Liquid Phase Sintering of Alumina, I. Microstructure Evolution and Densification

The microstructure evolution and densification of alumina containing 10 vol% calcium aluminosilicate glass and 0.5 wt% magnesium oxide sintered at 1600°C were quantified by measuring the evolution of pore-size distribution, the redistribution of liquid phase, and the fraction of closed and open pores. The densification stopped at a limiting relative density during the final stage of sintering, and the small and large pores were filled simultaneously by glass during sintering. In addition, the results indicate that the pressure build-up of the trapped gases in pores causes a significantly negative contribution to the driving force, and consequently the observed reduction in densification during the final stage of liquid phase sintering.     

Effects of Applied Pressure on Densification During Sintering in the Presence of a Liquid Phase

Experimental measurements of the effects of an applied pressure on sintering of powdered materials containing a liquid phase indicate that the applied pressure can be effective by: ( a ) increasing the extent and rate of particle rearrangement, ( b ) increasing the rate of solution at particle contacts, and ( c ) causing plastic flow within the solid particles. Which of these processes predominates depends on the characteristics of each particular system and on the level of applied pressure.     

Liquid Phase Sintering of Alumina, III. Effect of Trapped Gases in Pores on Densification

The microstructure evolution and densification kinetics of alumina containing 10 and 20 vol% calcium aluminosilicate glass were studied, for sintering under vacuum and air at 1600°C. Residual porosity was always present in the air-fired samples. The kinetic analysis lent strong support to the notion that trapped gases inhibited the densification and limited the attainment of full density. The samples containing 20 vol% glass were able to reach full density during vacuum sintering. However, the samples containing 10 vol% glass contained some residual porosity even after vacuum sintering, which was attributed to the preferential volatalization of liquid phase.     

Grain-Growth Kinetics for Alumina in the Absence of a Liquid Phase

The kinetics of grain growth in fully dense Al₂O₃ with and without MgO solute additions were measured for high-purity samples containing no liquid phases. The MgO was found to suppress the grain-boundary migration rate by a factor of 50. Compensating lattice defects are suggested to play a role in grain-growth inhibition. Implications of these results to the sintering of Al₂O₃ are discussed.     

Effect of a Liquid Phase on the Morphology of Grain Growth in Alumina

In this investigation we have studied how the presence of a liquid phase affects the grain morphology and grain growth kinetics in Al₂O₃ at 1800°C using the growth of both matrix grains and large spherical single-crystal seeds growing into the matrix. The growth rates of the matrix grains were found to decrease in the following order: undoped Al₂O₃, AI₂O₃ with anorthite, AI₂O₃ with anorthite and MgO, and Al₂O₃ with MgO. Except for the samples doped with MgO alone, the matrix grains were faceted and appeared tabular in polished sections. In samples containing anorthite both with and without MgO, the single-crystal seeds exhibit basal facets with continuous liquid films and slow growth in the 〈0001〉 relative to all other crystallographic directions. When only MgO is added, the growth of the single-crystal seeds was not isotropic; however, no faceting was observed. We discuss how anisotropic growth rates caused by the anorthite additions can stimulate discontinuous grain growth in Al₂O₃.     

Cross-Linking in Spinning Solutions in the Presence of a Liquid Disperse Phase

The study of the kinetics of formation of interfacial layers on the cellulose triacetate in methylene chlorideaqueous solution of albumin interface and phase separation in the presence of a protein-containing liquid disperse phase showed that particles of the disperse phase can be additioal cross-linking sites as a result of association of macromolecules of the fibre-forming polymer near the phase boundary. A sharp increase in the viscosity of dispersions based on a solution of cellulose triacetate in methylene chloride was revealed when polyethylene oxide was incorporated in the protein-containing disperse phase. A mechanism of formation of the interfacial adsorption layer in the presence of protein and polyethylene oxide was proposed. It was shown that incorporation of compounds adsorbed on the phase boundary in both the disperse phase and the dispersion medium affect phase separation. Moscow State Textile University. Translated fromKhimicheskie Volokna, No. 6, pp. 24–27, November–December, 2000.     

Sintering of Oxide and Carbide-Metal Compositions in Presence of a Liquid Phase

Observations of microstructure changes in several systems and the rate of densification during sintering of magnesium oxide, titanium carbide, and tungsten carbide in the presence of a liquid phase indicate that the densification rate is controlled by diffusion through a liquid film between particles. Dependence of the sintering rate on time, particle size, and temperature are in agreement with predictions. Theoretical estimations of the sintering rate are in reasonable agreement with experimental measurements.     

Adsorption of Colloidal Silica on Alumina and of Colloidal Alumina on Silica

The mutual adsorption of colloidal silica on alumina and of colloidal alumina on silica and silicate materials occurs in aqueous suspension at about pH 4. It is shown that the adsorption of colloidal particles on the surface of opposite charge is limited to essentially a monoparticle layer. An adsorbed layer of fibrils of colloidal alumina on the surfaces of silica, asbestos, graphite, and finely divided clay is shown in electron micrographs. The effect of the adsorbed colloid on dispersibility of the substrate materials is discussed.     

