The influence of MgO,Y2O3 and ZrO2 additions on densification and grain growth of submicrometre alumina sintered by SPS and HIP

Spark plasma sintering followed by hot isostatic pressing was applied for preparation of polycrystalline alumina with submicron grain size. The effect of additives known to influence both densification and grain growth of alumina, such as MgO, ZrO₂ and Y₂O₃ on microstructure development was studied. In the reference undoped alumina the SPS resulted in some microstructure refinement in comparison to conventionally sintered materials. Relative density >99% was achieved at temperatures >1200 °C, but high temperatures led to rapid grain growth. Addition of 500 ppm of MgO, ZrO₂ and Y₂O₃ led, under the same sintering conditions, to microstructure refinement, but inhibited densification. Doped materials with mean grain size <400 nm were prepared, but the relative density did not exceed 97.9%. Subsequent hot isostatic pressing (HIP) at 1200 and 1250 °C led to quick attainment of full density followed by rapid grain growth. The temperature of 1250 °C was required for complete densification of Y₂O₃ and ZrO₂-doped polycrystalline alumina by HIP (relative density >99.8%), and resulted in fully dense opaque materials with mean grain size<500 nm.     

The influence of additives on microstrucutre of sub-micron alumina ceramics prepared by two-stage sintering

For various systems two-stage sintering has been reported as a successful way of suppressing the grain growth in the final stage of densification of polycrystalline ceramics. Our previous results on two-stage sintering of high purity submicrometre polycrystalline alumina indicate limited efficiency of the process with respect to suppression of grain growth. The present work deals with the influence of deliberate additions of various metal oxides (500 ppm of MgO, Y₂O₃ or ZrO₂) whose grain growth retarding effect in conventional sintering has been well documented, on two-stage sintering of submicrometre alumina ceramics. The addition of MgO was observed to enhance densification. Addition of yttria and zirconia impaired densification, but addition of all three dopants resulted in suppression of the grain growth and microstructure refinement in comparison to undoped alumina.     

Two-stage master sintering curve applied to two-step sintering of oxide ceramics

Tetragonal (3 mol% Y₂O₃) and two cubic zirconia (8 mol% Y₂O₃) as well as alumina green bodies were used for the construction of the Master Sintering Curve (MSC) created from sets of constant-rate-of-heating (CRH) sintering experiments. The activation energies calculated according to the MSC theory were 770 kJ/mol for Al₂O₃, 1270 kJ/mol for t-ZrO₂, 620 kJ/mol and 750 kJ/mol for c-ZrO₂. These values were verified by an alternative approach based on an analysis of the densification rate in the intermediate sintering stage. The MSCs established from the Two-Step Sintering (TSS) experiments showed at high densities a significant deflection from those constructed from the CRH experiments. This deflection was explained by lower sintering activation energy in the closed porosity stage. A new two-stage MSC model was developed to reflect the change in sintering activation energy and to describe TSS. The efficiency of TSS of four materials under investigation was correlated with their activation energies during the final sintering stage.     

The effect of carbon nanotubes on the sintering behaviour of zirconia

The sintering behaviour and activation energy of Y₂O₃ partially stabilised ZrO₂ and ZrO₂–CNT (0.5 and 2 vol%) composites was determined using spark plasma sintering (SPS) under isothermal conditions. The sintering activation energy for the Y₂O₃ partially stabilised ZrO₂ was found to be 456 kJ/mol. The addition of 2 vol% CNTs reduced the sintering activation energy to 172 kJ/mol. The significant reduction of the activation energy with the addition of only 2 vol% CNTs is attributed to the formation of a percolating network of CNTs providing a lower energy diffusion pathway. The sintering mechanism was found to be grain boundary diffusion for all samples suggesting that the presence of CNTs does not change the sintering mechanism but does lower the activation energy for the rate limiting step in the sintering process.     

