Precoarsening to Improve Microstructure and Sintering of Powder Compacts

MgO and Al₂O₃ were sintered by two types of processes: a conventional isothermal sintering and a two-step sintering consisting of an initial low-temperature precoarsening treatment before conventional isothermal sintering. The final microstructure from two-step sintering can be more uniform and finer than that of compacts sintered conventionally. A narrow-size-distribution alumina powder was sintered under constant-heating-rate conditions, with and without a precoarsening treatment, and the results were compared. The differences between two-step and conventional processing were clarified by experiments on precoarsened and as-received ZnO powders. These compacts were precoarsened at 450°C for 90 h with virtually no increase in the overall density. The resulting grain size was 1.7 times the starting one, but the standard deviation of the precoarsened powder size distribution was smaller than that of the asreceived powder. Precoarsened compacts sintered to nearly full density showed improved homogeneity. The sintering stress of the precoarsened ZnO was approximately 0.8 that of the as-received one. A computational model has been used with two components of coarsening to describe the differences in pore spacing evolution between the precoarsened and the as-received system. The benefit of two-step sintering is attributed to the increase in uniformity resulting from precoarsening. The increased uniformity decreases sintering damage and allows the system to stay in the open porosity state longer, delaying or inhibiting additional coarsening (grain growth) during the final stage of densification. Two-step sintering is especially useful for nonuniform powder systems with a wide size distribution and is a simple and convenient method of making more uniform ceramic bodies without resorting to specialized powders or complicated heat schedules.     

Sintering behaviour of a ZnO waste powder obtained as by-product from brass smelting

The effect of two sintering methods (conventional sintering and two-step sintering) and of alumina addition on the sintering behaviour of a ZnO-rich waste powder (ZnO > 95 wt%), a by-product from brass smelting industry, was studied aiming to improve the sintered density and grain size. Both conventional sintering and two-step sintering methods did not lead to fully dense powder compacts, as densification was conditioned by abnormal grain growth and the particle size of the ZnO-rich residue. When two-step sintering was used the grain growth was reduced comparatively to conventional sintering method. The highest relative sintered density (about 90%) was achieved when samples of ZnO waste and samples of ZnO waste with 2 wt% added Al₂O₃ were processed by two-step sintering and corresponded to a mean grain size of around 18 µm and 7 µm, respectively. XRD and SEM results indicated that alumina addition helped to inhibit grain growth due to the formation of gahnite spinel (ZnAl₂O₄) precipitates in the grain boundaries of zincite (ZnO) grains.     

Induced electromagnetic pressure during microwave sintering of ZnO in magnetic field

This paper presents a unique technological approach for producing a tailored and controlled microstructure in pure zinc oxide using two different sintering methods. A microstructural comparative study between conventional and 2.45 GHz microwave sintered pure ZnO ceramics has been established. Data on the sintering behavior and grain growth as a function of the nature of the heating cycle are collected. The use of two step sintering cycles showed that high density can be achieved with almost complete suppression of grain growth. Compared to conventional sintering, microwave heated samples revealed a denser structure, as two step heated samples presented highest final densities for shorter sintering times. As a semiconductor, the material showed greater heating behavior in H-field which is traduced by higher energy absorption (higher ramp) at the beginning of the heating cycle. H-field sintered pellets showed higher densities and grain size uniformity than the ones sintered in E-field for identical heating cycles. This is likely due to an electromagnetic pressure induced by the combined effect of current loops submitted to a MW–H field.     

Hot pressing of nanocrystalline zinc oxide compacts: Densification and grain growth during sintering

Sintering behavior of nanocrystalline zinc oxide (ZnO) powder compacts using hot pressing method was investigated. The sintering conditions (temperature and total time) and results (density and grain size) of two-step sintering (TSS), conventional sintering (CS) and hot pressing (HP) methods were compared. The HP technique versus CS was shown to be a superior method to obtain higher final density (99%), lower sintering temperature, shorter total sintering time and rather fine grain size. The maximum density achieved via HP, TSS and CS methods were 99%, 98.3% and 97%, respectively. The final grain size of samples obtained by HP was greater than that of TSS method. However, the ultra-prolonged sintering total time and the lower final density (88 ks and 98.3%) are the drawbacks of TSS in comparison with the faster HP (17 ks and 99%) method.     

