Made available in DSpace on 2015-06-17T19:33:38Z (GMT). No. of bitstreams: 0 Previous issue date: 2014-07-03. Added 1 bitstream(s) on 2015-06-18T12:48:18Z : No. of bitstreams: 1 000831389.pdf: 2171410 bytes, checksum: 8516ec39315e5fd0cac80b4a540a7e3d (MD5) / Proposição: O objetivo do estudo foi avaliar o efeito da limpeza com ácido fosfórico após condicionamento da cerâmica e do tratamento térmico do silano na resistência de união de um cimento resinoso à cerâmica de dissilicato de lítio submetido ao envelhecimento. Método: Foram confeccionados sessenta e quatro blocos de cerâmica de dissilicato de lítio (IPS e-­‐max CAD, Ivoclar Vivadent) e de resina composta (7x8x4mm). Os corpos de prova foram divididos aleatoriamente em 4 grupos (n=16) que receberam os seguintes tratamentos: HFS (grupo controle): ácido fluorídrico 10 % e silano; HFPS: ácido fluorídrico, ácido fosfórico 37% e silano; HFSa: ácido fluorídrico e silano aquecido (45◦C ± 5◦C); HFPSa: ácido fluorídrico, ácido fosfórico e silano aquecido. Os espécimes foram cimentados com um cimento resinoso dual, posteriormente os corpos de prova foram divididos em duas condições de envelhecimento (n=8): N - sem envelhecimento e TC: termociclagem 12.000X, 5◦C - 55 ◦C. Foram submetidos ao teste de microtração em uma máquina de testes com velocidade de 0,7mm/min. As superfícies fraturadas foram examinadas para determinar o modo de falha. Os dados estatísticos foram analisados através da Anova de 2 fatores e as médias comparadas por meio do teste Tukey (p< 0.05). Resultados: o grupo HFSa envelhecido apresentou o maior valor de resistência de união (21,49 ± 2,29 MPa), entretanto, sem diferença estatística para o grupo controle (p<0,05). Não houve diferença estatisticamente significante entre as amostras envelhecidas e não envelhecidas, entretanto, foi observada uma diferença estatisticamente significante no grupo HFSa. (p<0,05). Importância: O tratamento térmico do silano e a limpeza pós-­‐condicionamento com ácido fosfórico não potencializou a resistência de união da cerâmica à resina / Purpose: The aim of this study was to evaluate the effect of cleaning with phosphoric acid after etching of ceramic and heat treatment of the silane with a stream of hot air on the bond strength of a resin cemente to lithium dissiliacte ceramic submitted to aging. Method: Sixty-­‐four blocks-­‐ceramic lithium silicate (IPS e-­‐max CAD, Ivoclar Vivadent) and composite resin were fabricated (7x8x4mm). The specimens were randomly divided into 4 groups (n = 16) that received the following treatments: HFS (control group): 10% hydrofluoric acid and silane; HFPS: hydrofluoric acid, 37% phosphoric acid and silane; HFSA: hydrofluoric acid and silane heated (45 ◦ C ± 5 ◦ C); HFPSa: hydrofluoric acid, phosphoric acid and heated silane. The specimens were cemented with a dual resin cement, later the specimens were divided into two aging conditions (n = 8): N -­‐ no aging and TC: thermocycling, 12,000 x 5◦C -­‐ 55◦C. They were submitted to microtensile test in a testing machine with a speed of 0.7 mm / min. Fractured surfaces were examined to determine the failure mode. Statistical data were analyzed by ANOVA with 2 factors and the averages compared by Tukey test (p <0,05). Results: The group HFSa aged showed the highest bond strength (21.49 ± 2.29 MPa), however, without statistical difference for the control group. There was no statistically significant difference between aged and non-­‐aged samples, except for, a statistically significant difference in the HFSA group (p <0.05). Significance: The heat treatment of the silane and cleaning after etching with phosphoric acid did not increase the bond strength of ceramic resin

Orientador: Flávio Henrique Baggio Aguiar / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Odontologia de Piracicaba / Made available in DSpace on 2018-08-27T07:51:28Z (GMT). No. of bitstreams: 1 HernandesdaFonseca_NataliaMariaAparecida_D.pdf: 1562377 bytes, checksum: a4799c4175306d178b320a7dce350a1e (MD5) Previous issue date: 2015 / Resumo: Este estudo in vitro avaliou a influência do pré-aquecimento na resistência de união de três agentes utilizados para a cimentação de pinos de fibra de vidro Reforpost nº 2. Para tal propósito, foram utilizadas 42 raízes de pré-molares humanos previamente extraídos e com tratamento endodôntico realizado e foram divididos, aleatoriamente, em 6 grupos (n=7) de acordo com o agente de fixação (um cimento resinoso dual Rely X ARC; um cimento autoadesivo Rely X U200; e uma resina composta de baixa viscosidade SureFil SDR flow) e temperatura de pré-aquecimento (23ºC; 54ºC). Todos os agentes de cimentação foram fotoativados através de uma fonte de luz LED com irradiância de 1100 mW/cm² durante 40 segundos. As raízes foram armazenadas em água destilada à 37ºC por sete dias e foram cortadas em fatias com espessura de 1,0 mm cada, os quais foram divididos de acordo com o terço do canal radicular (cervical; médio; apical). Em seguida, as amostras foram submetidas ao teste de resistência ao