Sintering deformation caused by particle orientation in uniaxially and isostatically pressed alumina compacts

Effect of particle orientation on deformation during sintering is reported for model systems; one made with industrial grade low soda alumina, which has an elongated particle shape, and the other a special alumina with a spherical particle shape. To ensure the homogeneous packing density of particles, compacts were made by uniaxial pressing followed by cold isostatic pressing. The particle orientation was examined with a polarized light microscope and was found to be an important cause of sintering deformation. In a green body, for elongated shape of particles, the particle orientation occurred during uniaxial pressing, causing the anisotropic sintering shrinkage during sintering and thus the sintering deformation. No particle orientation nor shrinkage anisotropy was noted in the system made with the powder of spherical particle shape.     

Densification of Alkoxide-Derived Fine Silica Powder Compact by Ultra-High-Pressure Cold Isostatic Pressing

Powder compacts of alkoxide-derived fine silica powders were consolidated into a highly dense and uniform structure by ultra-high-pressure cold isostatic pressing of granules with controlled structure. The diameters of spherical and nearly monosized amorphous silica particles, prepared from metal alkoxide, were successfully controlled in the range of 9 to 760 nm by varying the concentration of ammonia. Close-packed granules of these powders were produced by spray drying. These powders were isostatically pressed up to 1 GPa at room temperature. Although the average particle diameter was less than 100 nm, the maximum relative density of the compacts was more than 78% of theoretical density. The optimum particle size to obtain highly dense compacts was in the range of 30 to 300 nm at 1 GPa. Furthermore, the ratio of mode pore diameter in these compacts to particle diameter was less than 0.155, which corresponded to the minimum ratio of calculated three-particle pore channel radii for hexagonal close packing. Viscous deformation of particles under ultra-high isostatic pressure played an important role in the densification of the compacts.     

A quantitative evaluation method for particle orientation structure in alumina powder compacts

A quantitative evaluation method was developed to analyze weak-moderate particle orientation in alumina green compacts based on the optical anisotropy measured with a polarized light microscope. Alumina compacts of various structures were prepared in high magnetic fields 0–10 T by a casting method. The compact was made transparent with an immersion liquid, and the retardation of polarized light through it was measured quantitatively using a polarized light microscope with a Berek compensator. The degree of particle orientation was defined as the ratio of birefringence of the compact to that of alumina single crystal perpendicular to the c-axis. The degrees of orientation thus evaluated were compared to those calculated from X-ray diffraction analysis for samples with high orientation, and were found to agree very well.     

Infrared Microscopy for Examination of Structure in Spray-Dried Granules and Compacts

Novel infrared microscopy has been developed to improve the liquid-immersion method, which is a technique that has been developed by the authors to study the packing structures of powder particles in ceramic green bodies. This paper demonstrates the high potential of the novel technique by presenting clear structures of Si₃N₄ powder granules and their compacts.     

Particle Orientation During Tape Casting in the Fabrication of Grain-Oriented Bismuth Titanate

Slurries containing platelike Bi₄Ti₃O₁₂ particles have been tape cast to prepare green sheets with aligned particles. The slurries contain well-dispersed particles and show nearly Newtonian flow behavior. The effect of slurry composition and casting conditions on the particle orientation has been examined. The particle orientation in the green sheet is determined mainly by powder content; other parameters, such as binder content, casting speed, and blade opening, have little effect. The interaction between particles is a main cause for particle alingnment. The slurry with a large powder content is favorable for preparing dense grain-oriented ceramics.     

Validity of Using Mercury Porosimetry to Characterize the Pore Structures of Ceramic Green Compacts

The ability of mercury porosimetry in characterizing particle packing and pore structures of dense ceramic green compacts is evaluated. Differences in intrusion spectra between the dry-pressed and slip-cast compacts demonstrate the utility of mercury porosimetry for particle-packing analysis. Of the voids embedded in the matrix, only those at or extending to the matrix surface are detectable. Intrusion—extrusion spectra show hysteresis, but otherwise do not provide added insight into bulk defect structure.     

