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OBJECTIVES: The purpose of this study was to investigate the influence of saliva contamination and subsequent surface treatments on the shear bond strength of two different resin cements to zirconia. MATERIALS AND METHODS: One hundred sintered zirconia specimens were divided into two groups (n=50), one for each resin cement to be tested. Each group was divided into five sub-groups (n=10) based on the surface treatment the zirconia plates were going to receive; namely control (CL), saliva contaminated (SC), water washed (WW), Ivoclean (IC) and air abrasion (AA). In the control group, no contamination or surface treatment was performed. Specimen surfaces of the rest of the experimental groups were contaminated with saliva, and then submitted to drying with air only (SC); washed with water (WW); treated with Ivoclean cleaning paste (IC); or sandblasted with aluminum oxide particles (Al2O3) (AA). Multilink Automix (MA) and RelyX Ultimate (RU) resin cement cylinders were made and bonded to conditioned zirconia specimens using the Ultradent jig method. All bonded specimens were placed inside glass containers filled with deionized water inside an incubator at 37 °C for 24 h. After 24 h, the shear bond strength of the bonded specimens was tested using an Instron Universal Testing Machine with a crosshead speed of 0.5 mm/minutes. Statistical analysis was performed by ANOVA and data were analyzed with Tukey-Kramer HSD multiple comparison tests at the 0.05 level of significance. RESULTS: Within the limitations of this in vitro study, it was determined that saliva contamination significantly reduced resin bond strengths to zirconia ceramic. Airborne-particle abrasion was the most effective cleaning and surface treatment. It significantly increased the shear bond strength of (MA) (13.73 ± 1.39 MPa) and (RU) (6.34± 0.8 MPa). The IC was effective in removing saliva contamination and enhancing the resin bond strength of (MA) (10.9 ± 1.28 MPa) and (RU) (3.1± 0.16MPa). Water did not remove saliva contamination and did not improve (RU) bond strength to zirconia (1.73 ± 0.25 MPa). There was no significant difference (p>0.05) between the shear bond strengths of (MA), water washing (4.7± 0.64 MPa), and control groups (4.9± 0.27 MPa). CONCLUSIONS: If contamination occurs, a surface treatment is required to guarantee an adequate interaction between the resin cement and the zirconia surface. Airborne-particle abrasion and Ivoclean surface treatments are effective in removing saliva contamination and enhancing the resin bond strength. Washing with water alone did not improve resin bond strength.

Currently, industrial processes that produce silicon occur in batch units which are energy intensive, capital intensive, and emit harmful pollutants into the atmosphere. A new technology, solid oxide membrane (SOM) processing, seeks to produce silicon without direct emissions and with lower energy and capital costs. Previous studies have shown that this technology can produce silicon; however, the proof-of- concept cell was incapable of producing large volumes of silicon due to restrictions in the molten salt. Current research has engineered an oxyfluoride molten salt to be more efficient in four main ways: higher amount of silica in the molten salt, chemistry stable with the yttria-stabilized zirconia (YSZ) membrane, low volatility, and high electrical conductivity. The newly designed salt allows for up to 25 at% of silicon oxide to dissolve into the flux, removing mass transfer limitations. The mixture utilizes calcium oxide to stabilize the presence of silicon oxide, giving the flux a volatility of less than 0.1 µg/cm 2 *s. The presence of calcium oxide also increases the optical basicity of the system, allowing the flux to be compatible with the YSZ membrane showing no signs of corrosion. Lastly, the new flux composition has a conductivity of 2.87 and 4.38 S/cm, at 1050 °C and 1100 °C, respectively, which is above the desired value of 1 S/cm. vii Combining these improvements in the salt with pre-existing techniques, silicon crystals were produced in the new SOM cell. Two distinct SOM cell configurations were attempted, one with a liquid cathode (tin) and one with a solid cathode (molybdenum). Both cells were able to successfully make silicon metal. The tin cathode was able to produce high purity silicon crystals extracted via acid etching. The molybdenum cathode produced a plated layer of molybdenum disilicide. Samples were examined by using scanning electron microscopy (SEM) and energy dispersive x-ray spectroscopy (EDS). An equivalent circuit model for the SOM process was developed to calculate polarization losses during the electrolysis process.

