Permeability, Drying, and Sintering of Pressure Filtered Ceramic Nanopowders
Open Access
- Author:
- Sweeney, Sean M.
- Graduate Program:
- Materials Science and Engineering
- Degree:
- Doctor of Philosophy
- Document Type:
- Dissertation
- Date of Defense:
- April 22, 2002
- Committee Members:
- David John Green, Committee Chair/Co-Chair
Merrilea J Mayo, Committee Member
Randall M German, Committee Member
James Hansell Adair, Committee Member
Gary Lynn Messing, Committee Member - Keywords:
- permeability
drying
sintering
zirconia
boehmite
silica
pressure filtration
adsorbed water
drying stress - Abstract:
- Three aspects of nanocrystalline ceramic body formation are examined in this work: permeability, drying stress, and sintering behavior. The permeabilities of nanocrystalline 3 mol% yttria-stabilized zirconia (3Y-TZP), silica, and boehmite powder compacts are measured during their formation by constant rate pressure filtration. The classic Carman-Kozeny equation with no account for the effect of adsorbed water often overestimates by a factor of 2 or more the measured permeabilities, with increasing deviation with decreasing permeability. A permeability equation from the literature and one derived here, both taking into account the effect of adsorbed water, show significant improvement over the classic Carman-Kozeny equation for predicting measured permeabilities. The equation derived here allows straightforward predictions to be made of how permeability will change as the critical point of drying (when shrinkage stops) is approached. An approximate expression for the maximum tensile stress occurring in an elastic finite cylinder during drying from all sides is derived. Numerical calculations of the exact state of stress during drying show that for cylinder length-to-diameter ratios up to 2/3, the present expression is more accurate than equations from the literature for an infinite plate and an infinite cylinder. For cylinders with length-to-diameter ratios greater than 2/3, numerical calculations show an equation from the literature for the drying stress in an infinite cylinder to be more accurate. To test the validity of the present expression, the drying rates above which fracture occurs are determined for disk-shaped samples of pressure filtered nanocrystalline 3Y-TZP, boehmite, and silica powders. These maximum safe drying rates are used with the present expression to calculate the maximum drying stresses that can be sustained without fracture, and these stresses are compared to diametral compression-measured strengths of similar samples dried to the critical point of drying (when fracture is most likely during drying). Agreement between maximum safe drying stresses and measured sample strengths is found to be good (to within better than a factor of 2) for boehmite samples, but not very good (off by a factor of ~7) for nanocrystalline 3Y-TZP samples. Sub-critical crack growth is indicated as the source of this deviation in nanocrystalline 3Y-TZP samples. Literature studies of the sintering of chloride-derived 3Y-TZP nanopowders have documented numerous sintering problems including inability to reach full density, desintering, cracking, and the formation of a dense shell with less dense interior. To explain the poor sintering behavior of samples of one nanocrystalline 3Y-TZP powder, the origin of such a dense shell microstructure is determined. Three possible reasons for a dense shell microstructure are examined and rejected: exothermic reactions with the sintering atmosphere, pre-existing density gradients in the green compact, and thermal gradients occurring during sintering. A combination of gas flow/diffusion, thermodynamic, and sintering calculations are used to show that the evolution of a structure-coarsening gas (hydrogen chloride) during sintering causes the formation of a dense shell microstructure, and explains the poor densification behavior of this system. Two solutions to the problem are compared: 1) a thermal treatment composed of an extended hold at 1000°C to allow HCl gas removal before the onset of closed porosity (at about 90-93% of theoretical density), and 2) a chemical treatment performed by washing pre-sintered (500 °C/30 min) samples at room temperature using a concentrated ammonium hydroxide solution to remove chlorides. The thermal treatment is found to be superior for removing residual chlorine and allowing full density to be achieved during sintering.