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.     

Processing of Al2O3/SiC nanocomposites—part 2: green body formation and sintering

Pressure filtration was used to form green compacts from aqueous slurries of alumina with 5 vol.% silicon carbide. Green densities of 64%TD were achieved for slurries containing a 50 vol.% solids loading. Lower green densities were obtained for a very fine alumina due to the practical limits on maximum slurry solids loading when using finer powders. The samples were dried in a purposely built humidity cabinet to limit sample cracking. It was found that a higher consolidated layer permeability gave a higher initial drying rate. Near fully dense (99% TD) nanocomposites were produced, via pressureless sintering at 1900 °C. Poor sintered densities were obtained in the case of the fine alumina because of localised sintering of these low green density compacts. The required intra/inter-granular nanocomposite microstructures have been obtained for several different systems, with an average grain size of approximately 5 μm. Abnormal grain growth was noted for samples containing the larger particle size silicon carbide. This shows that a maximum particle size limit exists when selecting the powders for a 5 vol.% nanocomposite.     

Synthesis of Silicon Carbide Ceramics Using Chemically Modified Polycarbosilanes as a Compaction Binder

A chemically modified polycarbosilane (PC) containing organofluoric groups (PCOCF) has been synthesized from PC and fluoroalkylmethyldimethoxysilane. PCOCF acts as an efficient compaction binder for SiC powders and as a coating material with excellent oxidation resistance in wet air. PCOCF-coated SiC powders also show excellent packing properties because of the organofluoric side chains, which give highly dense green compacts. PCOCF provides a high ceramic yield of 75% and highly dense SiC ceramics. Four-point bending strength increases and the scatter in strength values decreases significantly by PCOCF coating.     

On the effect of mould temperature on the orientation and packing of particles in ceramic injection moulding

Particle packing and orientation in Ceramic Injection Moulding are caused by shear rate variations along the part, which are complicated by cooling rates and depend on material properties and process parameters. This work studies particle orientation and packing for a ceramic feedstock in relation to mould temperature, with a focus on the influence from Rapid Heat Cycle Moulding (RHCM). A sample part consisting of bars having different thicknesses (0.4 mm to 6 mm) was injection moulded using first ambient mould temperature and then a rapid heating approach; subsequently, green part microstructure was analysed to detect particle orientation and packing. Results show a more uniform orientation at thick sections using RHCM, with a 15% enlargement of a core layer characterised by randomly oriented particles, as well as a higher homogeneity of powder packing between thin and thick sections. Thus, this study demonstrates that not only can RHCM be used to enhance feature replication capability, but also has the potential to improve critical microstructural properties of green components, which highly influence sintered parts quality.     

Effect of Internal Lubricants on Defects in Compacts Made from Spray-Dried Powders

The role of internal lubricants in the closure of large intergranular pores during dry-pressing was investigated. Alumina was spray-dried with and without an internal lubricant to yield granules with similar characteristics other than lubricant effects. Green and sintered microstructures were evaluated at different compaction pressures. The defects were quantified by evaluating the fracture surface of ∼90% dense sintered compacts. The samples that contained an internal lubricant had higher green densities and fewer defects at comparable compaction pressures. The internal lubricant did not cause any significant reduction in green strength or increase in springback.     

Effect of Relative Humidity on the Viscoelastic and Mechanical Properties of Spray-Dried Powder Compacts

Spray-dried powder compacts exhibit viscoelastic properties such as stress relaxation, creep, and delayed elastic strain. This behavior is attributed to the organic binder, which forms bridges between the particles in spray-dried granules, thereby affecting their deformation characteristics. The viscosity and distribution of the binder within the powder compact can affect its mechanical and viscoelastic properties. In this study, the powder was conditioned at different ambient relative humidity (RH) levels, to vary the binder viscosity. Load deformation, stress relaxation, fracture strength, and fracture toughness behavior of ferrite powder compacts were studied as a function of ambient RH both before and after compaction. The loading rate was found to significantly affect the time-dependent response, and the relaxation times decreased at high humidity levels during compaction. It is proposed that increasing the humidity level during compaction increases the number of particle–particle contacts. This simple mechanism of binder redistribution led to slower relaxation times, increases in fracture strength, and elastic modulus of the green bodies, without significantly altering the fracture toughness when powders were compacted at high humidity to a given density.     