cisalhamento por extrusão para a mensuração em cada terço do canal radicular. Os dados foram submetidos à ANOVA 3 critérios com parcelas subdivididas e teste de Tukey (? = 0,05). Foram encontradas diferenças significativas entre os três cimentos resinosos. (P < 0,0017); no entanto não foram encontradas diferenças entre os grupos não aquecidos e os grupos pré-aquecidos, diferentes regiões da raiz ou para qualquer interação entre os fatores (p > 0,05). Os grupos cimentados com o cimento resinoso Rely X ARC apresentou maiores resultados de resistência de união do que os grupos cimentados com a resina de baixa viscosidade SureFil SDR flow. O cimento autoadesivo Rely X U200 obteve resistência de união intermediária, sem diferença estatística para RelyX ARC ou SureFil SDR flow. Assim, conclui-se que, a utilização de cimento dual convencional pode ser indicada para cimentação de pinos de fibra de vidro e que o pré-aquecimento de cimentos resinosos não é efetivo para o aumento da resistência de união de pinos pré-fabricados / Abstract: This in vitro study investigated the influence of pre-heating on the bond strength of three agents used for cementing fiber posts Reforpost # 2. For that, forty-two human premolars roots with endodontic treatment performed were randomly divided into 6 groups (n = 7), according with the luting agent (a dual resin cement Rely X ARC; a self-adhesive cement Rely X U200; and a flowable composite SureFil SDR flow) and the pre-heating temperature (23° C; 54° C). All luting agents were light-cured with a LED unit ¿ 1,100 mW/cm² for 40 seconds. The roots were stored in distilled water at 37° C for seven days and after that, the roots were cut into slices of 1.0 mm thickness each, which were divided according to the third of the root canal (cervical; middle; apical). Then the specimens were submitted to push out test to measure the bond strength in each third of the root canal. Data were submitted to three-way split-spot ANOVA and Tukey's test (? = 0.05). Significant differences were found among the three luting agent studied (p < 0.0017); however, no difference was found among the pre-heating temperature, root segments or for any interaction between the factors (p > 0.05). Groups luted with resin cement Rely X ARC showed significant higher retentive strength than flowabe composite SureFil SDR flow. Rely X U200 showed intermediary retentive strength means, without statistical difference for Rely X ARC or SureFil SDR flow. Thus, it is concluded that the use of conventional dual cement should be indicated to luting fiber posts and the resin cement pre-heating is not effective to increase the retentive strength of fiber post / Doutorado / Dentística / Doutora em Clínica Odontológica

A utilização dos implantes cone morse muito favorece a estética peri-implantar e seu uso em conjunto com próteses cimentadas favorece ainda mais a estabilidade do sistema, simplificando também os procedimentos protéticos. O presente estudo histológico e histomorfométrico utilizou os implantes cone morse com o intuito de avaliar o comportamento tecidual com relação à posição da margem da cimentação protética em relação ao tecido ósseo quando se faz o uso próteses cimentadas. Foram utilizados quatro cães, os quais tiveram todos os pré-molares inferiores extraídos numa primeira fase cirúrgica. Após três meses, realizou-se a segunda fase cirúrgica, na qual foi realizada a técnica da carga imediata, com a instalação dos implantes juntamente com os pilares protéticos. Foram instalados vinte e quatro implantes numa profundidade de 3 mm infra óssea e eles foram igualmente divididos entre os grupos Controle e Experimental. Os pilares protéticos utilizados foram do tipo munhão universal e apresentavam diferentes alturas transmucosas iguais a 1.5 mm, 3.5 mm, e 5.5 mm. Isto fez com que a margem da cimentação se posicionasse a 1.5 mm infra óssea, a 0.5 mm supra óssea e a 2.5 mm supra óssea. No grupo Controle, foi realizada a instalação dos implantes e dos pilares protéticos somente. No grupo Experimental, foi realizada a instalação dos implantes, dos pilares protéticos e, sobre estes, foram cimentados cilindros de alumina. Os animais permaneceram sobre controle de placa durante 10 semanas subsequentes a instalação dos implantes, sendo este o tempo final do experimento através da realização da eutanásia. As amostras foram preparadas para análise histológica e avaliação dos tecidos peri-implantares. A região de interesse foi medida através da distância entre a margem do pilar protético e a porção mais coronal da crista óssea peri-implantar. Foram utilizados os testes estatísticos ANOVA a três critérios com medidas repetidas e teste de Tukey com o nível de significância de p < 0.05. Os resultados mostraram que não houve diferenças estatisticamente significantes entre os grupos Controle e Experimental (p = 0.2764) e que os pilares de 1.5 mm mostram menos perda óssea comparada aos outros pilares, considerando que a distância média da remodelação óssea foi menor neste grupo (0.6859 mm) comparada