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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
171

Analys och utredning av värmebeständiga keramer för användning i hybriddrivlinor för fasta bränslen / Analysis and investigation of heat resistant ceramics for use in hybrid powertrains for solid fuels

Jonsson, Niklas January 2015 (has links)
Uppdragsgivaren Precer Group erbjuder tekniska lösningar för produktion av el genom ren förbränning av olika typer av fasta bränslen. Tekniken är anpassningsbar för att användas som återladdningskälla i olika typer av hybridfordon samt för produktion av el till bostäder och fritidshus. Arbetet har som syfte att presentera keramiska material till två olika zoner i Precers generation 2 drivlina där metallbränslen förbränns i en temperatur på 1800 °C. I Zon1 ska keramen klara en maximal temperatur på 2300°C och ha isolationsegenskaper. Till Zon2 önskas förmågan att motstå vidhäftning av heta partiklar och materialet ska kunna appliceras som ytbeläggning på befintligt rostfritt stål. Maximal temperatur i denna zon är 1100°C. Av de material som presenteras i arbetet är fullt stabiliserad Zirkoniumoxid (ZrO2) det enda materialet som klarar temperaturskravet i Zon1. ZrO2 har en låg värmeledningsförmåga på 2W/m*°C vilket resulterar i en god isolationsförmåga. Stora delar av arbetet är riktat till Zon2 där tester påvisar att keramiska material har en bättre förmåga att motstå vidhäftning av heta metallpartiklar än det befintliga rostfria stålet. De tre ytbeläggningar som testades var aluminiumoxid, zirkoniumoxid, och aluminia. Väljs istället att använda solida keramiska material ökar utbudet och material så som kiselkarbid( SiC), aluminiumtitanat(Al2TiO2), och kiselnitrid (Si3N4) är också tänkbara. Ett slutgiltigt materialval ansågs vara svårbedömt då konstruktionsunderlag saknades. / The Client Precer Group offers technical solutions for the production of electricity through clean combustion of various types of solid fuels. The technology is adaptable for use as a recharge source in different types of hybrid vehicles and for the production of electricity to homes. The aim of this exam paper is to examine the possibility to use ceramics in Precers new drivetrain where metal fuels are burned at a temperature of 1800 °C. There are two different zones to examine. In Zon1, the ceramic should withstand a maximum temperature of 2300°C and have insulation properties. The ability to resist adhesion of hot metall particles is desirable in Zone 2, where the maximum temperature is 1100°C. There is also a request that the ceramic is to be applied as a coating. Of the materials that where found, fully stabilized zirconia (ZrO2) is the only material that can withstand the demanding temperature in Zone1. The material has a low thermal conductivity at 2W/m°C that results in good insulation. The ability to withstand adhesion was estimated and the results indicate that ceramic materials have a higher capacity to withstand adhesion of hot metall particles than the existing stainless steel. The three coatings tested where pure Alumina, Zirconia, and Alumina 3% Titania. If solid ceramics are to be used instead, the range of materials is increased. Materials such as Silconcarbide (SiC), Aluminimtitanate (Al2TiO2) and siliconnitride (Si3N4) are also possible candidates. A final choice of materiel was considered to be hard because the lack of design documentation.
172

Einfluss verschiedener Reinigungsmethoden auf die Haftkraft rezementierter implantatgetragener Zirkoniumdioxid-Kronengerüste / Influence of different cleaning methods on the bond strength of re-cemented implant supported zirconia crown frameworks

