Sintering Behavior of Fully Agglomerated Zirconia Compacts

Fully agglomerated superfine zirconia powders were prepared with the coprecipitation and spray-drying method. The compaction of such powders shows no fragmentation of the agglomerates. The sintering behavior of the compacts was studied and two sintering stages were identified: densification within agglomerates at temperatures not higher than 1250°C and the removal of interagglomerate pores at temperatures above 1600°C. The interagglomerate pores are difficult to remove, and sintering between agglomerates even at 1600°C is still insignificant. Heating of the compacts at temperatures above 1600°C leads only to grain growth and the entrapping of pores in large grains.     

Microstructural evolution during sintering in MgO powders precipitated from sea water under induced agglomeration conditions

Green compacts pressed by means of uniaxial compaction with Magnesia (MgO) powders precipitated from sea water and calcined at different temperatures were sintered under H₂ atmosphere at 1700 °C. The calcination, carried out between 900 and 1200 °C had a great influence in the final density and the microstructure. The densification of MgO agglomerated powders seems to be predictably related to grain growth and thus coarsening kinetics. At calcination temperatures higher than 900 °C, the volume of large pores was increased notably suggesting that the inhibited grain growth adversely affected the thermodynamics of pore sintering. Relative densities between 74 and 98% of theoretical density were reached in compacts obtained at different compaction pressures. The microstructural differences were examined by Scanning Electron Microscopy (SEM).     

Analysis of agglomerated packings

Results of computer simulation of the packing of particles in compacts from agglomerated powders are presented. The effect of the characteristics of agglomerated powders, such as the number of particles in the agglomerates, the size distribution of agglomerates, and the volume share of the fine fraction (individual particles) on the factors that determine the sinterability of compacts, i.e., the density, the mean number of contacts per particle, and the mean size and the mean coordination number of the pores, is investigated. It is established that compared to compacts from individual particles the presence of agglomerates sharply worsens the packing characteristics. The worst effect is due to agglomerates containing less that 30 – 40 particles. The packing characteristics can be improved by using powders with a wide size distribution of agglomerates or by adding unagglomerated particles. It is interesting that computer models of powder compacts can be used for predicting the strength properties of the materials sintered from these powders. Data on the influence of the packing characteristics on the mean strength and the Weibull modulus are presented.Translated from Ogneupory, No. 4, pp. 14–17, April, 1995.     

Grain growth during the sintering of compacted submicron powders

The kinetics of grain growth in compacts made of submicron titanium powders obtained by controlled hydrolysis of titanium alcoholates was studied. It was established that inhomogeneous packing of the particles in a compact made of agglomerated powder stimulates intense grain growth even in the early stage of sintering. It is shown that a material obtained by sintering homogeneously packed compacts composed of coarse non-agglomerated particles possesses, despite a low density, a homogeneous highly disperse structure and exhibits a much higher strength than a material obtained upon sintering a finely divided but agglomerated powder to maximum density. Translated from Ogneupory i Tekhnicheskaya Keramika, No. 4, pp. 18–22, April, 1997.     

Enhanced Densification of In2O3 Ceramics by Presintering with Low Pressure (5 MPa)

Sintering of In₂O₃ has been carried out in air to full density. Because of the difference in densification between the agglomerates and the matrix, large interagglomerate pores were observed to form at the initial stage of sintering. Such pore formation could be prevented by applying a small external pressure which resulted in the beneficial rearrangement of agglomerates.     

Characterization of the compaction and sintering of hydroxyapatite powders by mercury porosimetry

Mercury porosimetry was used to measure the bulk and real densities, pore volumes and pore size distributions of compacts of hydroxyapatite before and after sintering. The hydroxyapatites were prepared by two different methods and had widely different surface areas. The properties were determined as a function of compaction force and sintering temperature. Densities from porosimetry were in good agreement with geometric densities. A linear relation was found between pore volume and log of the applied force. There was also a linear relationship between bulk volume and pore volume of the compacts. A bimodal pore size distribution was observed for the high surface area hydroxyapatite which disappeared with increasing compaction loads. Pressurization and depressurization measurements indicated that the main body of the pores in the compacts attained a more regular “spherical” shape with increasing compaction force than did the “necks”. The pore volume, percent porosity, and bulk density of the compacts remained unchanged up to 600°C; however, the surface area and the average pore diameter changed at 400°C. The distribution of pores became more uniform, narrower in distribution, and larger in size as the sintering temperature increased. The change in pore area with pore volume indicated that two mechanisms were operating during sintering. The pore area proved to be the most sensitive indicator of changes during sintering.     