com os pilares de 3.5 mm (1.2917 mm) e 5.5 mm (1.0823 mm). Conclui-se que não há influência da profundidade da margem da cimentação protética no comportamento da crista óssea e que a utilização de diferentes alturas dos pilares protéticos não parece alterar o tecido ósseo marginal ao redor dos implantes Cone Morse. / The use of Morse taper implants has increased because of some positive features. Cemented crowns can be extensively used, taking advantage of the system connection stability, also simplifying the prosthetic procedures. The present histological and histomorphometric study used Morse taper implants with the purpose of evaluating bone behavior with respect to the cementation margin position of the prosthetic crown. Four dogs had all premolars extracted at a first surgical procedure. After three months, there was a second surgical procedure with simultaneous installation of implants and abutments, submitted to immediate load. Twenty four implants were installed 3 mm below the bone level and they were equally divided between Control and Experimental groups. The universal post abutments used had three different transmucosal heights, 1.5 mm, 3.5 mm and 5.5 mm. Thus there were implants with the level of the cementation margin positioned 1.5 mm below the bone level, as well as 0.5 mm and 2.5 mm above the bone level. In the Control group, installation of implants and abutments only was performed. In the Experimental group immediately after the placement of implants and abutments alumina cylinders were cemented. The animals were kept on plaque control for 10 weeks after implant placement and then euthanized. Samples were prepared for histological analysis and evaluation of peri-implant tissues. The region of interest was measured by the distance between the prosthetic margin of the abutment to the most coronal peri-implant bone crest. ANOVA test at three criteria with repeated measures and Tukey test with a significance level of p < 0.05 were applied. The results showed no statistically significant differences between Control and Experimental groups (p = 0.2764). The 1.5 mm abutments presented less bone loss compared to all other abutments tested, because the distance average of bone remodelation was shorter in this group (0.6859 mm) compared to the 3.5 mm abutment (1.2917 mm) and the 5.5 mm one (1.0823 mm). Conclusion: There is no influence of the depth of prosthetic marginal cementation on the behavior of bone crest and the use of different transmucosal heights of abutments does not seem to change the marginal bone surrounding morse taper implants.

Este estudo teve o objetivo de avaliar, por meio do ensaio de microtração, o efeito na resistência adesiva e no modo de fratura da Y-TZP quando cimentada a blocos padronizados de resina composta com um cimento resinoso autoadesivo (RelyX Unicem 3M ESPE, Saint Paul/ Minnesota, EUA), sob diferentes tratamentos de superfície, antes e após o envelhecimento. Doze amostras de Y-TZP foram divididas em seis grupos, de acordo com os seguintes tratamentos de superfície: Ru (sem tratamento de superfície); Ap (Alloy Primer); Zp (Z-Prime Plus); Na (solução de hidróxido de sódio - NaOH); NaAp (solução de NaOH, seguida pela aplicação de Alloy Primer); NaZp (NaOH, seguida pela aplicação de Z-Prime Plus). Após os tratamentos de superfície e a cimentação, de acordo com as recomendações do fabricante, os blocos foram armazenados por 24h em água destilada e cortados em seguida. O teste de microtração aconteceu em dois momentos: 72h após os procedimentos de corte e após seis meses de envelhecimento (E). Ao final do teste de microtração, os espécimes foram analisados em estereomicroscópio e no microscópico eletrônico de varredura (MEV), para caracterização do modo de fratura. A distribuição Weibull a dois parâmetros (Synthesis 9, Weibull ++; Reliasoft, Tucson, AZ, USA) foi utilizada para cálculo da probabilidade de sobrevida em função da resistência adesiva em 10 MPa, 15 MPa e 20 MPa. A comparação entre os grupos também foi realizada com o módulo de Weibull e a resistência característica (resistência adesiva). As resistências adesivas imediatas e após o envelhecimento foram: (Ru 15,26 MPa e RuE 12,15 MPa; Ap 13,82 MPa e ApE 10,72 MPa; Zp 14,19 MPa e ZpE 9,72 MPa; Na 17,92 MPa e NaE 13,15 MPa; NaAp 21,25 MPa e NaApE 18,13 MPa; NaZp 16,25 MPa e NaZpE 8,66 MPa). Nos grupos imediatos, a utilização da solução básica, sozinha ou associada aos primers, apresentaram maior quantidade de falhas mistas, porém, após o envelhecimento, as falhas adesivas foram mais frequentes para esses tratamentos. Através dos resultados obtidos, pôde-se concluir que a solução de NaOH associada ao Alloy Primer, foi o único tratamento de superfície que apresentou os maiores valores de resistência adesiva, antes e após o envelhecimento, apresentando modo de fratura predominantemente mista. O tempo de armazenamento levou a uma redução da probabilidade de sobrevida em função da carga de 10 MPa e 15 MPa para todos os tratamentos, exceto para o NaAp. / This study