Cracking and shape deformation of cylindrical cavities during constrained sintering

During constrained sintering of thin films, in which a cylindrical cavity with axis perpendicular to the substrate has been introduced before sintering, cracks emerge that initiate at the cavity surface. By combining experiments with continuum mechanical and particle based simulations, the fundamental causes and effects of this kind of crack formation are identified. A stress analysis performed by finite element (FEM) simulations matches with the cracking behavior observed in experiments. A comparison of discrete element (DEM) results with experiments shows the applicability of this simulation method to describe the effect of cross-sectional stripe dimensions and cavity diameters on the cracking behavior. Moreover, DEM simulations reveal that hair-line cracks in narrow stripe samples formed during pre-sintering manufacturing steps might be a dominant cause for the observed crack damage in such systems.     

Effect of diopside addition on sintering and mechanical properties of alumina

In this paper, diopside was introduced in alumina as a sintering aid and fine structural alumina matrix ceramic materials were fabricated by pressureless sintering. The relative density, hardness, fracture toughness and bending strength of the new fabricated composites were measured. Tribological tests were carried out at a given rotation speed of 160 rpm and in a normal load ranged from 50 to 200 N. The experiment results show that the introduction of diopside can enhance densification rate, which may contribute to the improvement in mechanical properties and result in enhanced wear resistances. The effects of diopside on mechanical properties and microstructures of fine structural alumina matrix ceramic materials were analyzed and discussed.     

Flash sintering of alumina/reduced graphene oxide composites

The flash sintering behavior of Al₂O₃/reduced graphene oxide (rGO) composites was investigated. rGO was used as a composite component and a conductive additive. Under the electric fields of 250–400 V cm⁻¹, the flash event occurred at extremely low temperatures of 236–249 °C. The current density limit played a significant role in the degree of densification. A larger current density resulted in a higher density of the sample. However, current densities larger than 33.33 A cm⁻² resulted in broken samples because of the localization of high current density coupled with the formation of hot spots. Flash sintering at a furnace temperature of 800 °C, electric field of 300 V cm⁻¹ and current density limit of 33.33 A cm⁻² produced nearly completely dense Al₂O₃/rGO composites. In addition to the current limit, the furnace temperature is also a key parameter that controls the degree of densification to achieve “safe” flash sintering.     

Effect of temperature and holding time on the densification of alumina obtained by two-step sintering

The two-step sintering technique is a process of controlling the sintering curve, which provides materials with higher density and smaller grain size when compared to conventional sintering. This technique was evaluated by optical dilatometry with three commercial alumina powders of different purity (92, 96 and 99 wt% of Al₂O₃) and particle size (between 0.73 and 2.16 µm). Different sintering conditions in the first (temperature, T1) and second (temperature, T2, and holding time, t2) steps were studied in order to evaluate the effect of these variables on densification and grain growth. Considering T1 as the temperature at which a relative density (D_rel) of 83% was achieved, and for the range of conditions tested, it was found that higher D_rel values and lower grain size of alumina were obtained with higher T2 and lower t2. Alumina with 99 wt% purity sintered at T1 of 1550 °C for 5 min and T2 of 1500 °C for 4 h showed the best relationship between higher densification (~96% relative density) and reduced grain size (0.94±0.15 µm). Thus, this work demonstrated that suppression of grain growth can also be obtained for commercial alumina.     

Coupling additive manufacturing and microwave sintering: A fast processing route of alumina ceramics

In this paper, a quick and efficient route to produce complex-shape alumina is reported. Alumina pieces are shaped by additive manufacturing (stereolithography) and densified by microwave sintering. Two raw powders are investigated in terms of both printing and microwave sintering: one alumina grade appropriate for additive manufacturing but not for microwave sintering, and vice-versa for the other grade. The mixture of the two raw powders allows both stereolithography printing and microwave sintering. Alumina parts processed by additive manufacturing followed by microwave sintering were successfully prepared and exhibited relative densities of about 93%, elastic modulus up to 236 GPa and Vickers hardness up to 12 GPa. Notwithstanding the part properties, the as-proposed coupling resulted in a time saving of 30%.     

