Thesis (Ph. D.)--Columbia University, 1924. / Vita.

No description available.

The widespread use of high temperature superconductors through improved understanding of their underlying physics is in part dependent on the synthesis of large, high quality single crystals for physical research. Crucible corrosion is an important factor hindering the routine synthesis of large, high purity rare-earth barium cuprate superconductor single crystals. Molten BaCuO2-CuO fluxes required for the growth of such crystals are highly corrosive to substrate materials, and corrosion products may lead to chemical contamination of crystals and other practical difficulties. BaZrO3 is known to be inert to BaCuO2-CuO melts, but its use has remained restricted to a very small number of laboratories worldwide because it is very sensitive to the effects of off- stoichiometric or residual secondary phases which degrade its performance. BaZrO3 suitable for sustained melt containment is difficult to produce due to kinetic limitations of phase purity, difficulty in sintering to adequate density, and very narrow stoichiometry tolerances of finished ceramics. The existing literature provided a guide to the production of high quality BaZrO3, but was not sufficiently complete to readily allow production of crucibles suitable for this application. The two basic aims of this project were: To provide a comprehensive and quantitative description of the necessary attributes of crucibles for barium cuprate melt processing and to expand the knowledge of solid-state BaZrO3 processing to encourage its widespread application to crucible manufacture; To explore the application of solution chemical processes whose potential benefits could lead to routine application of BaZrO3 through improved ceramic quality and processing properties. / Based primarily on solid-state processing research, the optimal stoichiometry for corrosion resistant crucibles was observed over the narrow range of 1.003±0.003 Ba : (Zr + Ht) mole ratio. Residual ZrO2 must be strictly avoided even at very low levels because severe localized expansion of Z a grains during reaction with the melt severely reduces corrosion resistance. Although the effect of Ba-rich phases are less severe, their abundance must be suppressed as much as allowed by the production process. Solid-state derived crucibles with a large barium excess were unstable and readily attacked by water. TEM analysis clearly showed residual Zr02 was present as discrete grains and not as grain boundary films, and also the prevalence of intragranular defects in Ba-rich ceramics. Quantitative knowledge of the narrow range of required stoichiometry is critical for developing successful solid-state and solution chemical processes. Reliably achieving the required stoichiometry and phase purity is experimentally challenging and beyond the capability of many processing systems. Systematic investigation revealed sharp changes in physical properties of processed powders across the phase boundary. The resistance of BaZrO3, of the desired stoichiometry to grain growth during powder processing has not previously been reported in the available literature. At the desired stoichiometry for corrosion resistance, powder grain growth resistance combined with very precise control over stoichiometry makes the solid-state process more competitive with solution-based processes than previously acknowledged in the literature. The development of solution processes for BaZr03 precursors is complicated by aqueous chemistry of zirconium compounds. / This project developed the first chemically derived precursor process demonstrated to produce a ceramic of adequate quality for sustained barium cuprate melt containment. The barium acetate / zirconium oxychloride / ammonium oxalate system provided control over stoichiometry without requiring elevated solution temperatures, a large excess of barium reagents, or reagents containing alkalis. Despite showing the capability to supersede the solid-state process, the oxalate process still requires further refinement to more reliably achieve high sintered densities. Although the attributes required for sustained barium cuprate melt containment are now clear, its routine mass production remains reliant on further development of solution chemical techniques or improvements to the kinetics of solid-state processing. This project advanced ceramic design and processing technology in the BaZrO3 system and provided new approaches in meeting the challenging analytical needs of research and process control for high quality production of this compound.