Pohlmeyer, Franziska 29 October 2013 (has links)
Stetig steigende Ansprüche an ästhetisch ansprechenden festsitzenden Zahnersatz, haben zu einer enormen Entwicklung im Bereich der enossalen Implantologie geführt. Ebenso führte die Weiterentwicklung im Bereich dentaler Keramiken zu einer immer häufigeren Anwendung vollkeramischer Systeme. In der vorliegenden in-vitro-Studie wurde der Einfluss verschiedener Reinigungsmethoden auf die Haftkraft rezementierter implantatgetragener Zirkoniumdioxid-Kronengerüste untersucht. Die untersuchten Parameter waren: manuelle Entfernung der Zementreste mit Hilfe eines Heidemann Spatels, Säuberung durch Ausstrahlung der Suprakonstruktion mit Aluminiumdioxid (Korngröße: 110 μm, 2 bar, 15s Dauer), kombinierte manuelle Säuberung und Ultraschallreinigung (Isopropanolbad 99%ig). Für den Versuch wurden insgesamt 52 Probekörper mit den drei genannten Parametern, sowie eine Kontrollgruppe mit unbehandelten Zirkoniumdioxid-Käppchen je 13 Mal einem Abzugsversuch unterzogen. Zur Herstellung der Kronengerüste wurden die Titan-Abutments mit dem Cercon® eye Scanner (DeguDent, Hanau) eingescannt und die Zirkoniumdioxid-Käppchen daraufhin digital mit der CAD-Software Cercon® art modelliert und im Labor der Firma DeguDent, Hanau, gefräst. Anschließend wurden die Kronengerüste auf den Abutments mit TempBond® NE der Firma Kerr (Ratstatt, Deutschland) zementiert und in der Universalprüfmaschine Zwick Z007 (Zwick, Ulm) den Abzugsversuchen bis zur Dezementierung unterzogen. Die Auswertung der Abzüge erfolgte mit der Software „testXpert“. Die Ergebnisse zeigten, dass die Kombination aus manueller Reinigung und Ultraschallbad verglichen mit den anderen Methoden zu statistisch signifikant höheren Retentionswerten führte. Zwischen der reinen manuellen Säuberung und der Reinigung durch Ausstrahlen des Kronengerüstes zeigte sich kein klinisch relevanter und signifikanter Unterschied.
173

Thermal and non-thermal processes involving water on Apollo lunar samples and metal oxide powders

Poston, Michael Joseph 27 August 2014 (has links)
Water is of interest for understanding the formation history and habitability of past and present solar system environments. It also has potential as a resource - when split to its constituent oxygen and hydrogen - both in space and on the Earth. Determining the sources, evolution, and eventual fate of water on bodies easily reachable from Earth, especially Earth's moon, is thus of high scientific and exploration value to the private sector and government space agencies. Understanding how to efficiently split water with solar energy has potential to launch a hydrogen economy here on Earth and to power spacecraft more sustainably to far away destinations. To address the fundamental interactions of water with important surfaces relevant to space exploration and technology development, temperature programmed desorption (TPD) and water photolysis experiments under well controlled adsorbate coverages have been carried out and are described in detail in this thesis. TPD experiments under ultra-high vacuum (UHV) conditions were conducted on lunar surrogate materials and genuine lunar samples brought to Earth by the Apollo program. The TPD's were conducted to determine the desorption activation energies of water chemisorbed directly to the powder surfaces, knowledge of which can improve existing models of water evolution on Earth's moon and aid in interpreting data collected by spacecraft-based investigations at the Moon. The TPD experiments of molecular water interacting with two lunar surrogates (micronized JSC-1A and albite) in ultra-high vacuum revealed water desorption during initial heating to 750 K under ultra-high vacuum. Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) indicated possible water formation during the initial heating via recombinative desorption of native hydroxyls above 425 ± 25K. Dissociative chemisorption of water (i.e., formation of surface hydroxyl sites) was not observed on laboratory time scales after controlled dosing of samples (initially heated above 750 K) with 0.2 - 500 L exposures of water. However, pre-heated samples of both types of surrogates were found to have a distribution of molecular water chemisorption sites, with albite having at least twice as many as the JSC-1A samples by mass. A fit to the TPD data yields a distribution function of desorption activation energies ranging from ~0.45 eV to 1.2 eV. Using the fitted distribution function as an initial condition, the TPD process was simulated on the timescale of a lunation. A preview of these results and their context was published in Icarus (2011) 213, 64, doi: 10.1016/j.icarus.2011.02.015 by lead author Charles Hibbitts and the full treatment of the results from the TPD on lunar surrogates (presented here in Chapter 2) has been published in the Journal of Geophysical Research – Planets (2013) 118, 105, doi: 10.1002/jgre.20025 by lead author Michael J Poston. The desorption activation energies for water molecules chemisorbed to Apollo lunar samples 72501 and 12001 were determined by temperature programmed desorption (TPD) experiments in ultra-high vacuum. A significant difference in both the energies and abundance of chemisorption sites was observed, with 72501 retaining up to 40 times more water (by mass) and with much stronger interactions, possibly approaching 1.5 eV. The dramatic difference between the samples may be due to differences in mineralogy, surface exposure age, and contamination of sample 12001 with oxygen and water vapor before it arrived at the lunar sample storage facility. The distribution function of water desorption activation energies for sample 72501 was used as an initial condition to mathematically simulate a TPD experiment with the temperature program matching the lunar day. The full treatment of the TPD results from these two lunar samples (presented here in Chapter 3) has been submitted with the title "Water chemisorption interactions with Apollo lunar samples 72501 and 12001 by ultra-high vacuum temperature programmed desorption experiments" to Icarus for publication in the special issue on lunar volatiles by lead author Michael J Poston. A new ultra-high vacuum system (described in Chapter 4) was designed and constructed for planned experiments examining the possible formation of hydrated species, including water, from interaction of solar wind hydrogen with oxygen in the lunar regolith and to examine the effects of the active radiation environment on water adsorption and desorption behavior on lunar materials. This system has been designed in close collaboration with Dr. Chris J Bennett. An examination of a unique system for water photolysis - zirconia nanoparticles for hydrogen production from water with ultra-violet photons - was performed to better understand the mechanism and efficiency of water splitting on this catalyst. Specifically, formation of H₂ from photolysis of water adsorbed on zirconia (ZrO₂) nanoparticles using 254 nm (4.9 eV) and 185 nm (6.7 eV) photon irradiation was examined. The H₂ yield was approximately an order of magnitude higher using monoclinic versus cubic phase nanoparticles. For monoclinic particles containing 2 monolayers (ML) of water, the maximum H₂ production rate was ~0.4 µmole hr⁻¹ m⁻² using 185 + 254 nm excitation and a factor of 10 lower using only 254 nm. UV reflectance reveals that monoclinic nanoparticles contain fewer defects than cubic nanoparticles. A H₂O coverage dependence study of the H₂ yield is best fit by a sum of interactions involving at least two types of adsorbate-surface complexes. The first dominates up to ~0.06 ML and is attributed to H₂O chemisorbed at surface defect sites. The second dominates at coverages up to a bilayer. H₂ formation is maximum within this bilayer and likely results from efficient energy transfer from the particle to the interface. Energy transfer is more efficient for the monoclinic ZrO₂ nanoparticles and likely involves mobile excitons. These results (presented in Chapter 5) have been submitted with the title "UV Photon-Induced Water Decomposition on Zirconia Nanoparticles" for publication in the Journal of Physical Chemistry C by lead author Michael J Poston. This paper has been reviewed and will be accepted after minor modification.
174