Constrained sintering of 8 mol% Y2O3 stabilised zirconia films

Constrained sintering kinetics of 8 mol% Y₂O₃/92 mol% ZrO₂ (8YSZ) films approximately 10–15 μm thick screen-printed on dense YSZ substrates, and the resulting stress induced in the films, were measured in the temperature range 1100–1350 °C. The results are compared with those reported earlier for 3YSZ films.Both materials behave similarly, although there are differences in detail. The constrained densification rate was greatly retarded compared with the unconstrained densification rate due to the effect of the constraint on the developing anisotropic microstructure (3YSZ) and, in the case of 8YSZ, considerable grain growth. The stress generated during constrained sintering was typically a few MPa. The apparent activation energies for free sintering, constrained sintering, creep and grain growth are found to cover a wide range (135–670 kJ mol^?1) despite all probably being mainly controlled by grain boundary cation diffusion.     

Fabrication of reaction-bonded Cr2O3 ceramics

Reaction-bonding to form Cr₂O₃ can be achieved by gaseous oxidation of a Cr phase. The reaction-bonding process is best conducted by complete oxidation before sintering. Below ≈800 °C, the activation energy for oxidation is 220 kJ mol⁻¹, indicating the predominance of Cr³⁺ outward diffusion along high diffusivity paths, e.g., grain boundaries and dislocations. At higher temperatures, the activation energy is reduced to 52 kJ mol⁻¹ as a result of oxygen transport along lower-energy paths, e.g., along microcracks, and the internal and external surfaces. In spite of the decrease in activation energy, the access of oxygen to the inside of the powder compact is hindered by the progressive densification of the oxidizing powder compacts. Maximum densification is achieved for fully oxidized Cr/Cr₂O₃ compacts when the oxygen partial pressure is close to that of the Cr-Cr₂O₃ equilibrium. 0.1 wt% MgO addition increases the density and reduces the grain size of the reaction-bonded Cr₂O₃ samples due to the possible formation of the spinel phase MgCr₂O₄. ZrO₂ and MgO additions improve the fracture strength and toughness of conventionally sintered Cr₂O₃ and change its fracture mode from intergranular to intragranular. For reaction-bonded Cr₂O₃ samples with or without MgO addition, their fracture strength and toughness data are roughly the same as those of sintered Cr₂O₃ doped with ZrO₂ and MgO and their fracture surfaces are predominantly intragranular.     

Development of ZrO2–WC composites by pulsed electric current sintering

ZrO₂–WC ceramic composites with 40 vol% WC were consolidated by pulsed electric current sintering (PECS) for 4 min at 1450 °C under a pressure of 60 MPa. The effect of ZrO₂ stabilizers and the source of WC powder on the densification, phase constitution, microstructure and mechanical properties of the ZrO₂–WC composites were investigated and analyzed. The experimental results revealed that the amount and type of ZrO₂ stabilizers played a primary role on the phase constitution and mechanical properties of the composites in comparison to the morphology and size of the WC powder. The 2 mol% Y₂O₃-stabilized composites exhibited much better mechanical properties than that of 1.75 mol% Y₂O₃-stabilized or 1 mol% Y₂O₃ + 6 or 8 mol% CeO₂ co-stabilized composites. A Vickers hardness of 16.2 GPa, fracture toughness of 6.9 MPa m^1/2, and flexural strength of 1982 MPa were obtained for the composites PECS from a mixture of nanometer sized WC and 2 mol% Y₂O₃-stabilized ZrO₂ powder.     

Reaction sintering of AlN–AlON composites

Sintering behavior of three different compositions in the AlN–Al₂O₃ system using Y₂O₃ as a sintering aid was investigated. Samples with various ratios of AlN/Al₂O₃ were sintered in nitrogen atmosphere using a gas pressure furnace in the temperature range 1750–1950 °C. The densification of the samples was studied by shrinkage and relative density measurements. Results showed that samples containing 1 and 70 wt.% alumina were sintered to near theoretical density at 1800 °C; whereas the sample with 20 wt.% alumina never reached densities higher than 93% in the temperature range considered. It was found that the AlN/Al₂O₃ ratio and the sintering temperature had a great influence on the microstructure and crystalline phases present in the samples, namely, AlN, γ-AlON, 27R, and YAG. In the sample with 20 wt.% alumina, porosity formation prevented further densification. These porosities were probably due to the release of oxygen during sintering.     