aimed to evaluate, through microtensile test, the effect of bond strength and fracture modes of the Y-TZP when it is cemented to a standard composite resin blocks with a self-adhesive resin cement (RelyX Unicem - 3M ESPE, Saint Paul / Minnesota, USA) under different surface treatments before and after aging. Twelve samples of Y-TZP were divided into six groups, according to the following surface treatments: Ru (no surface treatment); Ap (Alloy Primer); Zp (ZPrime Plus); Na (sodium hydroxide solution - NaOH); NaAp (NaOH solution, followedby Alloy Primer); NaZp (NaOH solution, followed by Z-Prime Plus). After the surface treatment and cementation, according to the manufacturer\'s recommendations, the blocks were stored for 24 hours in distilled water and then cut. The microtensile testing was performed in two times: 72 hours after the cutting procedures and after six months of aging (E). At the end of microtensile test, the specimens were analyzed in stereomicroscope and scanning electron microscope (SEM) to characterize the fracture mode. The 2-parameter Weibull distribution (Synthesis 9, Weibull ++; Reliasoft, Tucson, AZ, USA) was used to calculate the survival probability function of the adhesive strength at 10 MPa, 15 MPa and 20 MPa. Comparisons between groups were also analysed with Weibull modulus and characteristic strength (bond strength). Results showed that the immediate and after aging bond strength were: (Ru 15.26 MPa and RuE 12.15 MPa; Ap - 13.82 MPa and ApE - 10.72 MPa; Zp - 14.19 MPa and ZpE - 9.72 MPa; Na - 17.92 MPa and NaE - 13.15 MPa; NaAp 21.25 MPa and NaApE - 18.13 MPa; NaZp 16.25 MPa and NaZpE - 8.66 MPa). In the immediate groups, using the basic solution, alone or in association with primers the results showed an increased amount of mixed failures, but after aging, the adhesive failures was more frequent for such treatments. It was possible to conclude that the NaOH solution associated with the Alloy Primer was the only surface treatment that showed the highest bond strength values before and after aging, with predominantly mixed fracture mode. The storage time promoted a reduction in survival probability function load of 10 MPa and 15 MPa for all treatments except for the NaAp.

No presente trabalho, usando ensaios de remoção por tração, o objetivo foi avaliar a eficiência de 4 agentes (fosfato de zinco S. S.White, ionômero de vidro Ketac Cem Easymix, resina composta RelayX Luting 2 e resina acrílica especial Panavia 21 TC) usados para fixar coroas totais de NiCr a munhões tronco-cônicos, usinados em liga de Ti-6Al-4V. Dentre os cinqüenta munhões utilizados, 40 permaneceram com sua superfície original altamente lisa (como vieram de fábrica) e foram distribuídos em grupos de 10, para cada agente cimentante; no grupo dos 10 restantes existiu uma modificação por irradiação com LASER e cimentação apenas com fosfato. Os ensaios mecânicos foram realizados em uma máquina universal MTS 810, na velocidade de 0,5 mm/min. A respectiva Análise de Variância (ANOVA) apontou existir diferença significante entre os grupos e o teste de Tukey (p<0,05) também mostrou diferenças significantes entre eles, exceto nas comparações original/fosfato versus original/RelayX e original/fosfato versus original/KetcCem. Para os munhões não-irradiados, o melhor desempenho foi apresentado pela resina Panavia 21 (1.127,996 N); a resina composta RelyX (478,197 N) mostrou comportamento similar apenas ao do fosfato (430,662 N), o qual apresentou desempenho semelhante ao ionômero de vidro KetacCem (227,705 N). A modificação da superfície do munhão fez com que a magnitude da resistência à tração das coroas cimentadas com fosfato aumentasse para 1.514,872 N. / By means of tensile essays, NiCr total crowns were removed from usinated tronco-conical abutments composed by an Ti-6Al-4V alloy; the performance of 4 cementig agents (S. S. White zinc phoshate, Ketac Cem Easymix glass ionomer, RelayX Luting 2 composite resin and Panavia 21 TC special acrylic resin) was evaluated. Among a total of 50 abutments, 40 were used with it surface presenting high smoothness (as they come from manufacturer) and distributed in groups of 10 elements, each group for each cementing agent; the other 10 abutments had had its surfaces modified by LASER and were used only with phosphate. The mechanical essays were developed at a MTS 810 universal machine, adjusted to a 0.5 mm/m velocity. The ANOVA applied to data pointed out the existence of significant differences between groups; the subsequent Tukey´s test (p<0.05) also detected significant differences, except at comparisons of original/phosphate versus original/ RelayX and original/phosphate versus original/ KetacCem. To non-irradiated abutments, the better performance was presented by Panavia 21 (1,127.996 N); RelyX (478.197 N) showed itself similar only to phosphate (430.662 N), wich had a performance similar to that of KetacCem (227.705 N). The referred LASER irradiation promoted an increased resistance to the phosfate, which reached 1,514.872 N.

