In this thesis, the theory of metal crystal evaporation and of vapour pressure determinations are presented, followed by a literature survey on the evaporation characteristics of iron, chromium and alloys of iron - chromium. Results are presented for an investigation carried out on the free evaporation kinetics of iron base alloys containing 5 percent and 25 percent chromium for the temperature range 900°C to 1080°C. Also, a complete description of the surface topographies of evaporated specimens is presented using normal, hot stage and interferometric microscopic techniques. These results are correlated in terms of the evaporation theory and pertinent experimental data reported for other metallic systems. / Thesis / Master of Science (MSc)

A higienização das próteses removíveis é fundamental para a longevidade do tratamento e prevenção de patologias orais. O objetivo deste estudo foi avaliar o efeito de higienizadores de imersão nas superfícies da liga metálica e resina acrílica termopolimerizável de Prótese Parcial Removível (PPR), simulando 180 dias. Discos (12 mm x 3 mm) foram confeccionados com ligas metálicas de cobalto-cromo para PPR: Vera PDI® (VP) e DeguDent® (DD). Cada disco metálico foi incluído em mufla previamente preparada por matrizes de teflon (38 mm x 18 mm x 4 mm), incorporando-se o disco metálico à resina acrílica termopolimerizável. Os espécimes (n= 5) foram imersos nas seguintes soluções: água destilada (grupo controle - AD), hipoclorito de sódio 0,05% (HS), Cepacol® (cloreto de cetilpiridínio 0,005% - CE), Periogard® (digluconato de clorexidina 0,12% - PE), Corega Tabs® (peróxido alcalino e enzima - CT), Polident® (peróxido alcalino e enzima - PO) e Medical Interporous Dentures® (ácido cítrico - MI). Foram realizadas análise da estabilidade de cor por meio de espectrocolorímetro, análise visual da presença de manchas no metal, análise da perda de massa em balança de alta precisão e análise da rugosidade por meio de rugosímetro. Como estudo complementar, foram realizadas análises quantitativas da liberação de íons (cobalto e cromo) em cada solução com espectrômetro de massas e análises ópticas e qualitativas com microscópio eletrônico de varredura (MEV) e espectrometria de energia dispersiva de Raios-X (EDS). Os resultados de rugosidade, alteração de cor e massa apresentaram distribuição normal e homogênea, tendo sido submetidos à ANOVA e teste de Tukey (p< 0,05). Quanto à rugosidade (Ra&micro;m), não houve diferença estatisticamente significante entre as soluções e ligas tanto para o metal quanto para a resina. Com relação à alteração de cor da resina acrílica termopolimerizável (&Delta;E), houve diferença estatisticamente significante entre as ligas, soluções e na interação liga x solução. As soluções AD, CE e PE propiciaram menores valores que as demais. A resina associada à DD apresentou maior alteração de cor do que quando associada à VP (1,06 ± 0,51 e 0,51 ± 0,28, respectivamente). Com relação à presença de manchas no metal, o HS propiciou manchamento em 100% dos espécimes. O grupo MI/DD propiciou em 60% e o MI/VP em 40% dos espécimes. Quando avaliada a alteração de massa (g), as soluções CT e MI propiciaram maiores valores. Entre as ligas, a VP apresentou maior perda de massa. Com relação à liberação de íons cobalto e cromo, a solução de HS e a MI propiciaram maior liberação e quando comparadas as ligas, VP apresentou maior liberação de íons. Com o MEV pôde-se verificar que houve corrosão generalizada com o HS e por pites com a MI. Concluiu-se que as soluções CE, PE e PO não apresentaram efeitos deletérios podendo ser auxiliares à escovação para higienização de PPR. / The hygiene care of the removable dentures is required for the longevity of the treatment and prevention of oral diseases. The aim of this study was to evaluate the effect of denture cleansers on the surfaces of the alloys and heat-polymerized acrylic resin for removable partial denture (RPD), simulating a period of 180 days. Circular specimens (12 mm x 3 mm) had been fabricated with cobalt-chromium alloys: Vera PDI&trade; (VP) and DeguDent&trade; (DD). The cast specimens were centered in the moulds previously prepared by matrices of teflon (38 mm x 18 mm x 4 mm) and the acrylic resin was inserted. The specimens (n= 5) had been immersed in the following solutions: distilled water (control - DW), sodium hypochlorite 0.05% (SH), Cepacol&trade; (cetilpiridinium chloride 0.005% - CE), Periogard&trade; (chlorexidine gluconate 0.12% - PE), Corega Tabs&trade; (alkaline peroxide and enzyme - CT), Polident&trade; (alkaline peroxide and enzyme - PO) and Medical Interporous Dentures&trade; (citric acid - MI). The color stability was analyzed using a colorimeter, and the presence of tarnishes on the metal was performed by a visual analysis. The weight loss was measured with a precision balance and the surface roughness was analyzed with a surf-test analyzer. As complementary analyzes a quantitative study of ions release (cobalt and chromium) using inductively mass spectrometry and optical and qualitative analyses with scanning electron microscopy (SEM) associated to dispersive energy spectrometry were performed. The results of roughness, color stability and weight loss presented normal and homogeneous distribution and were submitted to ANOVA (p &le; 0.05) and Tukey test. There was no significant difference among the solutions and between the alloys for both metal and resin roughness (Ra &micro;m). The acrylic resin color stability (&Delta;E) was analyzed and showed significant difference among the solutions, alloys and interaction. AD, CE and PE solutions presented the lowest values of color changes. The resin associated to DD presented higher color change than when associated with the VP (1.06 ± 0.51 and 0.51 ± 0.28, respectively). The HS caused tarnishes on 100% of specimens. The MI/DD group provided 60% and the MI/VP in 40% of specimens. When was analyzed the mass loss (g), the solutions CT and MI had the higher values. Between the alloys VP presented higher weight loss. HS and MI presented greater ionic release and between the alloys, VP presented greater release. With the SEM it was possible observe the presence of widespread corrosion in the HS group and pites corrosion in the MI group. It was concluded that CE, PE, CT and PO solutions had no deleterious effects on the compounds of RPD and may be indicate as auxiliaries to brushing in the RPD hygiene care.