Liquid Phase Sintering of Alumina, II. Penetration of Liquid Phase into Model Microstructures

Alumina preforms containing artificial pores were sintered at 1630°C in air and vacuum. Glass penetration into the alumina preforms was conducted at 1600°C in air. It was found that the trapped gases in alumina preforms sintered in air caused the random and incomplete filling of the smaller and larger artificial pores. In contrast, the pores in the alumina preform sintered in vacuum were completely filled during glass penetration.     

Intermediate-Stage Densification in Vacuum Hot-Pressing of Alumina

The densification kinetics preceding the final-stage densification of Al₂O₃ hot-pressed in vacuum between 1150° and 1350°C and between 2000 and 6000 psi were analyzed. The analysis suggests a diffusion-controlled creep mechanism but is not necessarily consistent with a Nabarro-Herring vacancy model. The measured activation energy, 116 kcal/mol, agrees with the activation energy for the final stage of densification and for the self-diffusion of Al ions in Al₂O₃. It is proposed that the pore structure (i.e. open or closed) defines the stage of densification and, further, that pore structure has a profound effect on the apparent diffusion coefficients.     

Phase Transformation and Densification of an Attrition-Milled Amorphous Yttria-Partially-Stabilized Zirconia–20 mol% Alumina Powder

Phase transformations during consolidation treatments of an attrition-milled amorphous yttria-partially-stabilized zirconia (Y-PSZ: ZrO₂–3 mol% Y₂O₃)–20 mol% Al₂O₃ powder and the resulting microstructures have been investigated. A metastable cubic phase ( c -ZrO₂ solid solution) together with an α-Al₂O₃ phase is formed in the amorphous matrix by consolidation at temperatures below 1204 K. The metastable cubic phase transforms to a stable tetragonal phase ( t -ZrO₂ solid solution) with an increase in the consolidation temperature. Fully dense bulk samples consisting of extremely fine tetragonal grains together with a small amount of α-Al₂O₃ particles could be obtained by consolidation at temperatures above 1432 K. Important features concerned with the densification behavior are as follows: (1) Marked increase in the relative density occurs after cubic crystallization and subsequent cubic-to-tetragonal transformation. (2) All of the consolidated bulk samples show extremely fine grain structure with grain sizes of several tens of nanometers, irrespective of the consolidation temperature. (3) The regularity of the lattice fringe contrast in each tetragonal grain seems to be kept in the vicinity of grain boundaries. These results suggest that densification of the attrition-milled amorphous powder proceeds via superplastic flow and/or diffusional creep, rather than viscous flow of the initial amorphous phase before crystallization.     

Final Stage Densification in Vacuum Hot-Pressing of Alumina

The kinetics of the final stage of densification of fine-grained aluminum oxide were studied by vacuum hot-pressing between 1150° and 1350°C and from 2000 to 6000 psi. The kinetics are consistent with the Nabarro-Herring diffusional creep model. The activation energy for the final stage densification is 115 kcal/mole which agrees with the activation energy for diffusion of aluminum ions. Densification takes place by particle rearrangement and by diffusional creep. The extent of densification in the initial stage depends on the amount of sliding, fragmentation, and plastic flow. The final stage of densification takes place by diffusional creep and is controlled by aluminum ion diffusion in aluminum oxide. It is shown that gases entrapped within pores of the hot-pressed compact will produce end-point porosities. A technique is described for removing adsorbed water when it is the source of the Presented at the Fall Meeting of the Basic Science Division and the Seventeenth Pacific Coast Regional Meetings of the American Ceramic Society, San Francisco, California, October 30, 1964.     

Nonstoichiometry and Sintering of Bismuth-Germanium Binary Oxides in the Presence of Liquid Phase

Results of a study of the effect of deviation from stoichiometry of the compositions of binary bismuth-germanium oxides with structures of sillenite and eulitine on the sinterability in the presence of liquid phase are presented. It is established that the change in the degree of nonstoichiometry of the substances determines the substantial contribution to the driving force of the sintering process and increases considerably the efficiency of the latter.     

Densification and Grain Growth of Porous Alumina Compacts

Densification and grain growth of porous alumina compacts during various high-temperature processes were investigated. Experimental data were obtained for densification and grain growth of alumina powder during hot pressing. A set of constitutive equations was proposed based on the constitutive equations by Helle et al. ¹ for hydrostatic response and by Rahaman et al. ² for deviatoric response. Theoretical results from the proposed constitutive equations were compared with various experimental data for alumina powder compacts in the literature, including pressureless sintering, sinter forging, and hot pressing. The proposed model well predicts the densification and grain growth of alumina compacts.     