A utilização dos implantes cone morse muito favorece a estética peri-implantar e seu uso em conjunto com próteses cimentadas favorece ainda mais a estabilidade do sistema, simplificando também os procedimentos protéticos. O presente estudo histológico e histomorfométrico utilizou os implantes cone morse com o intuito de avaliar o comportamento tecidual com relação à posição da margem da cimentação protética em relação ao tecido ósseo quando se faz o uso próteses cimentadas. Foram utilizados quatro cães, os quais tiveram todos os pré-molares inferiores extraídos numa primeira fase cirúrgica. Após três meses, realizou-se a segunda fase cirúrgica, na qual foi realizada a técnica da carga imediata, com a instalação dos implantes juntamente com os pilares protéticos. Foram instalados vinte e quatro implantes numa profundidade de 3 mm infra óssea e eles foram igualmente divididos entre os grupos Controle e Experimental. Os pilares protéticos utilizados foram do tipo munhão universal e apresentavam diferentes alturas transmucosas iguais a 1.5 mm, 3.5 mm, e 5.5 mm. Isto fez com que a margem da cimentação se posicionasse a 1.5 mm infra óssea, a 0.5 mm supra óssea e a 2.5 mm supra óssea. No grupo Controle, foi realizada a instalação dos implantes e dos pilares protéticos somente. No grupo Experimental, foi realizada a instalação dos implantes, dos pilares protéticos e, sobre estes, foram cimentados cilindros de alumina. Os animais permaneceram sobre controle de placa durante 10 semanas subsequentes a instalação dos implantes, sendo este o tempo final do experimento através da realização da eutanásia. As amostras foram preparadas para análise histológica e avaliação dos tecidos peri-implantares. A região de interesse foi medida através da distância entre a margem do pilar protético e a porção mais coronal da crista óssea peri-implantar. Foram utilizados os testes estatísticos ANOVA a três critérios com medidas repetidas e teste de Tukey com o nível de significância de p < 0.05. Os resultados mostraram que não houve diferenças estatisticamente significantes entre os grupos Controle e Experimental (p = 0.2764) e que os pilares de 1.5 mm mostram menos perda óssea comparada aos outros pilares, considerando que a distância média da remodelação óssea foi menor neste grupo (0.6859 mm) comparada com os pilares de 3.5 mm (1.2917 mm) e 5.5 mm (1.0823 mm). Conclui-se que não há influência da profundidade da margem da cimentação protética no comportamento da crista óssea e que a utilização de diferentes alturas dos pilares protéticos não parece alterar o tecido ósseo marginal ao redor dos implantes Cone Morse. / The use of Morse taper implants has increased because of some positive features. Cemented crowns can be extensively used, taking advantage of the system connection stability, also simplifying the prosthetic procedures. The present histological and histomorphometric study used Morse taper implants with the purpose of evaluating bone behavior with respect to the cementation margin position of the prosthetic crown. Four dogs had all premolars extracted at a first surgical procedure. After three months, there was a second surgical procedure with simultaneous installation of implants and abutments, submitted to immediate load. Twenty four implants were installed 3 mm below the bone level and they were equally divided between Control and Experimental groups. The universal post abutments used had three different transmucosal heights, 1.5 mm, 3.5 mm and 5.5 mm. Thus there were implants with the level of the cementation margin positioned 1.5 mm below the bone level, as well as 0.5 mm and 2.5 mm above the bone level. In the Control group, installation of implants and abutments only was performed. In the Experimental group immediately after the placement of implants and abutments alumina cylinders were cemented. The animals were kept on plaque control for 10 weeks after implant placement and then euthanized. Samples were prepared for histological analysis and evaluation of peri-implant tissues. The region of interest was measured by the distance between the prosthetic margin of the abutment to the most coronal peri-implant bone crest. ANOVA test at three criteria with repeated measures and Tukey test with a significance level of p < 0.05 were applied. The results showed no statistically significant differences between Control and Experimental groups (p = 0.2764). The 1.5 mm abutments presented less bone loss compared to all other abutments tested, because the distance average of bone remodelation was shorter in this group (0.6859 mm) compared to the 3.5 mm abutment (1.2917 mm) and the 5.5 mm one (1.0823 mm). Conclusion: There is no influence of the depth of prosthetic marginal cementation on the behavior of bone crest and the use of different transmucosal heights of abutments does not seem to change the marginal bone surrounding morse taper implants.