Electrochemical Promotion of Gold Nanoparticles Supported on Yttria-Stabilized Zirconia

Kim, Jong Min 23 November 2011 (has links)
The feasibility of highly dispersed gold nanocatalyst supported on yttria-stabilized zirconia (YSZ) for the model reactions of C2H4 and CO oxidation is demonstrated for the first time. Gold nanoparticles are synthesized on YSZ powder by chemical reduction of the precursor salt in the mixture of ethanol, water and polyvinylpyrrolidone (PVP). Resulting metal loading of the catalysts are 1 wt.% with average particle sizes ranging from 6 to 9 nm. Results of CO and C2H4 oxidation display catalytic activity at 65 0C and 25 0C for CO and C2H4 oxidation, respectively. The catalytic properties of the catalysts are different due to their average particle size. Electrochemical Promotion of Catalysis (EPOC) of C2H4 oxidation is demonstrated. Application of constant potential difference between two electrodes in the bipolar electrochemical cell led to increase in C2H4 conversion. A proposed mechanism explains the bipolar EPOC phenomenon through formation of O2- flux across the electrochemical cell, resulting in the change of Work Function of gold nanoparticles placed in between the electrodes and is electronically isolated.
175

Fundamental investigation of refractory reactions occurring at high temperatures in continuous steel casting process

