应用现状进行综述，最后对电子束辐照和其他的水处理工艺进行了比较，就其自身可以实现对有毒有害有机物混合液的同时处理、与γ辐射相比具有操作方便、安全的特点，但是自由基与有机物反应的选择性差、易受自由基消耗剂的影响，所需剂量一般较大。并对其在水处理中的应用前景进行了展望。     

电子束辐射硫化的原理及应用

介绍电子束辐射硫化技术的原理和辐射剂量对橡胶物理性能的影响。与传统化学硫化工艺相比,电子束辐射硫化工艺可提高胶料耐老化性能,且硫化速度加快。以全钢和半钢子午线轮胎过渡层胶料为例,使用电子束辐射预硫化可减小过渡层胶料厚度或取消过渡层,在节省轮胎生产成本的同时,还可提高轮胎的均匀性和高速性能。     

Size effect on hardness for micro-sized and nano-sized YAG transparent ceramics

Traditional micro-sized and nano-sized YAG transparent ceramics were tested by nanoindentation at different peak loads. The micro-sized YAG transparent ceramics show a marked indentation size effect (ISE). However, for the nano-sized YAG transparent ceramics, the hardness was constant in the whole investigated range without any evidence of ISE. We show that the absence of indentation size effect for nano-sized YAG transparent ceramics can be accurately modeled using the plastic deformation mechanism of grain boundary sliding.     

Bulk boron carbide nanostructured ceramics by reactive spark plasma sintering

Bulk boron carbide (B₄C) ceramics was fabricated from a boron and carbon mixture by use of one-step reactive spark plasma sintering (RSPS). It was also demonstrated that preliminary high-energy ball milling (HEBM) of the B+C powder mixture leads to the formation of B/C composite particles with enhanced reactivity. Using these reactive composites in RSPS permits tuning of synthesized B₄C ceramic microstructure. Optimization of HEBM + RSPS conditions allows rapid (less than 30 min of SPS) fabrication of B₄C ceramics with porosity less than 2%, hardness of ~35 GPa and fracture toughness of ~ 4.5 MPa m ^1/2     

Structure and morphology of isotactic polypropylene functionalized by electron beam irradiation

The structure and morphology of isotactic polypropylene (iPP), functionalized by electron beam irradiation at room temperature in air, are investigated by elementary analysis, FT‐infrared (FTIR) spectroscopy, electron spectroscopy for chemical analysis (ESCA), polariscope, and static contact angle. Elementary analysis reveals that the element oxygen has been introduced onto iPP chains after electron beam irradiation. In addition, as shown from FTIR spectra, oxygen‐containing groups, such as carbonyl, carboxyl, and ether groups, are introduced onto iPP molecular chains. The dependence of oxygenation extent (as measured by O_1S/C_1S value of ESCA spectra) on electron beam dose is obtained. Under polariscope, it can be observed that the dominant alpha phase appears to become more enhanced, and there is no crystalline phase transition. The static contact angle of iPP decreases with increasing dose. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 75–82, 2000