Carbonate rocks consider as significant reservoirs for hydrocarbon. More than 60% of the world's hydrocarbon is placed in carbonate reservoirs. Carbonate rocks are heterogeneous and contain complex pore system. This complexity causes the hydrocarbon recovery from these reservoirs difficult; having less than 35% of hydrocarbon is being recovered. The heterogeneity and the variation in pore system are a result of various depositional settings and successive diagenetic overprints. Diagenetic overprints account for most of the pore system complexity in subsurface. This project undertakes one of the important diagenetic processes, calcite cementation, which though to have major impact on reservoir quality. The project aims to better understand the controls on calcite cementation in five Lower Cretaceous Reservoirs, in particular the role of calcite cementation with relation to oil charge in reservoir quality. Other diagenetic processes were also asses including dolomitization, dissolution, micritization and chemical compaction. The five reservoirs (A, B, C, F & G) are from Field A which is located in Abu Dhabi, UAE. The reservoirs comprise of interbedded porous "Reservoir" and low porosity-permeability "Dense" limestones deposited in broad range of settings, ranging from restricted to open marine platform. Reservoir intervals are part of HSTs, deposited during higher sea level time. The dense intervals were deposited during TST and thought to be cemented early resulting in early compartmentalization in all reservoirs. The mMg/Ca and in-situ (SIMS) δ18OVPDB were measured through complete calcite cement stratigraphy obtained from equant, syntaxial and blocky calcite in all reservoirs. Both mMg/Ca and δ18OVPDB of oldest calcite cement zone are matching with published mMg/Ca and δ18OVPDB of Lower Cretaceous, suggesting precipitation from Lower Cretaceous seawater. The mMg/Ca and δ18OVPDB also vary from reservoir to another reflecting change in Cretaceous seawater. These data also coincide with trace element observations particularly Mn and Sr. All these parameters show fluctuations in Cretaceous seawater during 135-123Ma caused by global changes in climate and oceanic crust production rates. Lower reservoirs including F (133Ma) and C (130Ma) were more probably affected by the Hauterivian global cooling which resulted in higher δ18OVPDB in the early precipitated cements. Precipitation in upper Reservoir B (126Ma) was most likely affected by the abrupt warm episode just before the OAE1. Reservoir A (123Ma) precipitation may be affected by the Early Aptian cooling episode and the OAE1. Reservoir G is the only one not recording δ18OVPDB similar of Cretaceous seawater. Cementation in Reservoir G was affected by depleted δ18OVPDB fluids from early stage, perhaps hot, basinal waters. More interestingly, the mMg/Ca, δ18OVPDB Mn and Sr means of younger calcite cement zones which thought to be evolved during burial show similar trend to the oldest cement zones with various offsets. This suggests that calcite cement in each reservoir evolved in a relatively close system inferring by this that the reservoirs are compartmentalized. The compartmentalization is probably due to the sysedimentary or early cemented hardgrounds in the Dense Zones. The Dense Zones acted as seals for the reservoirs from early stage causing the later precipitated calcite cement which is diagenetically affected to behave in predictable and similar way. Moreover, calcite precipitation temperatures inferred from mMg/Ca and δ18OVPDB show progressive increase towards younger cement zones indicating fluid evolution with burial in also relatively close system. In-situ δ18OVPDB and oil inclusions suggest earlier oil charge in the shallower reservoirs compared with deeper reservoirs and coeval water leg. Consequently, cementation in the shallower reservoirs continued with lower rate and hence preserved some primary and secondary pores. Conversely, in the water leg cementation continue to occlude most of the pore spaces. Furthermore, early oil emplacement in the shallower reservoirs increased the cementation temperature of calcite in the oil leg to reach maximum precipitation temperatures of ~144˚C. Whereas, in the water leg and deeper reservoirs, cementation continued to a temperature of ~110˚C. Overall, reservoir quality in Thamama Group was affected by various diagenetic processes. Some have resulted in reservoir quality enhancement such as dolimitization which involves formation of microporosity as a result of replacive rhombic dolomite, dissolution particularly the late one which believed to be due organic acid, and micritization with yield microporosity particularly in Reservoir B. Open fractures might have also enhanced reservoir quality to some extent. Diagenetic events that have deteriorated reservoir quality include calcite and saddle dolomite cementation as well as stylolitization. Greater calcite cementation can be found in water leg compared with oil leg because oil thought to decrease cementation rate.