Faceting Behavior of Alumina in the Presence of a Glass

The faceting of alumina interfaces in the presence of a glass affects both grain growth and grain-boundary mobility during liquid-phase sintering. The geometry and movement of facets that form during this sintering process are expected to play an essential role in the development of the final microstructure, in particular, by their influence on the topology of the grain boundaries which ultimately control the properties of Al₂O₃ compacts. A new method for studying the interaction between Al₂O₃ and a glass has been developed. A thin sample of Al₂O₃ suitable for examination in a transmission electron microscope is prepared and examined and then reacted with SiO₂ and CaO via the vapor phase. This experimental approach allows the faceting behavior of glass/Al₂O₃ interfaces to be studied systematically without introducing unnecessary complications during subsequent sample preparation. Faceting occurs almost exclusively on the (0001) and {1 1 02} planes. The interaction between glass and certain structured grain boundaries in alumina has been studied using polycrystalline thin films.     

Constrained Densification Kinetics of Alumina/Borosilicate Glass + Alumina/Alumina Sandwich Structure

The densification kinetics and mechanism of a low-temperature cofirable borosilicate glass (BSG) + alumina during the constrained sintering of a sandwich structure of alumina/(BSG + alumina)/alumina has been studied. The densification kinetics becomes slower when the BSG + alumina tape is constrained during firing. However, a viscous flow-controlling mechanism of the BSG also is still operative during free and constrained sintering. The densification behavior of constrained sintering can be mathematically described by free sintering, using the viscous analogy for the constitutive equations of a porous sintering glass.     

Ni-mediated Liquid Phase Reduction of Carbonyl Compounds in the Presence of Atmospheric Hydrogen

An efficient reduction system of benzaldehyde with hydrogen under ambient pressure was developed using facile NiO catalyst. The non-aromatic solvents such as cyclohexane, tetrahydrofuran （THF） and n-hexane, and the additive with strong basicity e.g. KOH, were necessary for smooth conversion of the substrate. That the catalyst can be recovered and reused for nine times without loss of catalytic activity indicates that this catalyst is a recyclable one for benzaldehyde reduction.     

Densification Energy during Nanoindentation of Silica Glass

Load/unload displacement curves at room temperature (humidity 49%) for silica glass have been measured in the penetration range of 0.5–1.2 μm using a Vickers nanoindentation technique (load/unload speed 50 mN/s). Deformation energies have been estimated for the first time. The universal (dynamic) hardness, H _u, and elastic recovery, E _R, at the penetration depth, h _t, of 1.0 μm are H _u= 4.1 GPa and E _R= 0.7. The following energies for total deformation, U _t, elastic deformation, U _e, and plastic deformation (i.e., densification during loading), U _p, are obtained: U _t=190, U _e=135 and U _p= 55 kJ/mol at h _t= 0.5 μm and U _t= 139, U _e= 96 and U _p= 43 kJ/mol at h _t=1.0 μm. All these deformation energies increase with decreasing penetration depth. It is found that plastic deformation energies of 38–55 kJ/mol for 0.5 < h _t < 1.2 μm are very close to the activation energy (46–54 kJ/mol) for the recovery of densification in silica glass, but are very small compared with the single bond strength (443 kJ/mol for Si—O bond) of SiO₂.     

Alternative Explanation for the Role of Magnesia in the Sintering of Alumina Containing Small Amounts of a Liquid Phase

The microstructural evolution during sintering of Al₂O₃ was investigated to determine the role of MgO additive, particularly when its concentration is very low (<200 ppm). Compared with specimens without MgO, a few Al₂O₃ grains were observed to grow enormously after the addition of 50 or 100 ppm MgO. When MgO content was increased to 200 ppm, on the other hand, the overall grain growth process was accelerated and many growing grains impinged on each other. In this case, therefore, a fine and unimodal grained microstructure was obtained. Sintering of Al₂O₃ in a MgO atmosphere further supported the promotion of grain growth by MgO. It is proposed that MgO promotes the grain growth of Al₂O₃ either by lowering the edge energy or by roughening the interface structure.     

液相改性对白炭黑表面活性位点的影响

先采用偶联剂KH590与分散剂MOA液相改性白炭黑制备改性白炭黑水浆,然后分别制备干法混炼和湿法混炼天然橡胶(NR)/白炭黑母炼胶,再在后期混炼时补加偶联剂Si69,通过制备NR/白炭黑纳米复合材料并对其性能进行研究,考察液相改性后的白炭黑表面是否还有剩余活性位点与偶联剂Si69反应。结果表明,后期补加的偶联剂Si69无法接枝在白炭黑表面而起到偶联作用,不能改善白炭黑在橡胶基体中的分散性和NR/白炭黑纳米复合材料的性能,液相改性后的白炭黑表面活性位点已全部被占据。