Electrically Conductive Ceramic Powders

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New York State College of Ceramics at Alfred University. Kazuo Inamori School of Engineering.
Electrically conductive ceramic powders were investigated in this project. There are three ways to produce those materials. The first is doping alkali metal into the titanium dioxides in an inert or reducing atmosphere. The second is reducing un-doped titanium dioxide, forming a non-stoichiometric composition in a hydrogen atmosphere. The third is to coat a conductive layer, reduced titanium dioxide, on an insulating core such as alumina. Highly conductive powders have been produced by all these processes. The conductivity of powder compacts ranged between 10^-2 and 10^0 S/cm. A novel doping process was developed. All samples were doped by a solid-vapor reaction instead of a solid state reaction. Titanium dioxide was doped with alkali metals such as Na or Li in this study. The alkali metal atom contributes an electron to the host material (TiO2), which then creates Ti^3+ ion. The conductivity was enhanced by creating the donor level due to the presence of these Ti^3+ ions. The conductivity of those alkali doped titanium oxides was dependent on the doping level and charge mobility. Non-stoichiometric titanium oxides were produced by reduction of titanium dioxide in a hydrogen atmosphere at 800˚C to 1000˚C for 2 to 6 hours. The reduced titanium oxides showed better stability with respect to conductivity at ambient condition when compared with the Na or Li doped samples. Conductive coatings were prepared by coating titanium precursors on insulating core materials like SiO2, Al2O3 or mica. The titania coating was made by hydrolysis of titanyl sulfate (TiOSO4) followed by a reduction procedure to form reduced titanium oxide. The reduced titanium oxides are highly conductive. A uniform coating of titanium oxides on alumina cores was successfully produced. The conductivity of coated powder composites was a function of coating quantity and hydrolysis reaction temperature. The conductivity of the powder as a function of structure, composition, temperature, frequency and moisture was studied. Three classifications of structure were identified for alkali-doped titanium oxides: 1) Pure titanium dioxide phase with alkali ions located in interstitial positions. 2) The titanium bronze phases. 3) Alkali-doped titanium oxides. Highly conductive powders were obtained in the first and second classifications with conductivity of 10^-2 to 10^0 S/cm. Materials in the third classification had poor conductivity below 10^-3 S/cm. The conductivity of a powder was determined mainly by the grain conductivity and the grain contact conductivity. The present results of impedance spectroscopy suggested that the grain contact resistance was a major factor of the electrical resistance of the samples. The aging effect at different moisture conditions was also caused by an increase of the contact resistance. Both sodium-doped and reduced titanium oxides showed re-oxidation at elevated temperature (above 140˚C) in air, which is most probably caused by oxidizing the Ti^3+ ions under those conditions. Lithium doped titanium oxides did not show this re-oxidation at temperatures up to 200˚C. Theoretical models were applied to describe the effects of porosity, contact configuration and grain surface on conductivity of powder compacts. Percolathion theory was used in the present study to demonstrate the effect of mixtures of conductive and non-conductive powders, which is one of applications for conductive ceramic powders when they are used as filler materials in paper, paints or plastics.
Advisory committee members: Vasantha Amarakoon, Doreen Edwards. Dissertation completed in partial fulfillment of the requirements for the degree of Doctorate of Philosophy in Ceramics at the Kazuo Inamori School of Engineering, New York State College of Ceramics at Alfred University