Red-brown hardpan occurs extensively in Western Australia in the arid and semi-arid regions of the Murchison, Pilbara and Eastern Goldfields divisions, between longitudes 115ºE and 124ºE and latitudes 23ºs and 30ºs. It occupies an area of about 360,000 sq. km, two thirds of which occurs in the Yilgarn Craton. The purpose of this research is to map the distribution of red-brown hardpan in the Yilgarn Craton of Western Australia; study the relationship between landscape, soil texture and vegetation; investigate the physical characteristics, petrology, mineralogy, geochemistry and cementing agents; and thereby determine the processes invaded in forming red-brown hardpan. The relation of red-brown hardpan to gold is investigated and determined its implications in mineral exploration. The main case study areas were the Goldfields Gas Pipe Line, the Federal Open Pit Gold mines and the Menzies district in the Kalgoorlie-Menzies region of the Eastern Goldfields; areas in and around the Woolgorong Station in the Murchison Province and at the Wiluna Gold Mines in the Northeastern Goldfields. The findings and conclusions of this research are summarised below. Red-brown hardpan occurs at or near the land surface and may vary from less than one metre to more than 10 m thick. It is exclusively developed in colluvium and alluvium, showing varying stages of cementation ranging from weakly cemented through moderate to strongly cemented. In addition, calcrete and red-brown hardpan occurs together in many places, south of the Menzies line, and this distribution suggests that red-brown hardpan was once more extensive and has been subsequently replaced by carbonate to form calcareous red-brown hardpan and calcrete. Red- brown hardpan predominantly occurs in regions with Q50 mm annual rainfall. / In present-day higher rainfall (400 to 500 mm) regions, red-brown hardpan is being weathered. There is no relationship between the distribution of mulga (Acacia aneura) and red-brown hardpan. Red-brown hardpan is exclusively developed in colluvium containing a minimum of 20% quartz, 15% clays and 2% iron oxides. It is bright reddish brown to reddish brown, earthy, with a sandy loam texture, blocky structure and porous. Red-brown hardpan is hard (up to 12 MPa), being characterised by sub-horizontal laminations predominantly of uncemented kaolinite. Ped surfaces may be coated by Mn oxide and carbonate which may be precipitated along the laminations. The mineralogy of the cement is complex. Data from XRD, SEM, TEM, EFTEM, FTIR and NIR investigations show poorly-ordered kaolinite and opal-A as the main components. Illuvial multilayered argillaceous cutans containing silica and alumina in a ratio of 2:l form the cement. Secondary silica (SiO2-95%) coatings are common, mainly as opal-A, on ped surfaces and on the inner walls of voids and vughs. Etch pits are developed in these coatings and some of them are filled by kaolinitic clays. Selective dissolution experiments using acid ammonium oxalate show that oxalate- soluble amorphous and poorly ordered silica and alumina in red-brown hardpan have molar ratios of about 1.6 to 2 A1203:SiO2. / These results suggest that red-brown hardpans were formed where there was sufficient water during the wet season to dissolve alumina and silica, but insufficient to leach them. During the subsequent dry season, the dissolved alumina and silica was precipitated as poorly-ordered kaolinite and opal-A. Successive dissolution and precipitation led to fusion of poorly-ordered kaolinite and opal-A at a nanometre scale to progressively cement the colluvium. The age of the red-brown hardpans, estimated by paleomagnetic dating of hematite, is from Pleistocene to present. Based on the findings of this research, the red-brown hardpan is redefined and primarily classified on its degree of cementation as: (1) weakly cemented, (2) moderately cemented and (3) strongly cemented. It is further classified chemically into: (1) siliceous, (2) calcareous and (3) ferruginous. In the Yilgarn Craton, red-brown hardpan is believed to occur mainly north of the 'Menzies Line'. However, this study reveals the presence of red-brown hardpan 75- 150 km south of the Menzies Line and the new southern boundary is closer to latitude 29ºs. Geochemical investigation at the Federal Open Pit Gold mines, Broad Arrow, north of Kalgoorlie indicate that there are Au anomalies in red-brown hardpan. Gold concentration is up to 50 ppb against the background anomaly of 10 ppb. Sequential and partial extraction analyses show significant correlation of Au with Ag, Ca, Ce, Co, Mg, Mn and Ni. This suggests that the Au concentration in red-brown hardpan is due to: (a) mechanical dispersion due to reworking of Au-bearing clasts in the sediment and (b) hydromorphic dispersion from the underlying mineralisation. It can therefore be used as a useful sampling medium for gold exploration.