Effect of dual liquid phase sintering aids on the densification and microstructure of low temperature sintered alumina ceramics

Alumina ceramics was prepared by pressureless sintering technology in which a CuO–TiO₂–Bi₂O₃ mixture (0–4.0 wt% Bi₂O₃ and 4.0 wt% CuO and TiO₂) was added as dual liquid phase sintering aids. The phase compositions, microstructural feature, and sintering behaviour of the alumina ceramics were analyzed. The results showed that adding 2.5 wt% Bi₂O₃ to alumina ceramics can increase the contribution rate of initial stage of sintering to the sintering process. The relative density of the sample reached 97.63% after sintering at 1200 °C for 90 min. Measurements from differential scanning calorimetry, with the addition of CuO–TiO₂–Bi₂O_3, demonstrated the formation of two liquid phase points, 827.4 and 936.8 °C. Notably, the solid solution temperature of TiO₂ and Al₂O₃ ceramics diminished thanks to the dual liquid phase sintering aids, and at the same time the activation energy required also dropped from 368.96 to 137.31 kJ/mol. Research indicates that the combined action of dual liquid phase sintering and solid-state reaction sintering has promoted the densification of alumina ceramics during the sintering process while at the same time inhibiting the growth of abnormal grains so that a homogeneous microstructure can be formed.     

Fabrication of ultrafine-grained alumina ceramics by two different fast sintering methods

The preparation of ultrafine-grained alumina ceramics by the fast sintering technique Self-propagating High-temperature Synthesis plus Quick Pressing (SHS-QP) method and spark plasma sintering (SPS) technique was reported. The effects of different heating rates (SHS-QP-1600 °C/min, SPS-200 °C/min) on the preparation of ultrafine structure were compared. The densification and grain growth as a function of sintering time and temperature were discussed. Within a short sintering time (<3 min), the full-dense alumina with ultrafine-grained structure was obtained by SHS-QP at 1550 °C under 100 MPa. By SPS, the sintering temperature was lower (1200 °C) than that of SHS-QP. The differences in densification parameters were explained by analyzing the thermodynamics of sintering process.     

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.     

Effect of carbon contamination on the sintering of alumina ceramics

The present work aimed with the carbon contamination in alumina ceramics and its influence on sinterability of alumina in low vacuum and atmospheres of argon and nitrogen. The commercially available alumina was coated with carbon and sintered at different atmospheres to investigate the effect of carbon presence on alumina sintering behaviour. The sintering conditions were: heating/cooling rates 5 °C/min and 1.7 °C/min until the maximum temperature of 1400 °C and a dwell time of 2 h. The microstructure of the samples was investigated from fracture and surface, prior to polishing, chemical or thermal etching. The non-densified (porous) surface layer was found in the samples sintered in nitrogen and vacuum, however, sintering in argon atmosphere showed a negligible effect on the surface. The core of investigated specimens exposes a transgranular/intergranular fracture mode and is dense in all cases. In the case of vacuum sintering, the strong carbon diffusivity was also noticeable by the dark grey color of the samples. Interestingly, the formation of aluminium nitride took place during sintering of carbon coated alumina samples in a nitrogen atmosphere at 1400 °C. The thickness of the reactive porous layer was approximately 15 μm beneath the surface. Such a porous layer is inappropriate to the desired features of final ceramic products. Presented results lead to better understanding of the sintering behaviour of ceramic and to suitable selecting of the set-up by densification conditions.     

Preparation and indirect selective laser sintering of alumina/PA microspheres

Indirect selective laser sintering (SLS) is a promising additive manufacturing technique to produce ceramic parts with complex shapes in a two-step process. In the first step, the polymer phase in a deposited polymer/alumina composite microsphere layer is locally molten by a scanning laser beam, resulting in local ceramic particle bonding. In the second step, the binder is removed from the green parts by slowly heating and subsequently furnace sintered to increase the density. In this work, polyamide 12 and submicrometer sized alumina were used. Homogeneous spherical composite powders in the form of microspheres were prepared by a novel phase inversion technique. The composite powder showed good flowability and formability. Differential scanning calorimetry (DSC) was used to determine the thermal properties and laser processing window of the composite powder. The effect of the laser beam scanning parameters such as laser power, scan speed and scan spacing on the fabrication of green parts was assessed. Green parts were subsequently debinded and furnace sintered to produce crack-free alumina components. The sintered density of the parts however was limited to only 50% of the theoretical density since the intersphere space formed during microsphere deposition and SLS remained after sintering.     