O objetivo da pesquisa foi avaliar a resistência de união entre o titânio fundido e cimentos resinosos, comparada com a de uma liga de níquel-cromo. Os fatores estudados foram: cimentos (Enforce, Cimento de resina 3M, Cement-it); conjugação liga/ revestimento ( titânio obtido com revestimento com a case e sem a case e liga de níquel-cromo, com fosfatado); tratamento superficial ( jateamento com óxido de alumínio e sistema Siloc); desgaste (cimentação antes do desgaste e depois). Para os espécimes foram obtidos discos por fundição, que foram jateados com óxido de alumínio. A metade foi cimentada depois desse tratamento e outra após a aplicação do Siloc. A armazenagem foi por 5 dias fazendo-se termociclagem (1.000 ciclos). Após o rompimento dos espécimes, por ensaio de tração, as superfícies cimentadas foram desgastadas com lixa n o 200 e novamente cimentadas. As conclusões foram: houve grande diferença entre cimentos; o titânio e o níquel-cromo nas devidas condições apresentaram retentividades semelhantes; o Siloc aumentou muito a retenção; o desgaste só influiu um pouco no titânio a case. / The Purpose of the research was to evaluate tensile bond strength of cemented titanium and nickel-chromium alloy cast discs. Factors studied were: Cements (Enforce, Resin cement 3M, Cement-it); Combination alloy/investment ( titanium obtained with a case and without a case investments, and nickel-chromium alloys); surface treatment (sandblasting with Al2O3 and Siloc application): surface abrading (test before and after).Cast discs with fixing stem were sandblasted and half of them were luted in this stage and the other one were luted after Siloc treatment. Specimens were stored for 5 days and thermalcycled (1,000 cycles). After tensile strength test surfaces were abraded and discs were luted again. The conclusions were: cements presented different bond strength; titanium and nickel-chromium alloy, under given condition, presented similar strength; Siloc system presented at least double strength; abrading of a case, titanium enhance only a little bond strength.

In 2005, over 200,000 Americans underwent a hip arthroplasty, the replacement of a hip joint with an artificial prosthesis. Of these arthroplasties, metal-on-metal type implants represent an increasing usage percentage. Metal-on-metal implants are selected largely for their low volumetric wear rate, durability, and resistance to corrosion. In spite of these advantages, little is known concerning the long-term consequences of heavy metal alloy use in the body, although early research indicates potentially carcinogenic results. This thesis is a preliminary investigation into these long term effects and their root causes. An improved comprehension of the corrosion kinetics and the rate of ion production from the high surface energy wear debris released by implant articulation can assist in illustrating the relative clinical significance of exposure to these metallic bodies over time. This thesis primarily focuses on developing a test methodology for the detection and analysis of ion dissociation in simulated body fluids. In order to validate this test methodology, the ion dissociation rates and surface characteristics of several predetermined diameters of cobalt chromium alloy spherical particles were analyzed. The effect of changing particle diameter, and thus surface area to volume ratio, on ion dissociation rate was determined to be significant when not affected by localized agglomeration. Additionally, preferential corrosion of cobalt within individual grains was observed and correlated to elevated cobalt concentrations in the electrolyte. These results suggest that ion dissociation kinetics for true wear particles can be determined through the refinement and application of the methodology developed.