Indiana University-Purdue University Indianapolis (IUPUI) / Statement of problem: Yttria-partially stabilized tetragonal zirconia polycrystal (Y-TZP) all-ceramic restorations have been reported to suffer from chipping or cracking of the veneering porcelain (VP) as the most common complication. There is little information in the literature regarding the influence of surface treatment on VP shear bond strength to Y-TZP after cyclic loading. Purpose of this study: The goals of this study were (1) to investigate the influence of zirconia surface treatments on veneering porcelain shear bond strength and (2) to investigate the influence of cyclic loading on the shear bond strength between VP and Y-TZP. Materials and Methods: 48 cylinder–shaped specimens (6mm in diameter and 4mm in height) were divided into 4 groups containing 12 specimens each according to the surface treatment. As a control group (C), no further treatment was applied to the specimens after grinding. Group H was heat-treated as a pretreatment according to the manufacturer’s recommendations. Group S was airborne-particle abraded with 50 µm alumina (Al2O3) particles under a pressure of 0.4 MPa for 10 seconds. In the group SH, the heat-treatment was performed after the airborne-particle abrasion. A VP cylinder (2.4 mm in diameter and 2 mm in height) was applied and fired on the prepared Y-TZP specimens. The shear bond strength was tested using a universal testing machine. Six specimens from each group were subjected to fatigue (10,000cycles, 1.5Hz, 10N load) before testing. Results: The 3-way ANOVA showed no statistically significant effect of surface treatment and cyclic loading on shear bond strength. The highest mean shear bond strength was recorded for the air-particle abrasion group without cyclic loading (34.1 + 10 MPa). The lowest mean shear bond strength was the air-particle abrasion group with cyclic loading (10.7 ± 15.4 MPa). Sidak multiple comparisons procedure demonstrated cyclic loading specimens had significantly lower shear bond strength than non-cyclic loading specimens after air-particle abrasion without heat treatment (p=0.0126) Conclusion: Within the limitations of this study, (1) Shear bond strength between Y-TZP and VP is not affected statistically by surface treatment using heat treatment, airborne-particle abrasion, and heat treatment after airborne-particle abrasion. (2) There is significant difference in shear bond strength with air-particle abrasion between with and without cyclic loading groups. This difference suggested that air-particle abrasion should be avoided in clinical situations as a surface treatment without heat treatment.

Indiana University-Purdue University Indianapolis (IUPUI) / The objectives: 1. To compare the flexural strength, flexural modulus, and fracture toughness of specimens fabricated from recently marketed translucent full-contour zirconia, traditional zirconia, and lithium disilicate glass ceramic. 2. To compare the load-to-failure of crowns fabricated from recently marketed translucent full-contour zirconia, traditional zirconia, and lithium disilicate glass ceramic at their recommended tooth-reduction thickness. Methodology: Four groups of translucent zirconia (BruxZir, KDZ Bruxer, CAP FZ, Suntech zirconia), one group of traditional zirconia (CAP QZ) and IPS e.maxCAD) were tested. Twelve bars of each material were made and tested for flexural strength, and fracture toughness. Fracture patterns were imaged under SEM. Forty-eight crowns (8 from each group) were fabricated with CAD/CAM technique following manufacturers’ recommendations for the amount of tooth reduction. All the crowns were cemented to prepared epoxy resin dies with RelyX Unicem and tested for static load to failure in a universal machine. Result: In bar-shape samples, CAP QZ (traditional zirconia) showed the highest flexural strength (788.12 MPa), fracture toughness (6.85 MPa.m1/2), and fracture resistance (2489.8 N). All translucent zirconia groups show lower mechanical properties than QZ. However, there were no differences between translucent and traditional zirconia in the fracture resistance of the crown-shape samples. There was no significant difference in fracture resistance between IPS e.max crowns at recommended thickness and other zirconia crowns at recommended thickness. Conclusion: With less reduction of tooth structure, a high inherent strength and chip resistance make full-zirconia crowns a good alternative to porcelain-fused-to-metal crowns and all other ceramic crowns.