Submicrometer Transparent Alumina by Sinter Forging Seeded γ-Al2O3 Powders

Seeding boehmite with α-Al₂O₂, followed by calcination at 600°C, results in an agglomerated alumina powder (<53 μm) that can be sinter forged to full density at 1250°C. Compressive strains as high as ɛ_x=−0.9, and radial flow (ɛ_x= 1.0) during sinter forging remove large, interagglomerate pores. The fully dense alumina has a grain size of 0.4 pm and is visually transparent. It is proposed that deformation of dense agglomerates is the primary mecha- nism responsible for large pore elimination and compact densification. The sinter forging of sol-gel-derived alumina powders offers a new technology to prepare highly transparent, optical ceramics at lower temperatures than conventional routes.     

Cold compaction molding and sintering of polystyrene

It is the objective of this paper to demonstrate the applicability of cold compaction molding followed by a sintering treatment to the processing of polystyrene powders. The influence of pressure, compaction speed, and peak pressure dwell time on the green (as compacted) density and the green tensile strength, as well as the effect of sintering on the tensile strength and dimensional change, were evaluated. The resulting data indicate that room temperature compaction alone is insufficient to provide adequate tensile strength for the compacts. Sintering the green compacts at temperatures of 150 to 173°C markedly improves the tensile strength while simultaneously causing a thickness change in the compacts. This thickness change results from gas evolution, pore shrinkage, and viscoelastic recovery of the residual stresses induced by pressure. For compacts of 0.225 in. thickness, an optimum sintering treatment of 173°C for 30 mins is recommended to provide a tensile strength of 4,000 psi and a thickness change of less than + 7 percent. Coining (repressing) the green compacts does not appreciably affect the sintered strength. However, a finer particle size improves the sintered properties. A review of the literature on the flow behavior of polystyrene suggests that a non-Newtonian viscous flow mechanism is followed by a Newtonian one as sintering progresses.     

Sintering of Mullite-Containing Materials: II, Effect of Agglomeration

The sintering behavior of mullite powder compacts which contained soft and hard agglomerates was studied, The maximum density achieved depended on the size and packing of the agglomerates. Although the initial % total pore volume was kept constant, the presence of larger pores in the green compact, due to larger agglomerates, resulted in lower final densities after sintering. Densification rates were enhanced by the breakdown of agglomerates by grinding. The particle and agglomerate packing arrangements caused densification substages to occur. A schematic model is presented which agrees well with the observed experimental behavior.     

Sintering of Nanosized MnZn Ferrite Powders

The sintering and microstructural evolution of nanosized MnZn ferrite powders prepared by a hydrothermal method were investigated. The microstructure of sintered ferrite compacts depends strongly on the strength of the agglomerates formed during the compacting of nanosized ferrite powders. It was found that at 700°C the theoretical density of sintered compacts can almost be reached, while above 900°C an increase of porosity was identified. The formation of extra porosity at higher sintering temperatures is caused mainly by the oxygen release which accompanies the dissolution of relatively large grains of residual alpha-Fe₂O₃ in the spinel lattice.     

