Date of Award

5-2010

Document Type

Dissertation

Degree Name

Doctor of Philosophy (PhD)

Legacy Department

Materials Science and Engineering

Committee Chair/Advisor

Ballato, John

Committee Member

Foulger , Stephen

Committee Member

Luo , Jian

Committee Member

Skaar , Eric

Abstract

Sesquioxides of yttrium, scandium, and lutetium, i.e., Y2O3, Sc2O3, and Lu2O3, have received a great deal of recent attention as potential high power solid state laser hosts. These oxides are receptive to lanthanide doping, including trivalent Er, Ho and Tm which have well known emissions at eye-safe wavelengths that can be excited using commercial diode lasers. These sesquioxides are considered superior to the more conventional yttrium aluminum garnet (YAG) due to their higher thermal conductivity, which is critical for high power laser system. Unfortunately, these oxides possess high melting temperatures, which make the growth of high purity and quality crystals using melt techniques difficult. Transparent ceramics are an attractive alternative route to laser hosts since the processing by-passes many of the challenges of refractory crystal melt growth. Moreover, transparent ceramics can possess added benefits relative to single crystals including faster production rates, the fabrication of larger sizes and composite laser structures, uniform doping concentrations, and better mechanical behavior.
In order to fabricate highly transparent ceramics, the starting powders must have good dispersion and high reactivity. In this work, sesquioxide nanopowders with high sinterability were synthesized by solution precipitation techniques. For Y2O3, the nanopowders were prepared using yttrium nitrate and ammonium hydroxide with the addition of a small amount of ammonium sulfate. Doping sulfate ions was found to reduce the agglomeration of Y2O3 nanopowders. The Y2O3 nanopowders with average particle size about 40 nm were obtained by calcining at 1050 °C for 4 hours. Unfortunately, this method failed to prepare well-dispersed Sc2O3 and Lu2O3 nanopowders. For Sc2O3 and Lu2O3, the nanopowders were synthesized by using scandium or lutetium sulfate and hexamethylenetetramine (HMT). The precipitate precursors were calcined at 1100 °C for 4 hours to yielded Sc2O3 and Lu2O3 nanopowders with average particle size 40 and 60 nm, respectively.
Transparent sesquioxide ceramics were successfully fabricated by vacuum sintering compacts of nanopowders at high temperature. These ceramics had relatively large grain sizes, ranging from tens to hundreds of micrometers, due to significant grain growth at the final stage of sintering. These large-grained ceramics tend to not offer significant enhancements to strength or thermal shock resistance that smaller grain-sized transparent ceramics afford.
Sub-micrometer-grained highly transparent sesquioxide ceramics were fabricated using a two-step sintering process followed by hot isostatic pressing (HIP). This process yielded full densification of the sesquioxide ceramics with drastically reduced grain growth. These sub-micrometer-grained ceramics exhibited a transparency equivalent to that of single crystals in the near-infrared spectral. The microhardness and fracture toughness of transparent ceramics fabricated by this method were found to exceed those of transparent ceramics fabricated by conventional sintering. The single-crystal-like transmittance of the sub-micrometer-grained yttria ceramics in the visible and IR region with high mechanical properties is an important advancement for the use of these materials in more extreme environments, including high power laser systems where reduction of scattering and thermal shock resistance are critical.

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