The increasing usage of metal-on-metal joint replacements consisting of a cobalt-chromium-molybdenum alloy requires increasing concern regarding the inevitable generation of metallic wear debris. Patients with these joint replacements exhibit elevated concentrations of cobalt and chromium ions within their serum, blood and urine. The presence of these metal ions suggests the potential for bodily damage and indicates corrosive processes are acting upon wear debris. To understand the behavior of these corrosive processes, powders of cobalt-chromium-molybdenum alloy F-75 were studied. Four powder sizes (44, 74, 105, and 420 µm diameter) were subjected to Hank’s Balanced Salt Solution (HBSS) for a 42 day immersion test within an incubating shaker set at 37°C. Samples were removed periodically and analyzed for cobalt and chromium content using Inductive Coupled Plasma – Optical Emission Spectroscopy (ICP-OES). The resulting data gathered allowed for an evaluation of the corrosion rate as a function of particle diameter and exposure duration. Two observations were noted from the results. First, cobalt concentration (no chromium was detected) increased as a logarithmic function of time. For the 44, 105, and 420 µm diameter powders, cobalt concentration increased rapidly within four days of exposure but corrosion reached a plateau afterwards. The development of an oxide layer that inhibited further corrosion was the cause for this behavior. Second, the cobalt concentration reached a different upper limit depending on the particle diameter. For the 44, 105, and 420 µm diameter powders, samples reached average limits of 0.0611, 0.0314, and 0.0291 ppm Co, respectively. This observation can be related to the increase in particle surface area as diameter decreases within a given volume of particles. Modeling of this data resulted in empirical relationships for cobalt concentration and corrosion rate as a function of time, and particle diameter or surface area. However, these relationships were not reliably accurate in predicting the results of external corrosion studies on submicron cobalt-chromium particles. Consequently, this model of particle corrosion does not predict what may occur with nano-scale particles.

O objetivo da pesquisa foi avaliar a resistência de união entre o titânio fundido e cimentos resinosos, comparada com a de uma liga de níquel-cromo. Os fatores estudados foram: cimentos (Enforce, Cimento de resina 3M, Cement-it); conjugação liga/ revestimento ( titânio obtido com revestimento com a case e sem a case e liga de níquel-cromo, com fosfatado); tratamento superficial ( jateamento com óxido de alumínio e sistema Siloc); desgaste (cimentação antes do desgaste e depois). Para os espécimes foram obtidos discos por fundição, que foram jateados com óxido de alumínio. A metade foi cimentada depois desse tratamento e outra após a aplicação do Siloc. A armazenagem foi por 5 dias fazendo-se termociclagem (1.000 ciclos). Após o rompimento dos espécimes, por ensaio de tração, as superfícies cimentadas foram desgastadas com lixa n o 200 e novamente cimentadas. As conclusões foram: houve grande diferença entre cimentos; o titânio e o níquel-cromo nas devidas condições apresentaram retentividades semelhantes; o Siloc aumentou muito a retenção; o desgaste só influiu um pouco no titânio a case. / The Purpose of the research was to evaluate tensile bond strength of cemented titanium and nickel-chromium alloy cast discs. Factors studied were: Cements (Enforce, Resin cement 3M, Cement-it); Combination alloy/investment ( titanium obtained with a case and without a case investments, and nickel-chromium alloys); surface treatment (sandblasting with Al2O3 and Siloc application): surface abrading (test before and after).Cast discs with fixing stem were sandblasted and half of them were luted in this stage and the other one were luted after Siloc treatment. Specimens were stored for 5 days and thermalcycled (1,000 cycles). After tensile strength test surfaces were abraded and discs were luted again. The conclusions were: cements presented different bond strength; titanium and nickel-chromium alloy, under given condition, presented similar strength; Siloc system presented at least double strength; abrading of a case, titanium enhance only a little bond strength.