Optical and mechanical properties of transparent alumina fabricated by high-pressure spark plasma sintering

Transparent alumina was fabricated from untreated commercial powder by high-pressure spark plasma sintering (HPSPS) at temperatures of 1000, 1050 and 1100 °C under pressures of 250-800 MPa. It was established that transparency strongly depends on the HPSPS parameters. At all temperatures, there was a certain point when increasing the pressure led to decreasing transparency. At 1100 °C, relatively high pressure led to excessive grain growth, as well as the formation of creep-induced porosity at the center of the samples. Hardness values decreased with pressure due to grain growth, correlated with the Hall-Petch relationship. The optimal combination of optical and mechanical properties (68% in-line transmittance at a wavelength of 640 nm and a hardness value of about 2300 HV2) was achieved after sintering at 1050 °C under 600 MPa.     

Dilatometric study of anisotropic sintering of alumina/zirconia laminates with controlled fracture behaviour

Al₂O₃ and ZrO₂ monoliths as well as layered Al₂O₃/ZrO₂ composites with a varying layer thickness ratio were prepared by electrophoretic deposition. The sintering shrinkage of these materials in the transversal (perpendicular to the layers, i.e. in the direction of deposition) as well as in the longitudinal (parallel with layers interfaces) direction were monitored using high-temperature dilatometry. The sintering of layered composites exhibited anisotropic behaviour. The detailed study revealed that sintering shrinkage in the longitudinal direction was governed by alumina (material with a higher sintering temperature), whilst in the transversal direction it was accelerated by the directional sintering of zirconia layers. For interpretation of such anisotropic sintering kinetics, the Master Shrinkage Curve model was developed and applied. Crack propagation through laminates with a different alumina/zirconia thickness ratio was described with the help of scanning electron microscopy and confocal laser microscopy.     

复合烧结剂对高铝质干式料烧结性能的影响

以粒度3～5mm,1～3mm,≤1mm,≤0.088mm的高铝矾土为主要原料,以粒度≤0.1mm的硼酸(H3BO3>99.6%)、粒度≤0.05mm的粘土、粒度≤0.1mm的钾长石和粒度≤0.1μm的硅灰(SiO2>90%)为复合烧结剂,按m(骨料)∶m(细粉)=65∶35的配比配料。将混合料在陶瓷模具中手工捣打成型,将成型好的试样分别在600℃、700℃、800℃、900℃和1000℃下均保温2h后脱模。测量热处理后各试样的耐压强度和显气孔率;采用XRD分析了试样的物相组成。结果表明:复合烧结剂中钾长石和硼酸在中温、低温下具有良好的烧结作用,在700～800℃热处理后,试样耐压强度和显气孔率明显增加。硼酸含量为2%的试样,在800～1000℃热处理后,显气孔率增幅较大。添加硅灰可以降低钾长石烧结温度;而复合烧结剂中的粘土在中温、低温下不利于干式料的烧结,低于800℃热处理后的试样,耐压强度和显气孔率没有随粘土含量增加而变化;900～1000℃热处理后的试样,耐压强度随粘土含量的增加而降低,显气孔率增加不大。     

Impact of microwave sintering on dielectric properties of screen printed Ba0.6Sr0.4TiO3 thick films

The influence of 30 GHz microwave sintering compared to conventional sintering has been investigated on polycrystalline Ba_0.6Sr_0.4TiO₃ (BST60) thick films with respect to an application as tunable dielectrics. The BST thick films were prepared as metal–insulator–metal (MIM) capacitors on alumina substrates. The average grain size (440 nm) and the porosity (approx. 30%) of the sintered films are only little affected by the sintering method. However, permittivity, dielectric loss and tunability have been influenced substantially. The dielectric improvement by microwave sintering is interpreted in terms of an increased crystal quality (ξ_S) and/or a decrease of defect concentrations. It is assumed that microwave sintering preferably heats up parts of the film where an increased defect density exists and therefore causes a selective heating process. This may heal up charged defects, inhomogeneities, and structural defects.     

Preparation of mullite from alumina/aluminum nitrate and kaolin clay through spark plasma sintering process

In the present study, the in-situ synthesized mullite has been prepared successfully by mixing kaolinite with alumina and aluminum nitrate nonahydrate (ANN) powders through high energy milling followed by spark plasma sintering (SPS). Using a high-energy ball-mill, the stoichiometric compositions of the starting powders, considering their final transformation to Al₂O₃ and SiO₂, have been mixed. The SPS process has been performed at 1400 and 1375?°C for the specimens containing Al₂O₃ and ANN, respectively. XRD patterns of the milled powders after 30?h showed the formation of quartz from kaolinite for both starting batches. The displacement-temperature-time (DTT) curves and the corresponded vacuum changes indicated the dehydration and phase transformation of ANN and kaolinite at different stages of the sintering process. The XRD patterns of the sintered samples revealed the formation of mullite alongside un-reacted Al₂O₃ and crystobalite for the batches containing Al₂O₃ and ANN, respectively. The results of the physical and mechanical properties tests showed higher amounts of bending strength (397?±?18?MPa), Vickers hardness (16.32?±?0.21?GPa) and fracture toughness (3.81?±?0.24?MPa?m^?1/2) alongside a lower porosity (0.070?±?0.02%) for the prepared sample containing Al₂O₃, than those of the sample containing ANN.     