OBJECTIVES: To evaluate various cements in vitro for adhesion to zirconia, light curing vs. self-curing, the effect of particle abrasion (APA) on the zirconia intaglio for maximizing retention, the effect of thermocycling, and the effect of cement space. METHODS: The tested cements included: Ceramir C&B (Doxa) Panavia F2.0 (Kuraray); Multilink Automix (Ivoclar); Theracem (Bisco); Duolink (Bisco); Bifix (Shofu); CemEZ (Zest Dental). For testing cements retention, custom made zirconia rings 12.5 mm outer diameter, 5.5 mm height and 6.147 mm inner diameter were used to emulate crowns. Round steel rods (McMaster) were manufactured to fit into the zirconia rings allowing a cement space of 50 Microns or 100 Microns. A cementing jig was used to keep the rods at the center of the zirconia rings. Cements were tested using light curing and self-curing (n=10 per each test). Groups of zirconia rings were air braded with 100 Microns aluminum oxide particles for 10 Sec. Half the specimens were stored in water for 24 hours at 37o C in dark environment or thermocycled for 5000 cycles. A ‘push-out’ test using an Instron universal machine at a crosshead speed of 0.5mm/min. Loads to failure were recorded to calculate cements retention. RESULTS: Statistical analysis was performed using JMP Pro 13 software. Data were analyzed using one way ANOVA, multiple t-test, and Tukey-Kramer HSD. For self curing method without APA, retention strength ranking for tested cements were: Ceramir C&B ≥ Theracem > Panavia F2.0 ≥ Duolink ≥ Multilink Automix ≥ Bifix. For light curing method without APA, retention strength ranking for tested cements were: CemEZ ≥ Theracem ≥ Multilink Automix ≥ Duolink ≥ Bifix ≥ Panavia F2.0. There was a significant influence in retention strength for light cured cements compared to self-curing method except for Theracem and Panavia F2.0. For the self-curing method with APA, retention strength ranking for tested cements were: Theracem > Duolink ≥ Panavia F2.0 ≥ Multilink Automix ≥ Bifix > Ceramir C&B. For the light curing method with APA, retention strength ranking for tested cements were: Theracem ≥ Multilink Automix ≥ CemEZ ≥ Duolink ≥ Panavia F.0 ≥ Bifix. A significant increase in retention strength with APA compared to self-curing method with APA. There was no significant effect of thermocycling treatment on retention strength of the cements tested. There was no significant effect of different cement spaces on retention strength except for Ceramir C&B without APA and Multilink Automix with and without APA (P < 0.0001). CONCLUSIONS: 1- There was a significant difference in retention strength to zirconia among tested cements in self and light curing methods. 2- Light curing resin cements influenced retention strength to zirconia for the tested cements. 3- APA influenced the retention strength to zirconia for tested cements except for Ceramir C&B. 4- Increasing the cement space from 50μm to 100μm had no significant difference in retention strength to zirconia except for Ceramir C&B without APA and Multilink Automix with and without APA. 5- Thermocycling had no significant effect of on retention strength to zirconia for the tested cements. / 2020-07-30T00:00:00Z

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第19729号 / 工博第4184号 / 新制||工||1645(附属図書館) / 32765 / 京都大学大学院工学研究科物質エネルギー化学専攻 / (主査)教授 江口 浩一, 教授 安部 武志, 教授 陰山 洋 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

Zirconia based ceramics are strong, hard, inert, and smooth, with low thermal conductivity and good biocompatibility. Such properties made zirconia ceramics an ideal material for different applications form thermal barrier coatings (TBCs) to biomedicine applications like femoral implants and dental bridges. However, this unusual versatility of excellent properties would be mediated by the metastable tetragonal (or cubic) transformation to the stable monoclinic phase after a certain exposure at service temperatures. This transformation from tetragonal to monoclinic, known as LTD (low temperature degradation) in biomedical application, proceeds by propagation of martensite, which corresponds to transformation twinning. As such, tetragonal to monoclinic transformation is highly sensitive to mechanical and chemomechanical stresses. It is known in fact that this transformation is the source of the fracture toughening in stabilized zirconia as it occurs at the stress concentration regions ahead of the crack tip. This dissertation is an attempt to provide a kinetic-based model for tetragonal to monoclinic transformation in zirconia. We used the phase field technique to capture the temporal and spatial evolution of monoclinic phase. In addition to morphological patterns, we were able to calculate the developed internal stresses during tetragonal to monoclinic transformation. The model was started form the two dimensional single crystal then was expanded to the two dimensional polycrystalline and finally to the three dimensional single crystal. The model is able to predict the most physical properties associated with tetragonal to monoclinic transformation in zirconia including: morphological patterns, transformation toughening, shape memory effect, pseudoelasticity, surface uplift, and variants impingement. The model was benched marked with several experimental works. The good agreements between simulation results and experimental data, make the model a reliable tool for predicting tetragonal to monoclinic transformation in the cases we lack experimental observations.