Fabrication of green and sintered bodies prepared by centrifugal compaction process using wet-jet milled slurries

Properties of green and sintered bodies prepared by high-speed centrifugal compaction process (HCP) using wet-jet milled slurries were investigated. At 30 vol.% solids loading, the relative packing density of compacted body prepared from wet-jet milled slurry was 67%. On the other hand, the density of compacted body prepared from ball-milled slurry was 56% at the same loadings. The difference in relative densities of the top and bottom of green bodies prepared from wet-jet milled slurry was decreased to one-third of the ones prepared from ball-milled slurry. Moreover, the linear shrinkage of the sintered bodies prepared from wet-jet milled slurries was almost constant at sintering temperatures above 1400 °C; it was found to be increasing for bodies prepared from ball-milled slurries with increasing sintering temperature. Furthermore, activation energy for grain-growth was estimated. The grain-growth of green bodies prepared from wet-jet milled slurries was promoted at lower-sintering temperatures.     

Influence of Slurry Parameters on the Characteristics of Spray-Dried Granules

A systematic study has been performed to determine how the characteristics of granules prepared by spray drying aqueous alumina slurries are influenced by processing parameters: binder type (PEG Compound 20M or PEG-8000), solids loading (30 or 40 vol%), ammonium polyacrylate deflocculant level (0.35-1.00 wt%), and spray-dryer type. Correlations between slurry rheology and granule characteristics have been made, and a model for granule formation is presented. The packing density of the primary particles within the granules is lower for slurries with higher yield stress and is dependent on the slurry solids loading. Granules prepared using 0.35 wt% deflocculant (0.14 mg/m²), which correspond to high slurry yield stress, are of solid morphology, whereas higher deflocculant levels result in hollow granules that contain a single large open pore or crater. The degree to which particles are able to rearrange during drying influences the final granule density and is determined by the strength of the floc structure, as indicated by the slurry yield stress. When the yield stress is low, a crater may form from the inward collapse of the surface of a forming granule when the particle packing density in a droplet continues to increase after the droplet size becomes fixed by the formation of a rigid shell, leaving an internal void with internal pressure lower than that of the surrounding atmosphere.     

Correlation between the morphology of cobalt oxalate precursors and the microstructure of metal cobalt powders and compacts

Metal cobalt powders of well-controlled size and morphology were synthesized by thermal decomposition under hydrogen of precipitated cobalt oxalates. Green compacts were prepared by uniaxial pressing of metal powders at 290 MPa. The bending green strength of the metal compacts was measured.A precipitation from ammonium oxalate and oxalic acid gives rise to the formation of β-CoC₂O₄·2H₂O particles of parallelepipedic and acicular morphology, respectively. An increase in the length to diameter ratio of the precursor particles favours an entanglement of the elementary grains during the thermal decomposition. Therefore, irregular and rough metal particles have been obtained. This specific morphology favours a mechanical interlocking of the particles during the compaction, leading to high values of green density and green strength of the metal compacts.     

Limitations on the sintering of graded particle systems

Improvement of compact density is commonly achieved by blending coarse and fine particles, but these compacts will not densify without the presence of a significant amount of liquid phase. It was proposed that two step sintering (TSS) could be applied to sinter the fine particle matrix, potentially accommodating the presence of inclusions of large particles. This hypothesis was false. Compacts were prepared with similar green density but with different ratios of coarse, medium, and fine particles and then subjected to TSS. The results indicated that constrained sintering limits densification on both ends of the particle packing spectrum: A fine particle matrix containing large particles fails to densify because the matrix cannot shrink around the inclusion; the densification of fine particle pockets in a skeletal network composed of large particles does not allow sufficient shrinkage in the pockets of small particles.     

