Low temperature sintering semiconducting barium strontium titanate

Low temperature sintering has become a very important research area in ceramics processing and sintering as a promising process to obtain grain size below 100nm. For electronic ceramics, low temperature sintering is particularly difficult, because not only the required microstructure but also the desired electronic properties should be obtained. In this dissertation, the effect of liquid sintering aids and particle size (micrometer and nanometer) on sintering temperature and Positive Temperature Coefficient Resistivity (PTCR) property are investigated for Ba1-xSrxTiO3 (BST) doped with 0.2-0.3mol% Sb3+ (x = 0.1, 0.2, 0.3, 0.4 and 0.5). Different sintering aids with low melting point are used as sintering aids to decrease the sintering temperature for micrometer size BST particles. Micrometer size and nanometer size Ba1-xSrxTiO 3 (BST) particles are used to demonstrate the particle size effect on the sintering temperature for semiconducting BST. To reduce the sintering temperature, three processes are developed, i.e. 1 using sol-gel nanometer size Sb3+ doped powders with a sintering aid; 2 using micrometer size powders plus a sintering aid; and 3 using nanometer size Sb3+ doped powders with sintering aids. Grain size effect on PTCR characteristics is investigated through comparison between micrometer size powder sintered pellets and nanometer size powder sintered pellets. The former has lower resistivity at temperatures below the Curie temperature (Tc) and high resistivity at temperatures above the Curie temperature (Tc) along with higher ρ max/ρmin ratio (ρmax is the highest resistivity at temperatures above Tc, ρmin is the lowest resistivity at temperatures below Tc), whereas the latter has both higher ρ max and ρmin. Also, ρmax/ρmin is smaller than that of pellets with larger grain size. The reason is that the solid with small grain size has more grain boundaries than the solid with large grain size. The contribution z at room temperature and high temperature and a lower ρmax/ρmin ratio value.

Elemental analysis and forensic comparison of soils by laser-induced breakdown spectroscopy (LIBS) and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS)

The elemental analysis of soil is useful in forensic and environmental sciences. Methods were developed and optimized for two laser-based multi-element analysis techniques: laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and laser-induced breakdown spectroscopy (LIBS). This work represents the first use of a 266 nm laser for forensic soil analysis by LIBS. Sample preparation methods were developed and optimized for a variety of sample types, including pellets for large bulk soil specimens (470 mg) and sediment-laden filters (47 mg), and tape-mounting for small transfer evidence specimens (10 mg). Analytical performance for sediment filter pellets and tape-mounted soils was similar to that achieved with bulk pellets. An inter-laboratory comparison exercise was designed to evaluate the performance of the LA-ICP-MS and LIBS methods, as well as for micro X-ray fluorescence (μXRF), across multiple laboratories. Limits of detection (LODs) were 0.01-23 ppm for LA-ICP-MS, 0.25-574 ppm for LIBS, 16-4400 ppm for μXRF, and well below the levels normally seen in soils. Good intra-laboratory precision (≤ 6 % relative standard deviation (RSD) for LA-ICP-MS; ≤ 8 % for μXRF; ≤ 17 % for LIBS) and inter-laboratory precision (≤ 19 % for LA-ICP-MS; ≤ 25 % for μXRF) were achieved for most elements, which is encouraging for a first inter-laboratory exercise. While LIBS generally has higher LODs and RSDs than LA-ICP-MS, both were capable of generating good quality multi-element data sufficient for discrimination purposes. Multivariate methods using principal components analysis (PCA) and linear discriminant analysis (LDA) were developed for discriminations of soils from different sources. Specimens from different sites that were indistinguishable by color alone were discriminated by elemental analysis. Correct classification rates of 94.5 % or better were achieved in a simulated forensic discrimination of three similar sites for both LIBS and LA-ICP-MS. Results for tape-mounted specimens were nearly identical to those achieved with pellets. Methods were tested on soils from USA, Canada and Tanzania. Within-site heterogeneity was site-specific. Elemental differences were greatest for specimens separated by large distances, even within the same lithology. Elemental profiles can be used to discriminate soils from different locations and narrow down locations even when mineralogy is similar.