In order to increase the efficiency and economic viability of solid oxide fuel cells (SOFCs), new materials for the cathode, anode, and electrolyte of the cells must be found. SOFCs have a ceramic electrolyte, which is commonly made of fully stabilized zirconia. Due to increased material degradation rates at elevated temperatures ( ~ 1000°C) of current SOFCs, materials for the manufacture of intermediate temperature SOFCs, which operate in the range of 700-800°C, are currently under study. In this study, the manufacturing process for scandia-ceria stabilized zirconia powder (1 0mol¾ Sc2O3, lmol¾ CeO2, 89mol% ZrO2), from Daiichi Kigenso Kagaku Kogyo (DKKK) is developed, including tape casting and sintering procedures to result in pellets of high enough quality to produce single button cells. It is found that a slip prepared with about 44 wt% zirconia powder and increased proportions of solvents, dispersant, binder and plasticizers produces a favorable viscosity of about 7 40cP after deairing, and will produce tapes that are reasonably smooth and of stable thickness. Since the single cell will be structurally based upon this electrolyte material, the physical properties of the pellets are important, in addition to the electrochemical properties of the constituent materials. Tapes cast at 500µm, at 50% feed rate with a 50°C drying temperature, laminated and sintered at 1500°C on setter plates will produce flat, smooth, stiff pellets for the production of single buttons for use as the electrolyte. Cathode (50-50 mixture of La0.6Sr0_4Fe0_8Co0.2O3 + 20mol% Gd2O3 80mol% CeO2) and Anode (35 wt% DKKK powder, 65 wt% NiO) materials were hand-painted on to either side of the electrolyte and sintered to create a complete SOFC cell consisting of cathode, electrolyte, and anode.

Processing of ceramics has always been difficult due to how hard and brittle the material is. Fused Deposition of Ceramics (FDC) is a method of additive manufacturing which allows ceramic parts to be built layer by layer, abetting more complex geometries and avoiding the potential to fracture seen with processes such as grinding and milling. In the process of FDC, a polymeric binder system is mixed with ceramic powder for the printing of the part and then burned out to leave a fully ceramic part. This experiment investigates a new combination of materials, zirconia and acrylic binder, optimizing the process of making the material into a filament conducive to the printer system and then performing trials with the filament in the printer to assess its feasibility. Statistical analysis was used to determine optimal parameter levels using response surface methodology to pinpoint the material composition and temperature yielding the highest quality filament. It was discovered that although the mixture had adequate melting characteristics to be liquefied and printed into a part, the binder system did not provide the stiffness required to act as a piston to be fed through the printer head. Further studies should be completed continuing the investigation of zirconia and acrylic binder, but with added components to increase strength and rigidity of the filament.