Liu, Fuhai, Material Science & Engineering, UNSW January 2007 (has links)
An in-depth study has been carried out to investigate refractory degradation during continuous steel casting processes. Slag/refractory interactions have been investigated through a study of the wetting behaviour and gas generation phenomena at the slag/refractory interface at 1550oC using sessile drop experiments. The influence of carbon content and slag composition was investigated. Two different steel casting slags (slag1: MnO 50%, SiO2 25%, Al2O3 25%; and slag2: MnO 40%, SiO2 60%) have been studied along with yttria stabilized zirconia refractory substrates respectively containing 10%, 15% and 20% carbon. The gas generation has been measured using the Infrared gas analyser, and its influence has also been investigated by taking optical images at varying times. The total amount of gases emitted has shown the dependence on the compositions of refractory substrates and the existence of casting slags. Under the investigation of zirconia-carbon refractory, a new phenomenon that the gas generated can push the liquid slags away and minimise the contact of slags and refractory substrates has been proven.
176

Estudos de blocos de zircônia / hidroxiapatita: perspectiva para novas aplicações como biomaterial. / Studies of zirconia / hydroxyapatite blocks: perspective for new applications as biomaterial.

GADELHA, Leonardo Sarmento Meira. 18 April 2018 (has links)
Submitted by Johnny Rodrigues (johnnyrodrigues@ufcg.edu.br) on 2018-04-18T17:04:56Z No. of bitstreams: 1 LEONARDO SARMENTO MEIRA GADELHA - DISSERTAÇÃO PPG-CEMat 2014..pdf: 1520712 bytes, checksum: 8f477b0a9d2403096c41524ecdb9cda1 (MD5) / Made available in DSpace on 2018-04-18T17:04:56Z (GMT). No. of bitstreams: 1 LEONARDO SARMENTO MEIRA GADELHA - DISSERTAÇÃO PPG-CEMat 2014..pdf: 1520712 bytes, checksum: 8f477b0a9d2403096c41524ecdb9cda1 (MD5) Previous issue date: 2014-08-07 / As cerâmicas são materiais sólidos não metálicos inorgânicos. Por apresentar natureza refratária, dureza e inércia química frente às condições adversas encontradas na cavidade bucal, as cerâmicas foram introduzidas como material odontológico devido a sua biocompatibilidade, estabilidade de cor em longo prazo, resistência ao desgaste e a sua capacidade de serem conformadas em formas precisas. Destacam-se entre as cerâmicas utilizadas nos implantes ortodônticos a zircônia e a hidroxiapatita por possuirem propriedades mecânicas muito semelhantes à de metais e cor semelhante à cor do dente. Baseado nestas informações este trabalho tem como objetivo estudar as propriedades de blocos sinterizados de Zircônia/Hidroxiapatita como perspectiva de aplicação como biomaterial. Verificou-se a possibilidade de obter blocos Zircônia/Hidroxiapatita, controlando suas características morfológicas e cristalinas pela adição de hidroxiapatita, com potencial para ser aplicado como biomaterial. / Ceramics are inorganic non-metallic solids. By presenting refractory nature, hardness and chemical inertness face of the adverse conditions found in the oral cavity, ceramics were introduced as dental material due to its biocompatibility, color stability for long-term wear resistance and its ability to be formed into precise shapes. Prominent among the ceramics used in orthodontic zirconia implants and hydroxyapatite to possess mechanical properties very similar to the metal and color similar to the color of the tooth. Based on this information this work was to study the properties of sintered blocks of zirconia / hydroxyapatite as application perspective as a biomaterial. It has been found the possibility to obtain zirconia / hydroxyapatite blocks, controlling their morphological and crystalline characteristics by adding hydroxyapatite, with a potential to be applied as a biomaterial.
177

Estruturas cer?micas a base de zirc?nia e alumina utilizadas na confec??o de infra - estruturas para coroas e pontes fixas