Two-Step Sintering of Nanocrystalline ZnO Compacts: Effect of Temperature on Densification and Grain Growth

Two-step sintering (TSS) was applied on nanocrystalline zinc oxide (ZnO) to control the accelerated grain growth occurring during the final stage of sintering. The grain size of a high-density (>98%) ZnO compact produced by the TSS was smaller than 1 μm, while the grain size of those formed by the conventional sintering method was ∼4 μm. The results showed that the temperature of both sintering steps plays a significant role in densification and grain growth of the nanocrystalline ZnO compacts. Several TSS regimes were analyzed. Based on the results obtained, the optimum regime consisted of heating at 800°C (step 1) and 750°C (step 2), resulting in the formation of a structure containing submicrometer grains (0.68 μm). Heating at 850°C (step 1) and then at 750°C (step 2) resulted in densification and grain growth similar to the conventional sintering process. Lower temperatures, e.g., 800°C (step 1) and 700°C (step 2), resulted in exhaustion of the densification at a relative density of 86%, above which the grains continued to grow. Thermogravimetric analysis results were used to propose a mechanism for sintering of the samples with transmission electron micrographs showing the junctions that pin the boundaries of growing grains and the triple-point drags that result in the grain-boundary curvature.     

A Novel Approach to Sintering Nanocrystalline Barium Titanate Ceramics

A novel approach to pressureless sintering based on the combination of rapid-rate sintering, rate-controlled sintering, and two-step sintering under a controlled atmosphere is proposed. This combined sintering method facilitates control of grain and pore morphology. The application of this sintering approach for pure nanocrystalline barium titanate powder enables the suppression of grain growth during the intermediate and final stages of sintering and the production of fully dense ceramics with 108 nm grain size. The grain growth factor is 3.5, which is three and 17 times smaller than rate-controlled and conventional sintering, respectively.     

Mechanical modelling of microwave sintering and experimental validation on an alumina powder

Microwave sintering (MW) allows fast heating (≤30 min) and densification of ceramic materials, like alumina Al₂O₃. In order to predict the final material properties (density, size and grain size) the mechanical SOVS (Skorohold Olevsky Viscous Sintering) model is adapted and validated for conventional sintering of alumina. The model is implemented on ABAQUS with UMAT subroutine. Secondly, the SOVS model is modified for the microwave sintering by adapting the shear viscosity Arrhenius type law. Pre-exponential and exponential coefficients are modified for MW sintering. The calculated relative densities are compared to experimental results from conventional and microwave sintering and the relative difference remains under 3%. The coefficients identified for the MW sintering reveal a decrease in the shear viscosity by around 10 and an increase by up to 50 times in the grain boundaries diffusion coefficient.     

Sintering paths and mechanisms of pure MgAl2O4 conventionally and microwave sintered

In this paper, a comparative study between conventional and microwave sintering of pure spinel MgAl₂O₄ is presented. The goal is to clarify and identify the possible microwave effects on densification and microstructure of the pure spinel. Sintering trajectories obtained for microwave and conventional sintering are similar and converge into a unique trajectory. Therefore, microwave processing does not refine the grain size of pure spinel. The dominant mechanism of initial and intermediate stages of sintering was determined from the shrinkage curves and sintering trajectory. It was shown that densification is mostly controlled by grain boundary diffusion for both processes. Porosity of microwave and conventionally sintered samples was also characterized by mercury porosimetry and BET analysis. The evolution of the open porosity and pore size distribution is the same whatsoever the process used. This work shows that microwave sintering does not differ that much from conventional sintering on pure MgAl₂O₄ material.     