OBJECTIVES: This in-vitro study aimed to evaluate the effect of hydrofluoric acid etching and airborne particle abrasion on zirconia bond strength, using three different types of cement. To assess the impact of hydrofluoric acid etching on zirconia surface roughness and investigate the effect of hydrofluoric acid etching on zirconia's surface topography, microstructure, and crystal structure. MATERIALS AND METHODS: Crown-abutment simulation systems were constructed, using a custom-made zirconia tapered ring model and tapered titanium pin-abutments. Twelve groups were included in the study and classified according to the surface treatment and type of cement used. Each group had 10 specimens for a total of 120 test specimens. The fully sintered zirconia ring was alumina particle abrasion (APA) treated with a 50-μm alumina and/or etched with 9.5% HF acid, solution for 1 minute. The Ti pin was APA treated with 125-μm alumina. Three different types of cement were used: one RMGIC (GC FujiCem Evolve) and two resin composite types of cement (Panavia SA Universal and Panavia V5). A cementing jig was used to standardize the cementation process of the titanium pins to the zirconia rings. An Instron was used to obtain the retention load values. The failure load between the zirconia ring and the titanium pin was determined using an axial pullout test and the values were statistically analyzed for the effects of etching treatment, APA treatment, and cement type using JMP Pro 16. Zirconia-disk specimens were constructed using a custom-made disk model. Thirteen groups were included in the study and classified according to the hydrofluoric acid etching concentrations, consistencies, and timing used. Each group had 3 specimens. The total specimen size was thirty-nine specimens. Disks were polished and etched using 5% HF, 9.5% HF, and 40% HF acid etching concentrations, gel, and solution consistencies, and for 1 and 15 minutes of etching time. Disks were examined with an SEM, X-Ray diffractometer, and a profilometer for microstructure, crystallography, and surface roughness, respectively. RESULTS: HF acid-etching treatment significantly increased retention load compared to non-etched groups. There was no significant difference in retention load between APA-treated and non-APA-treated groups. Groups cemented with Panavia V5 showed a higher retention load compared to GC FujiCem Evolve and Panavia SA Universal. There was no significant difference in the surface roughness among the etched groups and the control groups. Roughening of the crystal boundaries with irregularities and pits was observed under SEM. As etching time and concentration increased the surface became rougher and more irregular. There were no obvious crystal structure differences between the etched groups and non-etched groups. CONCLUSIONS: Significantly different retention loads were found among tested groups. Hydrofluoric acid etching increases the bond strength of zirconia and titanium, using resin composite cement. Using hydrofluoric acid etching to pre-treat the zirconia surface may be an alternative approach to obtain sufficient bonding strength.

Zirconia has been established as a promising material for dental implants. Various surface treatment methods have been utilized to promote better osseointegration and improve the success rate of dental implants. However, a better understanding of the influences of topographic characteristics on cell attachment, proliferation, and differentiation is needed. Different surface topographic zirconia specimens, As sintered, Mild rough, Moderate rough, and Rough zirconia groups were fabricated with sandblasting method in various distances and stages. The surface texture, microstructure, and wettability were inspected with the optical profiler, SEM, and contact angle measurement respectfully. Human primary osteoblast cells were cultured on the four groups of zirconia with different surface modifications in 24 well plates and on plates without test material as control. Crystal violet and triton X-100 solution were used to evaluate cell attachment efficiency at 9 hours and proliferation rate at 7, 14, and 21 days after seeding. ALP activity was measured with fluorometric assay. The expression of osteocalcin was measured with an ELISA kit. Alizarin red staining was conducted to evaluate the mineralization. The cell morphologies were inspected under SEM after cell fixation and critical point drying process. The data were analyzed with one-way ANOVA for experiment on each time interval and two-way ANOVA for all time points. Tukey post hoc test was used for pairwise comparison. P value < 0.05 was considered statistically significant. Topographic parameters and contact angle measured in As sintered, Mild rough, Moderate rough, and Rough surface groups were as follow: Sa = 0.23, 0.50, 2.13, 5 µm, Sal = 49.88, 21.20, 30.42, 49.87 µm, Sdq = 64.64, 248.60, 511, 734.66 µm/mm, Sk = 0.7, 1.54, 4.19,16 µm, Spk = 0.31, 0.64, 1.47, 5.13 µm, Svk = 0.35, 0.71, 5.96, 6.18 µm respectively, and contact angle = 64.6°, 55.2°, 43.5°, 38.6° respectively. The result showed that Rough zirconia group induced the highest cell attachment efficiency at 9 hours (p<.001). As sintered zirconia group promoted significant cell proliferation rate at 21 days (p<.001) while Rough zirconia group drastically down-regulated cell proliferation (p<0.001). The most elevated levels of ALP, osteocalcin, and mineralization expressions at 21 days were found in the Moderate rough group with significant differences (p<.001, p<.001, p<.001 accordingly) Within the limitations of this in vitro study, it can be concluded 1) the modified microroughened zirconia surfaces of Sa 5 µm would promote human osteoblast attachment but down-regulate cell proliferation, 2) the As sintered zirconia surface would stimulate cell proliferation, and 3) the microroughened surfaces of Sa 2 µm would up-regulate osteoblast differentiation. These findings could be incorporated into designing and fabricating the dental implant surfaces for optimal osseointegration.