Effects of ZrO2-La2O3 co-addition on the microstructural and optical properties of transparent Y2O3 ceramics

Commercial Y₂O₃ powder was used to fabricate Y₂O₃ ceramics sintered at 1600 °C and 1800 °C with concurrent addition of ZrO₂ and La₂O₃ as sintering aids. One group with different contents of La₂O₃ (0–10 mol%) with a fixed amount of 1 mol% ZrO₂ and another group with various contents of ZrO₂ (0–7 mol%) with a fixed amount of 10 mol% La₂O₃ were compared to investigate the effects of co-doping on the microstructural and optical properties of Y₂O₃ ceramics. At low sintering temperature of 1600 °C, the sample single doped with 10 mol% La₂O₃ exhibits much denser microstructure with a few small intragranular pores while the samples with ZrO₂ and La₂O₃ co-doping features a lot of large intergranular pores leading to lower density. When the sintering temperature increases to 1800 °C, samples using composite sintering aids exhibit finer microstructures and better optical properties than those of both ZrO₂ and La₂O₃ single-doped samples. It was proved that the grain growth suppression caused by ZrO₂ overwhelms the acceleration by La₂O₃. Meanwhile, 1 mol% ZrO₂ acts as a very important inflection point with regard to the influence of additive concentration on the transmittance, pore structure and grain size. The highest in-line transmittance of Y₂O₃ ceramic (1.2 mm in thickness) with 3 mol% of ZrO₂ and 10 mol% of La₂O₃ sintered at 1800 °C for 16 h is 81.9% at a wavelength of 1100 nm, with an average grain size of 11.2 µm.     

ZrO2-doped Y2O3 transparent ceramics via slip casting and vacuum sintering

Commercial Y₂O₃ powder was used to fabricate highly transparent Y₂O₃ ceramics with the addition of ZrO₂ via slip casting and vacuum sintering. The effects of ZrO₂ addition on the transparency, grain size and lattice parameter of Y₂O₃ ceramics were studied. With addition of ZrO₂ the transparency of Y₂O₃ ceramics increased markedly and the grain size of Y₂O₃ ceramics decreased markedly by cation diffusivity mechanism and the lattice parameter of Y₂O₃ ceramics slightly decreased. The highest transmittance (at wavelength 1100 nm) of the 5.0 mol% ZrO₂–Y₂O₃ ceramic (1.0 mm thick) sintered at 1860 °C for 8 h reached 81.7%, very close to the theoretical value of Y₂O₃.     

Sintering of Cr2O3 in H2/H2O Gas Mixtures

Sintering of Cr₂O₃ was performed at 1530°C under low pO₂ close to the Cr–Cr₂O₃ equilibrium generated by H₂/H₂O gas mixtures. Addition of 1 wt%ZrO₂ and 0·1 wt%MgO increases the density of Cr₂O₃ from 97% TD to nearly full density. Rapid densification and the higher density are attributed to the appearance of a transient CrO liquid phase as a result of the presence of ZrO₂ and MgO under the sintering conditions. A grain size reduction is also achieved owing to the presence of ZrO₂ particles and the possible formation of a MgCr₂O₄ spinel at grain boundaries. There is no connection between densification and loss of material due to evaporation. ©     