ABSTRACT This study was aimed to investigate the operational conditions for stabilizing and recycling copper sludge in electronic industry by serially using acid leaching, cementation and ferrite methods. The physical/chemical characteristics of copper sludge were examined, and TCLP (Toxic Characteristics Leaching Process) tests were conducted. Results show that the copper sludge from electronic industry is weakly alkaline and consists of 6-15.8% Cu and 50-75% moisture. The TCLP tests show that copper in the sludge exceeds the regulation standard. Acid leaching tests indicate that the optimal combination of control factor levels yielding more than 99% of copper extraction is: 2.0 N in sulfuric concentration (A3), pH = 1.5 (B3), 90 minutes in treatment time (C3), and 50 oC in treatment temperature (D3). Moreover, the sediment of treated sludge fulfills the standards of the TCLP, and is thus a general industrial waste. Cementation tests indicate that the optimal combination of control factor levels yielding 96.87% of copper recovery and 92% of copper purity is: addition mole ratio of iron element Fe/Cu = 2.0 (A2), pH = 1.0 (B1), agitation speed = 200 rpm (C1), and 50 oC in treatment temperature (D3). Ferrite tests indicate that the optimal combination of control factor levels yielding more than 99% of copper removal is: addition mole ratio of ferrous sulfuric acid Fe2+/Cu = 10.0 (A3), pH = 9.5 (B2), air supply rate = 3.0 L/min (C3), and 80 oC in treatment temperature (D3). The cost analyses indicate that the expenses would be NT $7.45 for the acid leaching-cementation-ferrite process, less expensive than NT $ 8.0 for the solidification process given the same copper sludge. Thus, the proposed method in this study is competitive and feasible. Keywords: Copper sludge, Acid Leaching, Cementation, Ferrite Process, Recycling

Macroscopic transport properties of porous media depend on textural rock parameters such as porosity, grain size and grain shape distributions, surface-to-volume ratios, and spatial distributions of cement. Although porosity is routinely measured in the laboratory, direct measurements of other textural rock properties can be tedious, time-consuming, or impossible to obtain without special methods such as X-ray microtomography and scanning electron microscopy. However, by using digital three-dimensional pore-scale rock models and physics-based algorithms researchers can calculate both geometrical and transport properties of porous media. Therefore, pore-scale modeling techniques provide a unique opportunity to explore explicit relationships between pore-scale geometry and fluid and electric flow properties. The primary objective of this dissertation is to investigate at the pore-scale level the effects of grain shapes and spatial cement distribution on macroscopic rock properties for improved understanding of various petrophysical correlations. Deposition and compaction of grains having arbitrary angular shapes and various sizes is modeled using novel sedimentation and cementation pore-scale algorithms. Additionally, the algorithms implement numerical quartz precipitation to describe preferential cement growth in pore-throats, pore-bodies, or uniform layers. Subsequently, petrophysical properties such as geometrical pore-size distribution, primary drainage capillary pressure, absolute permeability, streamline-based throat size distribution, and apparent electrical formation factor are calculated for several digital rock models to evaluate petrophysical correlations. Furthermore, two geometrical approximation methods are introduced to model irreducible (connate) water saturation at the pore scale. Consolidated grain packs having comparable porosities and grain size distributions but various grain shapes indicate that realistic angular grain shape distribution gives the best agreement of petrophysical properties with experimental measurements. Cement volume and its spatial distribution significantly affect pore-space geometry and connectivity, and subsequently, macroscopic petrophysical properties of the porous media. For example, low-porosity rocks having similar grain structure but different cement spatial distribution could differ in absolute permeability by two orders of magnitude and in capillary trapped water saturation by a factor of three. For clastic rocks with porosity much higher than percolation threshold porosity, pore-scale modeling results confirm that surface-to-volume ratio and porosity provide sufficient rock-structure character to describe absolute permeability correlations. In comparison to surface-to-volume ratio, capillary trapped (irreducible) water saturation exhibits better correlation with absolute permeability due to weak pore space connectivity in low-porosity samples near the percolation threshold. Furthermore, in grain packs with fine laminations and permeability anisotropy, pore-scale analysis reveals anisotropy in directional drainage capillary- pressure curves and corresponding amounts of capillary-trapped wetting fluid. Finally, results presented in this dissertation indicate that pore-scale modeling methods can competently capture the effects of porous media geometry on macroscopic rock properties. Pore-scale two- and three-phase transport calculations with fast computers can predict petrophysical properties and provide sensitivity analysis of petrophysical properties for accurate reservoir characterization and subsequent field development planning. / text