Silva, Cl?udia Angl?lica Melo da 29 March 2010 (has links)
Made available in DSpace on 2014-12-17T14:06:54Z (GMT). No. of bitstreams: 1 ClaudiaAMS_DISSERT.pdf: 2577371 bytes, checksum: 741bbb91aaccd5dd4b233f1b8017a831 (MD5) Previous issue date: 2010-03-29 / The continuous advances in ceramic systems for crowns and bridges infrastructure getting researchers and manufacturers looking for a material that has good mechanical properties and aesthetic. The purpose of this study was to verify in which composition and sintering temperature the ceramic system for infrastructure composed of alumina and zirconia would have the best mechanical properties. With this objective we made in UFRN laboratories 45 test bodies in the form of rectangular bars with the following dimensions: 30mm x 8mm x 3mm, where we separated by the sintering temperature: 1200?C, 1300?C and 1400?C, and by comp osition: 33% Zirconia + 67% Alumina; 50% Zirconia + 50% Alumina and 25% Zirconia + 75% Alumina, these test bodies were not infiltrated with glass. Also, were made nine test bodies by a technical from a laboratory with a commercial ceramic system: in the Ceram Zirc?nia (Vita - Zahnfabrik) with the following dimensions: 20mm x 10mm x 0.5mm, these test bodies following all recommendations of the manufacturer and were infiltrated with glass. Were realized optical and electronic microscopy analyses, hardness testing, resistance to bending in three points, porosity and bulk density. After analysis of the results we verified that with the increasing of sintering temperature, increased the value of resistance to bending, but with the same temperature there was no significant difference between the different compositions, samples made with the commercial ceramic that were infiltrated, presented a resistance to bending six times greater than the samples sintered to 1400?C and which have not been infiltra ted. There was no significant difference between the values of apparent porosity for the samples made in UFRN laboratories, but the samples of commercial ceramic obtained 0% in porosity apparent value. In tests of Rockwell Hardness there is an increase in the value of Hardness, with the increase of sintering temperature for the samples not infiltrated. Samples infiltrated showed similar values as the samples sintered in 1400?C. There was no significant difference between the values of apparent density among samples manufactured in UFRN laboratories and samples made with a commercial ceramic / Os avan?os constantes dos sistemas cer?micos para infra-estruturas de coroas e pontes fazem com que os pesquisadores e fabricantes busquem um material que tenha boas propriedades mec?nicas e est?ticas. O intuito deste trabalho foi verificar em qual composi??o e temperatura de sinteriza??o o sistema cer?mico a base de alumina e zirc?nia para infra-estrutura teria as melhores propriedades mec?nicas. Com este objetivo confeccionamos nos laborat?rios da UFRN 45 corpos-e-prova em forma de barras retangulares com as seguintes dimens?es: 30mm x 8mm x 3mm, onde os separamos por temperatura de sinteriza??o: 1200?C, 1300?C e 1400?C; e por composi??o: 33% Zirc?nia + 67% Alumina; 50% Zirc?nia + 50% Alumina e 25% Zirc?nia + 75% Alumina, estes corpos-de-prova n?o foram infiltrados com vidro. Foram confeccionados ainda nove corpos- e-prova por um t?cnico de laborat?rio com um sistema cer?mico comercial o In Ceram Zirc?nia (Vita Zahnfabrik) com as seguintes dimens?es: 20mm x 10mm x 0,5mm, estes corpos-de-prova seguiram todas as recomenda??es do fabricante e foram infiltrados com vidro. Foram realizadas an?lises por microscopia ?tica e eletr?nica, ensaios de dureza, de resist?ncia ? flex?o em tr?s pontos, porosidade e densidade aparente. Ap?s a an?lise dos resultados verificamos que com o aumento da temperatura de sinteriza??o, aumentamos o valor da resist?ncia ? flex?o, sendo que dentro da mesma temperatura n?o houve diferen?a significante entre as diferentes composi??es, as amostras confeccionadas com a cer?mica comercial e que foram infiltradas apresentaram uma resist?ncia ? flex?o seis vezes maior que as amostras sinterizadas ? 1400?C e que n?o foram infiltradas. N?o houve diferen?a significante entre os valores da porosidade aparente para as amostras confeccionadas nos laborat?rios da UFRN, j? as amostras da cer?mica comercial obtiveram um valor de 0% de porosidade aparente. Nos ensaios de Dureza Rockwell verifica-se um aumento no valor da Dureza, com o aumento da temperatura de sinteriza??o das amostras n?o infiltradas. As amostras infiltradas apresentaram valores similares aos das amostras sinterizadas ? 1400?C. N?o houve diferen?a significante entre os valores de densidade aparente entre as amostras confeccionadas nos laborat?rios da UFRN e as amostras confeccionadas com a cer?mica comercial
178

Propriedade fotoluminescente da ZrO2: Tb+3, Eu+3, Tm+3 obtida pelo m?todo de polimeriza??o de complexos