Sintering mechanisms of Yttria with different additives

The sintering behaviour of conventional yttria powder was investigated, with emphasis on the effect of sintering additives such as B₂O₃, YF₃, Al₂O₃, ZrO₂, and TiO₂, etc. at sintering temperatures from 1000 °C to 1600 °C. Powder shrinkage behaviour was analysed using a dilatometer. The powder sintering mechanisms were identified at different temperatures using powder isothermal shrinkage curves. This analysis showed that the sintering additives B₂O₃ and YF₃ could improve yttria sintering by changing the diffusion/sintering mechanisms at certain temperatures, while sintering additives TiO₂, Al₂O₃ and ZrO₂ appeared to retard the powder densification at temperatures around 1000 °C and are more suitable when used at temperatures in excess of 1300 °C. The powder with La₂O₃ added had the slowest densification rate throughout the test temperatures in this experiment and was also found to be more suitable when used at temperatures higher than 1550 °C.     

Phase,microstructure and sintering of aluminum nitride powder by the carbothermal reduction-nitridation process with Y2O3 addition

Aluminum nitride powders were synthesized by carbothermal reduction-nitridation method using Al(OH)₃, carbon black and Y₂O₃ as raw materials. The change of phase, microstructure and densification during the AlN synthesis and sintering process were investigated and the effects of Y₂O₃ was discussed. The results showed that Y₂O₃ reacted with Al₂O₃ to form yttrium aluminates of YAlO₃ (orthorhombic and hexagonal phases), Y₄Al₂O₉ and Y₃Al₅O₁₂ at the low temperature of 1350 °C. YAlO₃ could firstly be transformed into Y₂O₃ and then completely into YN when the firing temperature and holding time increased. However, YN could be oxidized into Y₂O₃ again after the carbon removal at 700 °C in the air atmosphere. There were two ways generating AlN when adding Y₂O₃ and the possible mechanism was proposed. Y₂O₃ from YN oxidation favored the densification of AlN ceramics because the liquid had better flowability and distribution in the sintering process at 1800 °C.     

Densification behaviour and microstructural development in undoped yttria prepared by flash-sintering

Conventional sintering of undoped Y₂O₃ requires temperatures above 1400 °C for a few hours. We show that it can be sintered nearly instantaneously to nearly full density at furnace temperature of 1133 °C under a DC applied field of 500 V/cm. At 1000 V/cm sintering occurs at 985 °C. The FLASH event, when sintering occurs abruptly, is preceded by gradually accelerated field-assisted sintering (FAST). This hybrid behaviour differs from earlier work on yttria-stabilized zirconia where all shrinkage occurred in the flash mode. The microstructure of flash-sintered specimens indicated that densification was accompanied by rapid grain growth. The single-phase nature of flash-sintered Y₂O₃ was confirmed by high-resolution transmission electron microscopy. The non-linear rise in conductivity accompanying the flash led to Joule heating. It is postulated that densification and grain growth were enhanced by accelerated solid-state diffusion, resulting from both Joule heating and the generation of defects under the applied field.     

Reaction and phases from monoclinic zirconia and calcium aluminate cement at high temperatures

Solid state reaction using m-ZrO₂ and high alumina cement as starting materials was studied. Various compositions containing different proportions of calcium aluminate cement (5–50 mol% CaO in ZrO₂) were reaction sintered at 1300–1500 °C. Crystalline phase formation and densification of Ca stabilized ZrO₂ composites was investigated by X-ray diffraction analysis, density and shrinkage measurements. Scanning electron microscopy (SEM) combined with energy dispersive X-ray spectroscopy was used to examine the microstructure. The main crystalline phases formed are related to the expected with the equilibrium phase diagram of the ZrO₂–CaO–Al₂O₃ system. Stabilized c-ZrO₂ is formed with the composition of Ca_0.15Zr_0.85O_1.85. The sintering of the mixtures leads to porous composites materials. Textural properties were analyzed considering the initial composition and the present crystalline phases.     

