Biodiesel is currently produced by homogeneous catalysis. More recently however, heterogeneous catalysis is being considered as a cheaper alternative to the homogeneous process. In this research project, heterogeneous catalysts of zirconium oxide were produced by impregnation. Zirconium oxide impregnation with sulfuric acid produced acidic solid catalysts. It was determined that impregnation and calcination at 550^oC (SO₄/ZrO₂-550^oC) produced the best catalyst for palmitic acid esterification with 10 wt % as the optimum concentration in esterification of palmitic acid. SO₄/ZrO₂-550^oC was successfully recycled for eight consecutive runs before permanent deactivation. Its sulfur content was 1.04 wt % using SEM-EDS and 2.05 wt % using XPS for characterization. BET surface area was 90.89 m2/g. The reaction mechanism over Brønsted acid (SO₄/ZrO₂-550^oC) and Lewis acid (Al₂O₃) catalysts obeyed Eley-Rideal kinetics with palmitic acid and methanol adsorbed on the active site respectively. Zirconium oxide was also impregnated with sodium hydroxide to produce basic catalysts. The best catalyst was produced when zirconium oxide was impregnated with 1.5 M NaOH and calcined at 600^oC. Soybean oil was completely converted to biodiesel with 10 wt % catalyst and 1:6 oil to methanol. A mixture of the base catalyst with 30 wt % SO₄/ZrO₂-550^oC effectively converted soybean oil containing 5% oleic acid indicating that this mixture could be used for waste oils. The reaction was first order with respect to triglyceride and second order with respect to methanol. The activation energy was 49.35 kJ/mol and the reaction mechanism obeyed Langmuir-Hinshelwood kinetics. / Master of Science

No description available.

published_or_final_version / abstract / Chemistry / Doctoral / Doctor of Philosophy

Call number: LD2668 .T4 1957 S57 / Master of Science

STATEMENT OF PROBLEM. Yttria-stabilized tetragonal zirconia polycrystal (Y-TZP) ceramic material has been reported to possess remarkably high flexural strength; however, after sintering zirconium dioxide (ZrO2) frameworks and fixed partial dentures, some may not fit properly when trying them on their master cast. PURPOSE. The objective of this study was to investigate joining fully sintered YTZ-P by various methods including adhesive cements or fusion with intervening materials. MATERIALS AND METHODS. 216 specimens were used in this study; bars were fabricated from Vita In-Ceram YZ blocks and three bars were joined using dental cements; RelyX Unicem 2 Clicker and Multilink Automix, or fusing them with VM9, Infusion Glass, Boron Oxide, Aluminum Oxide, LUDOX, Colloidal Zirconia and Mullite Zirconia. The load to failure in Newtons was determined using a 3-point bending test. RESULTS. Sandblasted bars for RelyX (64.38N, RelyX-A-Sb) and Multilink (48.58N, M-Sb) wasn’t significantly higher compared to as-sintered groups (45.87N, RelyX-A) and (34.69N, M-A). Coating the bars with Monobond-Plus had a significantly higher load to failure 123.22N, RelyX-A-MP and 136.06N, M-MP compared to as-sintered and sandblasted groups. VM9 at an end firing temperature (EFT) of 1200 °C was significantly higher (228.97N, V-5) compared to lower fusing temperatures. Glass at an end firing temperature of 1200 °C was significantly higher (460.32N, G-6) compared to lower fusing temperatures. Frit at an end firing temperature of 1200 °C was significantly higher (214.52N, F-6) compared to lower fusing temperatures. Optical microscopy showed that Glass group G-6 (1200°C, EFT) had a thickness range from .09 to 0.03 mm while for Glass-A (1050°C, EFT) it was 0.5 mm. CONCLUSIONS. Within the limitations of this study, we concluded that sandblasted bars didn’t significantly increase the means load to failure values compared to as-sintered groups. Coating the bars with Monobond-Plus had a significantly higher load to failure compared to as-sintered and sandblasted groups. VM9, Glass and Frit at an end firing temperature of 1200 °C showed significantly higher means load to failure compared to lower fusing temperature groups. / 2018-09-28T00:00:00Z

No description available.

The following thesis outlines work carried out during the last three years for the development and investigation of methodologies using amides as N- and O- acylating agents. Chapter 1 highlights the range of methodologies and protocols reported in the literature that use amides as precursors for the synthesis of both functionalised amides and esters. The introduction will highlight the range of catalysts and promoters used as well as the scope of the current methodologies. As well as this it will highlight the limitations of the methodologies so emphasising where the following research fits into these areas. Chapter 2 presents the development of a transamidation methodology using zirconocene dichloride as a catalyst. The scope with respect to functional group tolerance is presented as well as the investigations into the mechanism of the reaction. Chapter 3 builds on the research presented in Chapter 2 and details the development of a more catalytically active zirconocene transamidation methodology. By the addition of a catalytic additive the temperature or time required for the reaction to be carried out could be lowered. Investigations into the mechanism were also carried out highlighting the in situ formation of an active catalytic species. Chapter 4 details the development of an operationally simple methodology for the O-acylation of alcohols using amides. Using a catalytic amount scandium triflate the substrate scope of the reaction was explored with a proposed mechanism presented based on activation of the amide.