Effect of Solids Loading on Slip-Casting Performance of Silicon Carbide Slurries

The influence of solids loading and particle shape on the green microstructure of slip-cast bodies was investigated. Three commercial silicon carbide (SiC) powders (two coarse varieties with the same particle-size distribution (PSD) but different particle shapes and a finer powder) were used to prepare bimodal PSDs designed to maximize the packing density. Various surface-active agents (anionic, cationic, and non-ionic) were tested. Anionic dispersants were the most effective in dispersing aqueous SiC slurries. The effectiveness of dispersants was evaluated by sedimentation tests using very dilute slurries, by rheology, and by the packing density of slip-cast bodies prepared from suspensions loaded with 62.5 wt% solids, stabilized with a fixed amount of dispersant (0.25 wt%, relative to the solids). Then, the best dispersant was selected to study the effects of dispersant and solids concentrations on the degree of packing of bimodal suspensions that contained the sharper-edged coarse particles. It could be observed that the green density was dependent on both parameters, initially showing an increase to a maximum, followed by a decreasing trend. A high value of 74.5% of the theoretical density (TD) was obtained from suspensions that contained 70 wt% solids and 0.1 wt% dispersant. The substitution of the angular coarse particles by similarly sized but more spherical particles resulted in an additional increase in green density to >76 wt% TD. The results can be interpreted in terms of freedom of particles upon deposition on the cast layer, which enables particle rearrangement, and segregation phenomena.     

Better Sintering through Green-State Deformation Processing

Aqueous colloidal suspensions of alumina were processed in the dispersed state and the flocculated state by controlling the double-layer interactions between the particles. Repulsive particle forces led to high packing densities but the green bodies were mechanically so weak that they were unable to retain their shape (the dispersed case). Attractive forces led to good green strength but the packing density was low and the particles were agglomerated (the flocculated case). The agglomerated structure of the flocced specimens could be fragmented by mechanical deformation of the green compact; the deformation was carried out under a superimposed hydrostatic pressure of less than 1 MPa. The flow stess of the flocculated structures depended on the deformation rate, and on the magnitude of the superimposed hydrostatic pressure. The flow stress was 2.5 kPa at a strain rate of 0.1 s⁻¹. Deformation processing of the flocced structures increased the green (relative) density from 0.51 to 0.62. The sintering behavior of underformed and deformation-processed flocced structures was studied. Deformation-processed green bodies sintered more rapidly and yielded a final grain size that was smaller and more uniform than that obtained from the undeformed specimens. The ability to homogenize and densify the packing of flocculated structures by deformation processing suggests new opportunities in green-state processing, for example (i) uniform mixing of more than one kind of particle or particles and fibers, and (ii) net shape forming by injection molding or extrusion, without the use of organic binders.     

Effect of medium condition change on green body density during casting and drying

The present study examined whether the optimum slurry conditions in which the green body with the highest packing fraction was fabricated were the same regardless of whether tape or slip casting methods were used. Additionally, we investigated the optimum slurry evaluation method to predict the packing fraction of each green body. Specifically, aqueous dense alumina slurries, whose particle dispersion state was changed by varying pH and the amount of dispersant additive, were prepared. After changing the pH, the optimum slurry conditions were achieved regardless of the casting method. The most suitable amount of additive dispersant differed due to the changing solution conditions during the casting and drying process; the medium of the slurry permeated into the plaster during slip casting and dried on the substrate during tape casting. Thus, in slip casting, non-adsorbed polymers could also be permeated. Hence, it is crucial for slurry evaluation to predict the packing fraction of the slip cast body. A sedimentation test, which involved particle condensation as well as casting, was valid for the green sheet. Conversely, it was experimentally shown that the constant pressure filtration test, which involved the permeation of the medium in addition to particle condensation, was suitable for slip casting.