Indiana University-Purdue University Indianapolis (IUPUI) / The objective of this study was to evaluate the in vivo performance of the hydroxyapatite (HA) coating and hydrofluoric acid (HF) etching zirconia (ZrO) implants and to compare the result with titanium (Ti) implants treated in a similar manner. A total of four different implant types were tested in this study. Threaded zirconia implants with HA coating (Test 1) and zirconia implants with HF-treated surfaces (Test 2) were used to compare to the same size of titanium implants treated in identical fashion (control 1 and control 2). All implants measured about 3.5 mm at the thread diameter and 7.0 mm in total length. Each rabbit received two zirconia and two titanium implants treated in the same manner (either HA-coated or HF-etched). The samples were implanted into the rabbit tibias and retrieved at 6 weeks. Upon retrieval, 24 specimens (6 samples for each group) were fixed and dehydrated. The samples were then embedded undecalcified in PMMA for histomorphometry to quantify the bone-to-implant contact (BIC). Another 24 samples were kept in 0.9% saline and were evaluated using removal torque (RT) analysis to assess the strength of the implant-to-bone interface. The histomorphometric examination demonstrated direct bone-to-implant contact for all four groups. HA particle separation from the implants surface was seen in a majority of the HA-coated samples. No signs of inflammation or foreign body reaction were found during examination. Due to the HA particle smear contamination in the ZrO-HA group, no data was collected in this group. The mean BIC at the first three threads of the Ti-HA, Ti-HF and ZrO-HF were 57.78±18.22%, 46.41±14.55% and 47.41±14.05%, respectively. No statistically significant difference was found pair-wise among these three groups. When comparing the BIC data with the machined-surface implants, a statistically significant difference was found between the Ti-HA versus Ti implant group and the Ti-HF versus Ti implant group. The mean bone area (BA) at the first three threads for Ti-HA, Ti-HF and ZrO-HF showed statistically significant difference (p<0.05) between the ZrO-HF and Ti-HA groups, favoring the ZrO-HF group. The value of the peak removal force could only be collected from the Ti-HA group during the removal torque test. The mean RT value for the Ti-HA group was 24.39±2.58 Ncm. When comparing the RT result with our pilot study using machined-surface implants, the Ti-HA group showed statistically significant (p<0.05) higher values than the machined-surface Ti implants. The result of this study proves the in vivo biocompatibility of all four implant types tested. In the three measurable implant groups, the histomorphologic analysis showed comparable osseointegration properties in this animal model.

Indiana University-Purdue University Indianapolis (IUPUI) / The use of yttria-stabilized tetragonal zirconia polycrystal (Y-TZP), normally employed as a framework for all-ceramic restorations, has now started to be used without any veneering ceramics in patients with parafunctional activities. The aims of this study were to evaluate the influence of Y-TZP surface roughness on the wear behavior (volume/height loss) against glass-based ceramics (i.e., IPS Empress CAD and IPS e.max CAD, Ivoclar-Vivadent). Thirty-two Y-TZP full-contour zirconia (Ardent®) sliders (ϕ=2 mm, 1.5 mm in height) were milled in a CAD/CAM unit and sintered according to the manufacturer instructions. Sliders were embedded in brass holders using acrylic resin and then randomly allocated into 2 groups according to the surface treatment (n=16): G1-as-machined and G2-glazed (Diazir®). Empress and e.max antagonists were cut into tabs (13×13×2 mm) wet-finished and also embedded in brass holders. Two-body pin-on-disc wear testing was performed at 1.2 Hz for 25,000 cycles under a 3-kg load. Non-contact profilometry was used to measure antagonist height (μm) and volume loss (mm3). Qualitative data of the testing surfaces and wear tracks were obtained using SEM. Statistics were performed using one- and two-way ANOVAs (α=0.05). The results indicated that G1 yielded significantly higher mean roughness values (Ra=0.83 μm, Rq=1.09 μm) than G2 (Ra=0.53 μm, Rq=0.78 μm). Regarding antagonist loss, G1 caused significantly less antagonist mean height and volume loss (68.4 μm, 7.6 mm3) for Empress than G2 (84.9 μm, 9.9 mm3) while no significant differences were found for e.max. Moreover, Empress significantly showed lower mean height and volume loss than e.max (p<0.0001). SEM data revealed morphological differences on wear characteristics between the two ceramics against Y-TZP. Within the limitations of this study, e.max wear was not affected by Y-TZP surface roughness. However, Empress wear was greater when opposing glazed Y-TZP. Overall, based on our findings, surface glazing on full-contour Y-TZP did not minimize glass-ceramic antagonist wear when compared with as-machined group.