团聚体含量对氧化锆粉料烧结性能的影响

用共沉淀－喷雾干燥的方法制得了具有不同团聚性质的氧化锆粉料。粉料成型后团聚体可能破碎，也可能继续存在。通过团聚体对烧结影响的研究发现，烧结过程中团聚体含量是影响烧结密度和显微结构形成的主要因素，而成型后素坯中团聚体含量又取决于团聚体的强度。讨论了团聚体之间及团聚体与基体之间的相互作用对烧结的影响。     

Heterogeneities and defects in powder compacts and sintered alumina bodies visualized by using the synchrotron X-ray CT

The uniaxial die compaction and sintering is an important industrial production method for metal and ceramic components. While submicron- and nano-sized powders are finding increasing use for making dense materials with finest grain sizes, the uniformity of microstructure, and then, the reliability of the products depend on the heterogeneity in powder packing structure. Here we applied the synchrotron X-ray multiscale-CT to characterize the complex domain structures, i.e., agglomerates, in powder compacts, and revealed how heterogeneous distribution of fine residual pores is formed by the differential sintering of agglomerates by using a submicron alumina powder as a model. A crack-like defect was identified as the largest defect. This defect was formed along the boundary between a plate-shaped agglomerate and its surroundings. A technique was also proposed to visualize the heterogeneous distribution of residual pores by using SEM. These characterization methods will open up new possibilities for the optimization of ceramic processing.     

Impact of pressure in static and dynamic pressing of zirconia ultradisperse powders on compact density and compaction efficiency during sintering

This paper studies the impact of pressure in static and dynamic pressing on densification of stabilized zirconia ultradisperse powder compacts and on compaction kinetics during sintering. Ultradisperse powders of 97 ZrO₂ + 3 Y₂O₃ zirconia were synthesized using the plasma chemical method. Dry uniaxial static pressing and double-action magnetic pulse compaction were employed. It is shown that double-action magnetic pulse compaction provides the maximum density of the product in comparison to that obtained through static pressing. The dilatometric studies showed that the increased density of compacts from stabilized zirconia powders obtained in dynamic pressing does not make ceramics less compact during isothermal aging as it typically occurs during static pressing. This increases the density of ceramics and improves its mechanical characteristics.     

Compaction behaviour of agglomerated alumina powders

The effects of agglomerate properties, such as the binder type, binder content, moisture level, and agglomerate size, on a model compaction process was investigated by using green density-pressure interrelationships for a range of agglomerated alumina powders. The model compaction process involved single ended nominal uniaxial stress transmission in a cylindrical die. The influences of the sample aspect ratio, die wall lubrication, and compaction rate were also investigated. Two types of water soluble polymeric agents, a poly(vinyl alcohol) (PVA) and a poly(ethylene glycol) (PEG), were used. It was shown that certain agglomerate properties have a strong influence upon the compaction behaviour of these ceramic powders. The extent of the compaction is enhanced by using agglomerates with a low agglomerate yield point. In the PVA system, the agglomerate yield points decreased with increasing moisture content. The compaction behaviour of the agglomerates showed a rate dependency, that is, the compaction is retarded with increased pressing rate. The green densities of the compacts prepared in the unlubricated die were lower than those of the compacts prepared in the lubricated die due to the higher wall frictional forces operating in the unlubricated die.     

Processing-Related Fracture Origins: II, Agglomerate Motion and Cracklike Internal Surfaces Caused by Differential Sintering

Effects of differential sintering kinetics due to differential green density were studied by fabricating agglomerate-powder matrix specimens from two Al₂O₃/ZrO₂ (30 vol%) powders and subjecting them to a cyclic sintering schedule to allow intermittent observations. Low-green-density compacts sintered faster than high-density compacts, although high-green-density compacts reached end-point densities first. Specimens containing low-green-density agglomerates produced circumferential cracklike voids at the agglomerate/matrix interface. Agglomerates with a higher green density than the matrix were subjected to compressive strains by the matrix to produce agglomerate motion when the resulting stress field was non-symmetric. Such agglomerates also produced a variety of cracklike separations. Implications regarding sintering kinetics and end-point densities are discussed. Implications regarding strength of sintered bodies are obvious, viz. strength can be proportional to the square root of the agglomerate size.     