Low Temperature Sintering Semiconductive Barium Strontium Titanate

Low temperature sintering has become a very important research area in ceramics processing and sintering as a promising process to obtain grain size below 100nm. For electronic ceramics, low temperature sintering is particularly difficult, because not only the required microstructure but also the desired electronic properties should be obtained. In this dissertation, the effect of liquid sintering aids and particle size (micrometer and nanometer) on sintering temperature and Positive Temperature Coefficient Resistivity (PTCR) property are investigated for Ba1-xSrxTiO3 (BST) doped with 0.2-0.3mol% Sb3+ (x = 0.1,0.2,0.3,0.4 and 0.5). Different sintering aids with low melting point are used as sintering aids to decrease the sintering temperature for micrometer size BST particles. Micrometer size and nanometer size Ba1-xSrxTiO3 (BST) particles are used to demonstrate the particle size effect on the sintering temperature for semiconducting BST. To reduce the sintering temperature, three processes are developed, i.e. 1 using sol-gel nanometer size Sb3+ doped powders with a sintering aid; 2 using micrometer size powders plus a sintering aid; and 3 using nanometer size Sb3+ doped powders with sintering aids. Grain size effect on PTCR characteristics is investigated through comparison between micrometer size powder sintered pellets and nanometer size powder sintered pellets. The former has lower resistivity at temperatures below the Curie temperature (Tc) and high resistivity at temperatures above the Curie temperature (Tc) along with higher ñmax/ñmin ratio (ñmax is the highest resistivity at temperatures above Tc, ñmin is the lowest resistivity at temperatures below Tc), whereas the latter has both higher ñmax and ñmin. Also, ñmax/ñmin is smaller than that of pellets with larger grain size. The reason is that the solid with small grain size has more grain boundaries than the solid with large grain size. The contribution z at room temperature and high temperature and a lower ñmax/ñmin ratio value.

Elemental Analysis and Forensic Comparison of Soils by Laser-Induced Breakdown Spectroscopy (LIBS) and Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS)

The elemental analysis of soil is useful in forensic and environmental sciences. Methods were developed and optimized for two laser-based multi-element analysis techniques: laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and laser-induced breakdown spectroscopy (LIBS). This work represents the first use of a 266 nm laser for forensic soil analysis by LIBS. Sample preparation methods were developed and optimized for a variety of sample types, including pellets for large bulk soil specimens (470 mg) and sediment-laden filters (47 mg), and tape-mounting for small transfer evidence specimens (10 mg). Analytical performance for sediment filter pellets and tape-mounted soils was similar to that achieved with bulk pellets. An inter-laboratory comparison exercise was designed to evaluate the performance of the LA-ICP-MS and LIBS methods, as well as for micro X-ray fluorescence (μXRF), across multiple laboratories. Limits of detection (LODs) were 0.01-23 ppm for LA-ICP-MS, 0.25-574 ppm for LIBS, 16-4400 ppm for µXRF, and well below the levels normally seen in soils. Good intra-laboratory precision (≤ 6 % relative standard deviation (RSD) for LA-ICP-MS; ≤ 8 % for µXRF; ≤ 17 % for LIBS) and inter-laboratory precision (≤ 19 % for LA-ICP-MS; ≤ 25 % for µXRF) were achieved for most elements, which is encouraging for a first inter-laboratory exercise. While LIBS generally has higher LODs and RSDs than LA-ICP-MS, both were capable of generating good quality multi-element data sufficient for discrimination purposes. Multivariate methods using principal components analysis (PCA) and linear discriminant analysis (LDA) were developed for discriminations of soils from different sources. Specimens from different sites that were indistinguishable by color alone were discriminated by elemental analysis. Correct classification rates of 94.5 % or better were achieved in a simulated forensic discrimination of three similar sites for both LIBS and LA-ICP-MS. Results for tape-mounted specimens were nearly identical to those achieved with pellets. Methods were tested on soils from USA, Canada and Tanzania. Within-site heterogeneity was site-specific. Elemental differences were greatest for specimens separated by large distances, even within the same lithology. Elemental profiles can be used to discriminate soils from different locations and narrow down locations even when mineralogy is similar.