Analysis of Nanocrystalline and Microcrystalline ZnO Sintering Using Master Sintering Curves

Master sintering curves were constructed for dry-pressed compacts composed of either a nanocrystalline or a microcrystalline ZnO powder using constant heating rate dilatometry data and an experimentally determined apparent activation energy for densification of 268±25 and 296±21 kJ/mol, respectively. The calculated activation energies for densification are consistent with one another, and with values reported in the literature for ZnO densification by grain boundary diffusion. Grain boundary diffusion appears to be the single dominant mechanism controlling intermediate-stage densification in both the nanocrystalline and the microcrystalline ZnO during sintering from 65% to 90% of the theoretical density (TD). Based on both the consistency of the calculated activation energy as a function of density and the narrow dispersion of the sintering data about the master sintering curve (MSC) for the nanocrystalline ZnO, there is no evidence of either significantly enhanced surface diffusion or grain growth during sintering relative to the microcrystalline ZnO. The MSC constructed for the nanocrystalline ZnO was used to design time–temperature profiles to successfully achieve four different target sintered densities on the MSC, demonstrating the applicability of the MSC theory to nanocrystalline ceramic sintering. The most significant difference in sintering behavior between the two ZnO powders is the enhanced densification in the nanocrystalline ZnO powder at shorter times and lower temperatures. This difference is attributed to a scaling (i.e., particle size) effect.     

Demonstration of the cold sintering process study for the densification and grain growth of ZnO ceramics

With the cold sintering process (CSP), it was found that adding acetic acid to an aqueous solution dramatically changed both the densities and the grain microstructures of the ZnO ceramics. Bulk densities >90% theoretical were realized below 100°C, and the average conductivity of CSP samples at around 300°C was similar to samples conventionally sintered at 1400°C. Frequently, ZnO is also used as a model ceramic system for fundamental studies for sintering. By the same procedure as the grain growth of the conventional sintering, the kinetic grain growth exponent of the CSP samples was determined as N=3, and the calculated activated energy of grain growth was 43 kJ/mol, which is much lower than that reported using conventional sintering. The evidence for grain growth under the CSP is important as it indicates that there is a genuine sintering process being activated at these low temperatures and it is beyond a pressurized densification process.     

Fretting fatigue wear behavior of Y‐TZP dental ceramics processed by non‐conventional microwave sintering

The fretting wear behavior of self‐mated Y‐TZP dental materials obtained by nonconventional microwave and conventional sintering has been investigated. Two 3Y‐TZP materials, a widely utilized commercial dental ceramic (LAVA) and a lab‐prepared 3Y‐TZP powder based equivalent have been assessed. Relative density and mechanical properties as well as the grain size variations upon sintering have been evaluated. After exposure to selected gross slip regime fretting wear conditions, the wear tracks have been characterized allowing the measurement of the coefficient of friction, track profiles, and pit features. The results indicate that microwave sintering results in a similar fretting wear behavior as observed for conventional‐sintered 3Y‐TZP, as the measured volumetric wear loss is of a comparable order of magnitude. Regarding the influence of the grain size, the analysis revealed that a large grain size (>300 nm) results in an increased wear volume and that a higher resistance to fretting wear is constrained to a mid‐range particle size (100–250 nm). Since the fracture toughness of all investigated ceramic grades was comparable, the influence of the fracture toughness on fretting could not be assessed. Abrasive grooving, delamination, and microcracking have been identified as major wear mechanisms inside the wear tracks for both conventional‐ and microwave‐sintered 3Y‐TZP. In general, microwave sintering can provide 3Y‐TZP dental materials with a comparable fretting wear resistance as that observed for conventional sintering using lower dwell sintering temperatures and a shorter processing time.     