Effect of heat treatment of alumina granules on the compaction behavior and properties of green and sintered bodies

The effects of the heat treatment of Al₂O₃ granules on the fracture behavior and compressibility of the granules, as well as on the properties of the green and sintered bodies, were examined. Heat treatment contributed to increasing the strength of granules, resulting in poor deformability. However, the hard and brittle characteristics of the heat-treated granules did not hinder the promotion of uniform powder packing and the formation of a nearly cohesive compact under high compaction pressure. Although as-spray-dried granules were more deformable during compaction, they left clear interfaces between granules in the green bodies, resulting in the preservation of large pores in the samples after sintering. The high density and small pore size in green compacts formed with heat-treated granules contributed to reducing the pore-defect size in the sintered bodies, resulting in high fracture strength.     

Mercury porosimetry of ceramics

Mercury porosimetry has been used in ceramics for the characterization of products and for studies of processing. Specifications including PSD (pore size distribution by mercury porosimetry) are now applied to magnesia refractories used in basic oxygen furnaces and to building brick which may be exposed to frost. Other products cited as examples are the silica fiber tile used on the space shuttle, plasma sprayed coatings, carbon composites and filters.In ceramic processing research, PSD has proved valuable for evaluating the firing of basic refractories, brick and sanitary ware. Pore growth during the early stages of sintering several materials was first identified by PSD. The character of clay agglomerates and the presence of alumina aggregates in compacts have been measured, the latter showing bimodal PSD. The progressive change in PSD while compacting glass spheres outlines the stages of compaction. The most frequent pore diameter in plaster slip casting molds correlates directly with plaster consistency.In dense or vitrified ceramics, errors may occur due to closed pores or pores with narrow openings. However, in ceramic compacts and highly porous ceramics, pores have several openings so PSD is a realistic measure of structure.     

Compaction and sintering response of mechanically alloyed Cu-Cr powder

The present paper discusses the powder processing techniques of mechanically alloyed Cu-Cr powder. Mechanical alloying is required to obtain a nano-scale homogeneous mixture of Cu and Cr. Two processes to prepare Cu-Cr contacts are proposed from the present study for obtaining compacts having better properties. While the explosive compaction of the mechanically alloyed powder forcibly fills the pores to show excellent density and electrical conductivity, application of Cu coating to the mechanical alloyed powder gives a short-circuit diffusion path during sintering and thus, shows the best combination of properties compared to the presently used Cu-Cr compacts. Both the processes show near theoretical density, exceptionally high electrical conductivity and comparable hardness. Moreover, both the processes change the sintering process of Cu-Cr compacts from liquid phase sintering to solid-state sintering, thus making the process more energy efficient.     

Powder Processing for the Fabrication of Si3N4 Ceramics: I, Influence of Spray-Dried Granule Strength on Pore Size Distribution in Green Compacts

The effect of spray-dried granule strength on the micro-structure of green compacts obtained by isostatic pressing was quantitatively analyzed. The fracture strength of single granules of Si₃N₄ powder made with ultrafine A1₂O₃ and Y₂O₃ powders was measured directly by diametral compression. It was found that fracture strength increased notably with the increasing relative density of the granule and the decreasing size of agglomerates in suspension before spray-drying. Even when green bodies were prepared at an isostatic pressure of 200 MPa, intergranular pores, which negatively affected densification of the sintered bodies, occurred between unfractured granules. The volume and size of these pores in the green compacts increased with the increasing fracture strength of the granules. In the case of closely packed granules, an isostatic pressure of 800 MPa was required to completely collapse the intergranular pores. A simple equation was derived to calculate the isostatic pressure necessary for complete collapse of intergranular pores in the green compacts, and it was determined that granule strength must be kept as low as possible to obtain uniform green compacts.     

Agglomerates in nanopowders and ceramic technology

Questions are considered connected with use in ceramic technology of ultrafine powder raw material with agglomerated particles. It is shown that presence of agglomerates in nanopowders unavoidably leads to formation in sintered material of structural defects in the form of residual porosity and microcracks. Data are provided for a quantitative dependence of pore structure characteristics for a powder compact on the content of agglomerated particles and the connection of pore structure characteristics with sintering kinetics and the properties of the sintered material obtained.