Orientador: Gelson Luis Adabo / Banca: Renata Garcia Fonseca / Banca: Igor Studart Medeiros / Resumo: Este estudo caracterizou mecanicamente uma porcelana feldspática de aplicação convencional e uma porcelana feldspática prensada, indicadas para infraestrutura em zircônia, quanto a resistência à flexão biaxial, dureza Vickers e tenacidade à fratura. Além disso, foi investigado o efeito da taxa de resfriamento após o ciclo de sinterização do glaze da porcelana na resistência à flexão biaxial de bicamadas zircônia/porcelana. Espécimes monocamada de VM9 (n=15) e Vita PM9 (n=15) (12,0 mm de diâmetro x 1.2 mm de espessura) foram confeccionados conforme as recomendações do fabricante e submetidos ao ensaio de resistência à flexão biaxial (MPa). Um fragmento de cada espécime fraturado foi aleatoriamente selecionado para a mensuração da dureza Vickers (n=15) (VHN). A tenacidade à fratura aparente(MPa.m½) foi determinada pela técnica da indentação Vickers (n=15). Para o ensaio de flexão biaxial dos bicamadas, discos de zircônia (Vita In-Ceram YZ) foram recobertos com porcelana convencional Vita VM9 (n=30) ou com porcelana prensada Vita PM9 (n=30). Após a simulação da queima de glaze, os espécimes foram submetidos a resfriamento rápido (n=15) ou lento (n=15). Após o ensaio de resistência à flexão, os espécimes foram analisados quanto ao tipo de fratura. Teste de T-Student para espécimes monocamada mostrou que Vita PM9 apresentou valores significantemente maiores de resistência à flexão biaxial (p<0,01) e dureza (p=0,017) em relação a Vita VM9, mas não quanto a tenacidade à fratura (p= 0.41). ANOVA a dois fatores (porcelana e método de resfriamento), utilizada para análise dos bicamadas indicou significância apenas para porcelanas, com superioridade para a combinação Vita PM9/zircônia (p<0,01). Porcelanas prensadas parecem ser uma alternativa mais efetiva para recobrimento de zircônia em relação as convencionais. / Abstract: This study characterized mechanically a conventional and a pressed feldspathic porcelain indicated for zirconia core in terms of biaxial flexural strength, fracture toughness, Vickers hardness. In addition it was investigated the effect of the glaze cooling rate on the biaxial flexural strength of the zirconia/porcelain bilayer. Specimens monolayers of Vita VM9 (n=15) and Vita PM9 (n=15) (12.0 mm diameter x 1.2 mm thickness) were prepared according to manufacturer's recommendations for the biaxial flexural strength test (MPa). Afterwards, one fragment of each broken specimen was randomly selected for Vickers hardness measurements (n=15) (VHN). Apparent fracture toughness (MPa.m½) was determined by Vickers hardness indentation technique (n=15). For the biaxial flexural strength of bilayers, zirconia discs (Vita In-Ceram YZ) were veneered with the conventional porcelain Vita VM9 (n=30) or with the pressed porcelain Vita PM9 (n=30). After the glaze firing simulation, the specimens were submitted to fast (n=15) or slow cooling method (n=15). After the biaxial flexural test, the specimens were analyzed in relation to fracture pattern. T-Student tests were performed for the monolayer specimens, while two-way ANOVA (porcelain and cooling method) was used for the bilayer ones (α=.05). Vita PM9 exhibited significantly higher biaxial flexural strength (p<0.01) and hardness than VM9 (p=0.017). However, there was no significant difference (p= 0.41) in fracture toughness between the porcelains. The two-way ANOVA indicated significance only for the porcelain, with superiority for the combination Vita PM9/zirconia (p<0.01).The pressed porcelain seems to be a mechanically more effective alternative for zirconia veneering than the conventional one. / Mestre