A higienização das próteses removíveis é fundamental para a longevidade do tratamento e prevenção de patologias orais. O objetivo deste estudo foi avaliar o efeito de higienizadores de imersão nas superfícies da liga metálica e resina acrílica termopolimerizável de Prótese Parcial Removível (PPR), simulando 180 dias. Discos (12 mm x 3 mm) foram confeccionados com ligas metálicas de cobalto-cromo para PPR: Vera PDI® (VP) e DeguDent® (DD). Cada disco metálico foi incluído em mufla previamente preparada por matrizes de teflon (38 mm x 18 mm x 4 mm), incorporando-se o disco metálico à resina acrílica termopolimerizável. Os espécimes (n= 5) foram imersos nas seguintes soluções: água destilada (grupo controle - AD), hipoclorito de sódio 0,05% (HS), Cepacol® (cloreto de cetilpiridínio 0,005% - CE), Periogard® (digluconato de clorexidina 0,12% - PE), Corega Tabs® (peróxido alcalino e enzima - CT), Polident® (peróxido alcalino e enzima - PO) e Medical Interporous Dentures® (ácido cítrico - MI). Foram realizadas análise da estabilidade de cor por meio de espectrocolorímetro, análise visual da presença de manchas no metal, análise da perda de massa em balança de alta precisão e análise da rugosidade por meio de rugosímetro. Como estudo complementar, foram realizadas análises quantitativas da liberação de íons (cobalto e cromo) em cada solução com espectrômetro de massas e análises ópticas e qualitativas com microscópio eletrônico de varredura (MEV) e espectrometria de energia dispersiva de Raios-X (EDS). Os resultados de rugosidade, alteração de cor e massa apresentaram distribuição normal e homogênea, tendo sido submetidos à ANOVA e teste de Tukey (p< 0,05). Quanto à rugosidade (Ra&micro;m), não houve diferença estatisticamente significante entre as soluções e ligas tanto para o metal quanto para a resina. Com relação à alteração de cor da resina acrílica termopolimerizável (&Delta;E), houve diferença estatisticamente significante entre as ligas, soluções e na interação liga x solução. As soluções AD, CE e PE propiciaram menores valores que as demais. A resina associada à DD apresentou maior alteração de cor do que quando associada à VP (1,06 ± 0,51 e 0,51 ± 0,28, respectivamente). Com relação à presença de manchas no metal, o HS propiciou manchamento em 100% dos espécimes. O grupo MI/DD propiciou em 60% e o MI/VP em 40% dos espécimes. Quando avaliada a alteração de massa (g), as soluções CT e MI propiciaram maiores valores. Entre as ligas, a VP apresentou maior perda de massa. Com relação à liberação de íons cobalto e cromo, a solução de HS e a MI propiciaram maior liberação e quando comparadas as ligas, VP apresentou maior liberação de íons. Com o MEV pôde-se verificar que houve corrosão generalizada com o HS e por pites com a MI. Concluiu-se que as soluções CE, PE e PO não apresentaram efeitos deletérios podendo ser auxiliares à escovação para higienização de PPR. / The hygiene care of the removable dentures is required for the longevity of the treatment and prevention of oral diseases. The aim of this study was to evaluate the effect of denture cleansers on the surfaces of the alloys and heat-polymerized acrylic resin for removable partial denture (RPD), simulating a period of 180 days. Circular specimens (12 mm x 3 mm) had been fabricated with cobalt-chromium alloys: Vera PDI&trade; (VP) and DeguDent&trade; (DD). The cast specimens were centered in the moulds previously prepared by matrices of teflon (38 mm x 18 mm x 4 mm) and the acrylic resin was inserted. The specimens (n= 5) had been immersed in the following solutions: distilled water (control - DW), sodium hypochlorite 0.05% (SH), Cepacol&trade; (cetilpiridinium chloride 0.005% - CE), Periogard&trade; (chlorexidine gluconate 0.12% - PE), Corega Tabs&trade; (alkaline peroxide and enzyme - CT), Polident&trade; (alkaline peroxide and enzyme - PO) and Medical Interporous Dentures&trade; (citric acid - MI). The color stability was analyzed using a colorimeter, and the presence of tarnishes on the metal was performed by a visual analysis. The weight loss was measured with a precision balance and the surface roughness was analyzed with a surf-test analyzer. As complementary analyzes a quantitative study of ions release (cobalt and chromium) using inductively mass spectrometry and optical and qualitative analyses with scanning electron microscopy (SEM) associated to dispersive energy spectrometry were performed. The results of roughness, color stability and weight loss presented normal and homogeneous distribution and were submitted to ANOVA (p &le; 0.05) and Tukey test. There was no significant difference among the solutions and between the alloys for both metal and resin roughness (Ra &micro;m). The acrylic resin color stability (&Delta;E) was analyzed and showed significant difference among the solutions, alloys and interaction. AD, CE and PE solutions presented the lowest values of color changes. The resin associated to DD presented higher color change than when associated with the VP (1.06 ± 0.51 and 0.51 ± 0.28, respectively). The HS caused tarnishes on 100% of specimens. The MI/DD group provided 60% and the MI/VP in 40% of specimens. When was analyzed the mass loss (g), the solutions CT and MI had the higher values. Between the alloys VP presented higher weight loss. HS and MI presented greater ionic release and between the alloys, VP presented greater release. With the SEM it was possible observe the presence of widespread corrosion in the HS group and pites corrosion in the MI group. It was concluded that CE, PE, CT and PO solutions had no deleterious effects on the compounds of RPD and may be indicate as auxiliaries to brushing in the RPD hygiene care.