Indiana University-Purdue University Indianapolis (IUPUI) / THE EFFECT OF FULL-CONTOUR Y-TZP CERAMIC SURFACE ROUGHNESS ON THE WEAR OF BOVINE ENAMEL AND SYNTHETIC HYDROXYAPATITE: AN IN-VITRO STUDY by Alaa Hussein Aref Sabrah Indiana University School of Dentistry Indianapolis, Indiana Full-contour yttrium-stabilized tetragonal zirconia polycrystal (Y-TZP) restorations have been advocated recently in clinical situations where occlusal/palatal space is limited, or to withstand parafunctional activities. The objectives of this in-vitro study were to investigate the effects of different polishing techniques on the surface roughness of Y-TZP (Ardent Dental, Inc.) and to investigate the effects of different polishing techniques on the wear behavior of synthetic hydroxyapatite (HA) and bovine enamel. An in-vitro study was conducted by fabrication of 48 Y-TZP sliders (diameter = 2 mm × 1.5 mm in height) using CAD/CAM technique; then the samples were embedded in acrylic resin using brass holders. Samples were then randomly allocated into four groups according to the finishing/polishing procedure: G1-as-machined (n = 8), G2- glazed (n = 16), G3-diamond bur-finishing (Brasseler, USA) (n = 8) and G4- G3+OptraFine polishing kit (Ivoclar-Vivadent) (n = 16). Thirty-two sintered HA disks (diameter = 11 mm × 2.9 mm in height) and 16 bovine enamel samples with a minimum surface area of 64 mm2 were mounted in brass holders. Baseline surface roughness (Ra and Rq, in μm) were recorded using a non-contact profilometer (Proscan 2000) for all the samples. A two-body pin-on-disk wear test was performed for 25,000 cycles at 1.2 Hz in which the four zirconia groups were tested against HA, and only G2-glazed and G4- G3+OptraFine polishing kit (Ivoclar-Vivadent) were tested against bovine enamel. Vertical substance loss (μm) and volume loss (mm3) of HA were measured (Proscan). Zirconia height loss was measured using a digital micrometer. One-way ANOVA was used for statistical analysis. The results indicated that surface roughness measurements showed significant differences among the surface treatments with G1 (Ra = 0.84, Rq = 1.13 μm) and G3 (Ra = 0.89, Rq = 1.2 μm) being the roughest, and G2 (Ra = 0.42, Rq = 0.63 μm) the smoothest. The glazed group showed the highest vertical loss (35.39 μm) suggesting wear of the glaze layer, while the polished group showed the least vertical loss (6.61 μm). HA antagonist volume loss and vertical height loss for groups (G1, G2 and G3) were similar, while polished group (1.3 mm3, 14.7 μm) showed significant lower (p = 0.0001) values. Antagonist height loss and antagonist volume loss were significantly higher for bovine antagonist than for HA antagonist (197.6 μm/116.2 μm, and 28.5 mm3/17.7 mm3 for bovine against glazed/polished zirconia sliders, respectively) (p < 0.0001). From the results it can be concluded that glazed zirconia provided an initially smooth surface, but a significant increased antagonist wear compared with the polished surface was seen. Bovine enamel showed higher wear compared with HA, which suggested that more studies should be performed to validate the use of bovine enamel as a substitute for human enamel in wear studies.