Influence of the heating rate on grain size of alumina ceramics prepared via spark plasma sintering (SPS)

The dependence of grain size on the heating rate has been investigated for alumina ceramics prepared via spark plasma sintering (SPS). For this purpose, the local grain size has been determined via position-dependent microscopic image analysis, using two independent grain size measures (mean chord length and Jeffries grain size). For alumina ceramics prepared with heating rates between 5 and 100 °C/min (pressure 80 MPa, maximum temperature 1300 °C) it is found that for higher heating rates the grain size is smaller. However, the microstructural non-uniformity is so large that any grain size determination that does not take this non-uniformity into account becomes meaningless, because grain size gradients from the specimen periphery to the center are larger than the differences in grain size due to different heating rates. Temperature and pressure gradients are discussed as the most plausible reasons for the microstructural non-uniformity.     

Constrained sintering and thermal ageing behaviour of electrophoretically deposited Yb2Si2O7 environmental barrier coating

The oxidation of SiC and the formation of a thermally grown oxide layer (TGO) limit the lifetime of environmental barrier coatings. Thus, this paper focuses on the deposition of denser Yb₂Si₂O₇ coatings using electrophoretic deposition to reduce the TGO growth rate. The findings showed densification for Yb₂Si₂O₇ can be achieved with an optimized sintering profile (heating/cooling rate, temperature, and time). However, the addition of 1.5 wt% of Al₂O₃ to Yb₂Si₂O₇ promoted densification and lowered the required sintering temperature, 1380 °C using 2 °C/min heating/cooling rate for 10 h provided efficient coating density. Moreover, adding Al₂O₃ reduced the TGO growth rate by more than 70 % compared to the Al₂O₃-free coatings, without cracking in TGO after 150 h of thermal ageing at 1350 °C. Results within this study suggest electrophoretic deposition with Al₂O₃ addition produces promising Yb₂Si₂O₇ environmental barrier coatings on SiC substrate with low oxidation rates and increased lifetime.     

Effect of manganese addition on sintering behavior and mechanical properties of alumina toughened zirconia

The effect of MnO₂ additives on the sintering behavior and mechanical properties of alumina-toughened zirconia (ATZ, with 10 vol% alumina) composites was investigated by incorporating different amounts of MnO₂ (0, 0.5, 1.0, and 1.5 wt%) and sintering at various temperatures ranging from 1300 to 1450 °C. The addition of MnO₂ up to 1.0 wt% improved the sintered density, hardness, flexural strength, and fracture toughness of the composite. However, the addition of 1.5 wt% MnO₂ degraded the relative density, hardness, and flexural strength of the composite due to the transformation of the ZrO₂ phase from tetragonal to monoclinic and grain coarsening. Optimal results were obtained with 1.0 wt% MnO₂ and sintering at 1450 °C, which improved the mechanical properties (hardness: 13.5 GPa, flexural strength: 1.2 GPa, fracture toughness: 8.5 MPa m^1/2) and lowered the sintering temperature compared to the conventional sintering temperature of ATZ composites (1550 °C). Thus, the ATZ composite doped with MnO₂ is a promising material for structural engineering ceramics owing to its improved mechanical properties and lower sintering temperature.     

Influence of processing atmosphere on the microstructural evolution of submicron alumina powder during sintering

Investigations into the sintering of submicron oxide powders have revealed interesting behavior, particularly insofar as it concerns their microstructural evolution in the early, low temperature transformations during heating. In this work, experiments were conducted on a submicron alumina powder, whose microstructural evolution and densification were characterized after sintering from 900 °C to 1400 °C in air, dry air and high vacuum (10⁻⁸ atm). The results indicated that the processing atmosphere strongly influences the particle size distribution at low temperatures before shrinkage occurs. Shrinkage began concomitantly with grain growth and the sintering atmosphere influenced the sintering kinetics. This factor, which is associated with previous narrowing of the particle size distribution, may affect grain growth and densification during the final stage of sintering.