Thermal conductivity and stability of Al-doped ZnO nanostructured ceramics

Pure and Al-doped ZnO powders have been sintered by Spark Plasma Sintering. Al doping allows the ceramics to reach a relative density greater than 90% at a sintering temperature of 500?°C. The morphology of powder nanoparticles impacts the final grain size of the sintered bulk compounds. A ceramic sintered from isotropic nanoparticles of 30?nm in diameter can reach an average grain size of 110?nm, whereas a ceramic sintered from platelets and isotropic nanoparticles exhibits an average grain size in the submicrometric range. The influence of ceramic grain size on the thermal conductivity has been investigated. It shows that substantial decrease of the grain size from several microns down to 100?nm reduces the thermal conductivity from 29.5 to 7.8?W/m?K at 100?°C. The stability of nanostructured ceramic has also been checked. After SPS, an annealing at 500?°C in air also leads to grain growth.     

Microstructural evolution of a commercial ultrafine alumina powder densified by different methods

The densification and grain growth of bodies made from a commercial ultrafine alumina powder was investigated. The primary powder was initially subjected to dry (uniaxial cold pressing) and wet shaping (slip casting), followed by conventional (CS)-, two step (TSS)-, and microwave (MS) sintering to explore the effect of each series of treatments on the densification and microstructural evolution of the specimens. It was demonstrated that a uniform microstructure with higher density would be obtained using the wet shaping method. In addition, microwave sintering was found to be more effective into the densification of the specimens and in yielding a finer grain structure. It is believed that the high heating rate and effective particle packing are responsible for the improvements in these properties. On this basis, it was also demonstrated that the fracture toughness of the samples increased significantly through the application of microwave sintering.     

The Effect of Conformation Method and Sintering Technique on the Densification and Grain Growth of Nanocrystalline 8 mol% Yttria-Stabilized Zirconia

Uniaxial dry pressing (DP) and slip casting (SC) were used to form green bodies of nanocrystalline 8 mol% yttria-stabilized zirconia powder processed via the glycine-nitrate combustion method. The SC method was shown to be a more efficient, yielding more homogenous green bodies with higher green density (60% theoretical density) which contained smaller pores with narrower distribution. Improved green properties resulted in lowering the sintering temperature of SC bodies by about 200°C compared with DP compacts. Consequently, the grain growth in sintered bodies formed by SC was relatively abated. By taking the benefits of the wet conformation method, the final grain size of nearly full dense (>97% TD) structures was reduced by 39% (i.e. from 2.15 to 1.3 μm). To reveal the effect of sintering technique, DP bodies were sintered via both microwave and two-step sintering methods. While the grain size of two-step sintered samples was <300 nm, sintering via microwave radiation yielded a nearly full dense structure with a mean grain size of 0.9 μm. The results show that conventionally sintered SC bodies posses higher indentation fracture toughness (FT) (∼3 MPa·m^1/2) compared with DP samples (1.6 MPa·m^1/2). Interestingly, it was shown that, without applying any modified sintering technique, the hardness and FT of SC bodies with coarser structures are completely close to those of samples sintered via microwave heating.     

Influence of processing parameters on the densification and the microstructure of pure zinc oxide ceramics prepared by spark plasma sintering

Due to the sensitivity of nanopowders and the challenges in controlling the grain size and the density during the sintering of ceramics, a systematic study was proposed to evaluate the densification and the microstructure of ZnO ceramics using spark plasma sintering technique. Commercially available ZnO powder was dried and sintered at various parameters (temperature (400–900?°C), pressure (250–850?MPa), atmosphere (Air/Vacuum) etc.). High pressure sintering is desirable for maintaining the nanostructure, though it brings a difficulty in obtaining a fully dense ceramic. Whereas, increasing the temperature from 600 to 900?°C results in fully densified ceramics of about 99% which shows to have big impact on the grain size. However, a high relative density of 92% is obtained at a temperature as low as 400?°C under a pressure of 850?MPa. The application of pressure during the holding time seems to lower the grain size as compared to ceramics pressed during initial stage (room temperature).     