Microstructure and mechanical properties of silicon carbide pressureless sintered with oxide additives

It is known that SiC powders can be densified at relatively low temperatures (1850–2000 °C) with some oxide additions. In this work the densification behavior, microstructure and mechanical properties (bending strength, fracture toughness, hardness) of SiC ceramics pressureless sintered with different additions chosen from oxide groups: Al₂O₃ + Y₂O₃, Al₂O₃ + Y₂O₃ + MgO, were investigated. It was found that oxide additives facilitate densification of sinters and significantly improve mechanical properties of SiC ceramics. The best activating oxide additions have been identified.     

Master sintering curves of a nanoscale 3Y-TZP powder compacts

The sintering behavior of commercially available granulated ZrO₂–3 mol% Y₂O₃ (3Y-TZP) powder compacts with an aggregate size of 75 nm was studied. The shrinkage response of the powder compacts during non-isothermal sintering was measured in a sensitive dilatometer at different heating rates. Densification and grain growth were also studied after isothermal firing in air according to different sintering cycles. The sintering and grain growth activation energy was estimated to be Q_S = 485 ± 12 kJ mol^?1 and Q_G = 546 ± 23 kJ mol^?1, respectively. Using the estimated Q-values, the master curves for sintering and grain growth were established and used for prediction of the densification and microstructural development under different thermal histories. A good agreement between the model predictions and experimental result was obtained.     

Fabrication and properties of Y2O3 transparent ceramic by sintering aid combinations

Transparent Y₂O₃ ceramics were fabricated by the solid-state reaction and vacuum sintering method using La₂O₃, ZrO₂ and Al₂O₃ as sintering aids. The microstructure of the Y₂O₃ ceramics sintered from 1550 °C to 1800 °C for 8 h were analyzed by SEM. The sintering process of the Y₂O₃ transparent ceramics was optimized. The results showed that when the samples were sintered at 1800 °C for 8 h under vacuum, the average grain sizes of the ceramics were about 3.5 µm. Furthermore, the transmittance of Y₂O₃ ceramic sintered at 1800 °C for 8 h was 82.1% at the wavelength around the 1100 nm (1 mm thickness), which was close to its theoretical value. Moreover, the refractive index of the Y₂O₃ transparent ceramic in the temperature range from 30 °C to 400 °C were measured by the spectroscopic ellipsometry method.     

Microwave versus conventional sintering: Estimate of the apparent activation energy for densification of α-alumina and zinc oxide

A comparative study between the conventional and 2.45 GHz microwave multimode sintering behavior of insulator (α-Al₂O₃) and semi-conductive ceramic (ZnO) was systematically investigated. The apparent activation energy of nonisothermal sintering was determined by way of the Arrhenius plot of densification data at constant heating rates (CHR) and the concepts of Master Sintering Curves (MSCs), respectively. During microwave densification process, the apparent activation energy was about 90 kJ/mol less than the value for conventional sintering of Al₂O₃ applying these two estimation methods. However, an opposite result was obtained in the case of ZnO, although its densification process had been also accelerated by microwave as well as Al₂O₃. The significant differences in activation energy give a good proof of the difference in diffusion mechanism induced by the electromagnetic field underlying microwave sintering.     

Effect of spherical porosity on co-fired dense/porous zirconia bi-layers cambering

Geometrical instability leading to cambering is recorded during co-sintering of zirconia dense/porous bi-layered planar structures. Sintering strain in the bi-layers rises mainly from mismatch between the different porosity volume fractions at the layers and their interface. In this paper, we analyze the model case of dense taped of 8 mol% Y₂O₃-stabilized ZrO₂ laminated on ca. 400 μ thick 3 mol% Y₂O₃ doped zirconia porous tapes, with homogenous spherical porosity of 13 vol%, 46 vol%, and 54 vol%. Sintering stress during densification is evaluated from the shrinkage rates and viscoelastic behavior during sintering by thermo-mechanical analysis, using cyclic loading dilatometry. The camber development of the bi-layers is measured by in-situ optical dilatometry. In accordance with the model prediction, cambering can be controlled tuning the porosity while achieving a synergetic effect between densification and formation of open porosity at the bilayers.