Equal-channel angular pressing (ECAP) is one of the severe plastic deformation (SPD) to produce ultra-fine grain (UFG) material, and its principle and microstructural developments. The majority of papers on SPD materials have been devoted to the face centered cubic (FCC) structure materials such as Al, Cu and Ni. The UFG of high alloy ECAP processing has been difficult up to now, but we were successful in this study. Fe-20%Cr steel with extremely low C and N has different slip behavior from the FCC. The mechanical properties and corrosion resistance were investigated in term microstructural evolution during ECAP processing. / 博士(工学) / Doctor of Philosophy in Engineering / 同志社大学 / Doshisha University

The kinetics for sulphidation on a Ni-20 wt. % Cr alloy at 700ºC and sulphur potentials below 10⁻⁹ atmospheres have been studied using a thermogravimetric technique. The morphology of the reaction product was studied using optical microscopy, electron probe microanalysis and X-ray techniques. The kinetics were observed to be parabolic at sulphur potentials below 5 x 10⁻¹⁰ atmospheres with rates much slower than those reported for pure chromium under similar conditions. The parabolic kinetic reaction rate constant was found to vary as a semilogarithmic function of sulphur potential. The reaction product consisted of an external scale, identified as mainly Cr₃S₄, with dissolved nickel up to 5% and a subscale with morphological break-down of the alloy/external scale interface. Approximate determinations of the diffusivity of chromium in the alloy and the scale as well as sulphur diffusivity in the alloy have been made. Tentative mechanisms have been proposed to explain the diffusion control of the reaction and the stabilization of the external scale by dissolved nickel. / Thesis / Master of Engineering (ME)

A capacidade de resistência à corrosão sofrida pelas próteses dentais confeccionadas com ligas metálicas é de grande importância na clínica odontológica devido à ocorrência de possíveis reações biológicas, como por exemplo, sintomas alérgicos e degradação das restaurações. Em razão da presença de fatores diversos agindo no meio oral, todo material restaurador, metálico ou não, sofre uma ação de deterioração em sua superfície, seja por variação de pH, dieta alimentar, temperatura ou mastigação. Houve evolução de novas ligas metálicas, entre elas o titânio (Ti), que apresenta propriedades físicas e biocompatíveis excelentes, sendo um material muito utilizado em vários setores relacionados à área odontológica, principalmente na indústria de implantes dentais. Nesse estudo foi avaliada a rugosidade superficial de duas ligas metálicas (Ti e Ni Cr ) em três fases distintas, através de leituras realizadas pelo rugosímetro de superfície nos corpos de prova, submetidos à ciclagem térmica e submersos em saliva artificial à temperatura constante de 37 graus centígrados, por um período de 8 meses. Através dos resultados estatísticos obtidos, conclui-se que não existe diferença entre as ligas, no tocante aos fatores tempo e aspecto visual, havendo somente diferença significante entre as fases I e III do estudo. / The resistance capacity to corrosion to which the dental prosthesis made in mettalic alloys are subject has a major importance in the dental clinic, due to the occurance of possible biological reactions such as, for example, allergic symptoms and degradation of restorations. As there are several factors acting in the oral medium, every restoration material, either metallic or not, is subject to a deterioration action in its surface, caused by pH variation, alimentary diet, temperature and chewing. New metallic alloys have been developed, among them the Titanium (Ti), which presents excellent acceptance in the dentistry area , mainly in the industry of dental implants. This study appraised the superficial rugosity of two metallic alloys Titanium e Nickel Chromium (Ni Cr) in three different phases , through readings made by the surface rugosimeter in the test bodies, submitted to thermal cycling and submerged in artificial saliva at constant temperature of 37 degrees, for a period of 8 months. Through the achieved statistic results, it may be concluded that there is no difference between the alloys, concerning the time and visual aspect factors, there being a significant difference only between phases I and III of the study.