Grain growth in Mn-doped ZnO

Grain growth in ZnO doped with 0.1 to 1.2 mol% Mn was investigated during isothermal sintering from 1100 to 1300°C in air. Mn doping promotes the grain growth of ZnO during sintering, and this effect is enhanced by increasing the Mn doping level. The grain growth exponent is reduced from 3.4, for undoped ZnO, to 2.4, for ZnO doped with 1.2 mol% Mn, while the apparent activation energy for grain growth is reduced from 200 kJ/mol, for undoped ZnO, to 100–150 kJ/mol, for Mn-doped ZnO. Electrical measurements suggest that an excess of Mn probably exists at grain boundaries, either as a very thin second phase or as an amorphous film, which could benefit grain boundary diffusion, therefore promoting the grain growth of ZnO.     

Evidence for the Microwave Effect During Hybrid Sintering

A microwave/conventional hybrid furnace has been used to sinter three ceramics with different microwave absorption characteristics under pure conventional and a range of microwave/conventional hybrid heating regimes. The precursor powder particle size was also varied for each material. In each case it was ensured that every sample within a series had an identical thermal history in terms of its temperature/time profile. An increase in both the onset of densification and the final density achieved was observed with an increasing fraction of microwave energy used during sintering, the effect being greatest for the materials that absorbed microwaves most readily. Twenty-three percent greater densification was observed for submicron zinc oxide powder, the material with the largest microwave absorption capability, when sintered using hybrid heating involving 1 kW of microwave power compared with pure conventional power under otherwise identical conditions. For the ceramic with the lowest microwave absorption characteristic, alumina, the increase in densification was extremely small; partially stabilized zirconia, a moderate microwave absorber, was intermediate between the two. Temperature gradients within the samples, a potential cause of the effect, were assessed using two different approaches and found to be too small to explain the results. Hence, it is believed that clear evidence has been found to support the existence of a genuine "microwave effect."     

Kinetics of Initial Sintering with Grain Growth

Kinetic equations for initial sintering were obtained by combining the conventional kinetic equation with an empirical expression for grain growth in the initial stage. The equations describe the isothermal shrinkage of ZnO in O₂ at 80 torr and 800° to 950°C. The equation also successfully analyzed the sintering of powder compacts of Al₂O₃ studied by other workers.     

Comparison between microwave and conventional sintering on the properties and microstructural evolution of tetragonal zirconia

In this research, the comparison between microwave sintering and conventional sintering on the mechanical properties and microstructural evolution of 3?mol% yttria-stabilised zirconia were studied. Green bodies were compacted and sintered at various temperatures ranging from 1200?°C to 1500?°C. The results showed that microwave assisted sintering was beneficial in enhancing the densification and mechanical properties of zirconia, particularly when sintered at 1200?°C. It was revealed that as the sintering temperature was increased to 1400?°C and beyond, the grain size and mechanical properties for both microwave- and conventional-sintered ceramics were comparable thus suggesting that the sintering temperature where densification mechanism was activated, grain size was strongly influenced by the sintering temperature and not the sintering mode.     

High field ZnO varistors prepared by spark plasma sintering

Abstract

ZnO varistors with submicrometre and nanoscaled microstructures and enhanced electrical properties were prepared by spark plasma sintering (SPS). The densification, grain size and switch field of the varistors were compared with those of hot pressed material. The switching field increased with decreasing grain size, and very rapidly below 500 nm. Switching fields up to 180 kV cm^?1 were obtained for ceramics with submicrometre grain sizes (380 nm). This is nearly two orders of magnitude higher than those currently reported for commercial ZnO varistors. A nano powder, prepared by high energy milling, was sintered to a high density at much lower temperatures compared with the submicron powders and had a nanoscale grain size (45 nm). The nanoceramic broke down dielectrically under very high fields (>260 kV cm^?1) before a varistive response was apparent.