Orientador: Gelson Luis Adabo / Banca: Francisco de Assis Mollo Junior / Banca: Janaina Habib Jorge / Banca: Pedro Cesar Garcia de Oliviera / Banca: Sicknan Soares da Rocha / Resumo: Considerando o efeito das propriedades térmicas da zircônia (3Y-TZP) em infraestruturas anatômicas com maior volume, sobre a taxa de resfriamento da porcelana de cobertura e possível interferência sobre suas propriedades mecânicas, este estudo avaliou a influência da espessura da zircônia na resistência à fratura em coroas, dureza e tenacidade à fratura da porcelana e na resistência adesiva. Para o teste de resistência, foram obtidas infraestruturas em 3Y-TZP de coroas de 1º molar superior com três diferentes espessuras na oclusal: Grupo I - 1 mm, Grupo II - 2 mm e Grupo III - 3 mm. A porcelana VITA VM9 foi aplicada com espessura de 1,1 ± 0,1 mm pela técnica manual. A carga axial foi aplicada na cúspide mésiolingual por máquina de ensaios mecânicos (N=45). Para o teste de resistência de cisalhamento, foi aplicada a porcelana na forma cilíndrica com 1,2 mm de altura X 4 mm de diâmetro sobre placas de 3Y-TZP (5 x 5 mm) nas três espessuras (N= 30). O modo de falha foi analisado por microscopia óptica. Para medida da dureza Vickers e tenacidade à fratura da porcelana na interface com a 3Y-TZP e na superfície, foram usadas placas planas como descrito acima, e a porcelana aplicada, na extensão de uma das faces, com a espessura uniforme de 1,2 mm (N=24). Resultados: As médias e desvio padrão da resistência à fratura por compressão das coroas (N) foi: GI=1979 (523,5), GII=2266 (816,9) e GIII=2316 (672,9). A resistência ao cisalhamento (MPa) foi: GI=18,5 (2,44), GII=15,6 (3,80) e GIII=17,1 (3,17). A tenacidade à fratura (MPa.m1/2) foi: GI=1,53 e 1,48; GII=1,89 e 1,70 - GIII=1,84 e 1,72, respectivamente na interface e na superfície. ANOVA a um fator para resistência das coroas e ao cisalhamento, assim como a dois fatores para dureza e tenacidade a fratura não foram significantes. Concluiu-se que volumes...(Resumo completo clicar acesso eletrônico) / Abstract: Considering the possible effect of the cooling delaying of zirconia (3Y-TZP) in anatomical framework for higher volume, this study evaluated the influence of the framework thickness in the fracture load of porcelain veneered crowns, bond strength between zirconia and porcelain, hardness and fracture toughness of porcelain. For testing fracture load, maxillary first molar were prepared to accomplish three different thicknesses on the occlusal surfaces: Group I - 1 mm, Group II - 2 mm and Group III - 3 mm. The thickness of 1.1 ± 0.1 mm of porcelain VITA VM9 was applied by handmade technical stratification. The axial load was applied to the medial lingual cusp by means of a mechanical test machine (N = 45). The shear test was carried-out in flat plates (5 x 5 mm) in the three thicknesses of zirconia, and the porcelain was applied as cylindrical shape with 1,2 mm high for 4 mm in diameter (N=30). The shear bond strength test was performed by chisel. For measurement of the Vickers hardness and fracture toughness flat plates were fabricated as described above, and the porcelain was applied with uniform thickness of 1.2 mm (N=24). The measurements were done close to the surface and at the interface with zirconia. The mean and standard deviation for the test were: fracture load of the crowns (N) - GI = 1979 (523,5), GII = 2266 (816.9) and GIII = 2316 (672.9); sheer bond strength (MPa) - GI=18.5 (2.44), GII=15.6 (3.80) e GIII=17.1 (3.17); fracture toughness (MPa.m1/2) - GI = 1.53 and 1.48; GII = 1.89 and 1.70 - GIII = 1.84 and 1.72, respectively at the interface and close to the surface. Data from all trials analyzed by ANOVA were not significant for all the tests, revealing that the zirconia thicknesses did not affect the porcelain resistance of the crowns, hardness and fracture toughness and adhesion between the ceramic. Conclusion: The use...(Complete abstrat electronic access below) / Doutor

Magister Scientiae Dentium - MSc(Dent) / Introduction: The evolution of Dentistry witnessed an increase in fixed prostheses as opposed to removable ones. Zirconia (ZrO2) and Lithium disilicate (LDS) are becoming the material of choice in implant or tooth retained prostheses. Polyetheretherketone (PEEK) is a recent alternative as it is lighter and causes less wear of opposing retained teeth. Biofilm formation is a permanent daily struggle for patients as it can be found in nearly all surfaces exposed to the natural environment. Therefore, the interest in a new device capable of removing or reducing oral biofilm from fixed prostheses is increasing. Aquaflosser (AQ) and Waterpik (WP) are examples of these oral irrigating devices that were introduced to the dental market recently. They can be effective in removing dental biofilm from different surfaces. Purpose of study: The purpose of this study is to evaluate biofilm formation on three fixed dental substructures and to evaluate the efficacy of two oral irrigating devices on biofilm removal from these three substructures.