Lovisa, Laura Ximena 16 December 2013 (has links)
Made available in DSpace on 2014-12-17T14:07:17Z (GMT). No. of bitstreams: 1 LauraXL_DISSERT.pdf: 3047950 bytes, checksum: 570af1df35d3161d6677ac6ec832e390 (MD5) Previous issue date: 2013-12-16 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / Recent studies are investigating a new class of inorganic materials which arise as a promising option for high performance applications in the field of photoluminescence. Highlight for rare earth (TR +3 ) doped, which have a high luminous efficiency, long decay time and being able to emit radiation in the visible range, specific to each element. In this study, we synthesized ZrO2: Tb +3 , Eu +3 , Tm +3 nanoparticles complex polymerization method (CPM). We investigated the influences caused by the heat treatment temperature and the content of dopants in zirconia photoluminescent behavior. The particles were calcined at temperature of 400, 500 and 600 ? C for two hours and ranged in concentration of dopants 1, 2, 4 and 8 mol% TR +3 . The samples were characterized by thermal analysis, X-ray diffraction, photoluminescence of measurements and uv-visible of spectroscopies. The results of X-ray diffraction confirmed the formation of the tetragonal and cubic phases in accordance with the content of dopants. The photoluminescence spectra show emission in the region corresponding simultaneous to blue (450 nm), green (550 nm) and red (615 nm). According to the results, ZrO2 particles co-doped with rare earth ions is a promising material white emission with a potential application in the field of photoluminescence / Estudos recentes investigam uma nova classe de materiais inorg?nicos que surgem como uma op??o promissora em aplica??es de alto desempenho no campo da fotoluminesc?ncia. Destaque para f?sforos dopados com ?ons de terras raras (TR +3 ), que possuem uma alta efici?ncia luminosa, um longo tempo de decaimento e por serem capazes de emitir radia??es na faixa do vis?vel, espec?ficas de cada elemento. Neste trabalho, foram sintetizadas nanopart?culas de ZrO2:Tb +3 , Eu +3 , Tm +3 pelo m?todo de polimeriza??o dos complexos (MPC). Foram investigadas as influ?ncias causadas pela temperatura de tratamento t?rmico e pelo teor dos dopantes no comportamento fotoluminescente da zirc?nia. As part?culas foram calcinadas nas temperaturas de 400, 500 e 600?C durante duas horas e a concentra??o dos dopantes variou em 1, 2, 4 e 8% mol TR +3 . As amostras foram caracterizadas por an?lises t?rmicas (TG/ DSC), difra??o de raios X (DRX), medidas de fotoluminesc?ncia (FL) e espectroscopia na regi?o do UV-Vis?vel (UV-vis). Os resultados de difra??o de raios X confirmaram a forma??o das fases tetragonal e c?bica de acordo com o teor de dopantes. Os espectros de fotoluminesc?ncia apresentam emiss?es simult?neas correspondentes na regi?o do azul (450 nm), do verde (550 nm) e do vermelho (615 nm). De acordo com os resultados obtidos, as part?culas de ZrO2 codopadas com ?ons de terras raras apresentam-se como um material promissor para emiss?o no branco com um potencial de aplica??o no campo da fotoluminesc?ncia
179

Etude d'empilements multicouches colloidaux préparés par voie sol-gel : propriétés optiques et mécaniques / Study of colloidal multilayer stacks prepared by sol-gel process : optical and mechanical properties

Dieudonné, Xavier 10 November 2011 (has links)
Les procédés de dépôt de couches minces optiques par voie physique ou par voie sol-gel présentent par nature des limitations pour la réalisation de revêtements épais (>1 µm) et ont alors recours à des empilements multicouches pour la préparation de miroirs diélectriques ou de polariseurs. C'est pour ces raisons qu'il est intéressant d'étudier les conditions permettant d'augmenter l'épaisseur critique des films sol-gel notamment. Après avoir étudié la capacité d'empilements des couches colloïdales, trois principaux paramètres ont été identifiés permettant d'augmenter l'épaisseur critique d'empilements monomatériaux et multimatériaux. Ces paramètres sont : l'épaisseur déposée,les interactions chimiques entre les particules et le temps de séchage du film. Ils influencent la microstructure des empilements et par conséquent les propriétés optiques et mécaniques. En contrôlant tous ces paramètres, nous avons montré qu'il est possible de préparer des empilements colloïdaux de fortes épaisseurs ouvrent la voie à la préparation sol-gel de miroirs de hautes performances et/ou de polariseurs. En outre, un développement spécifique de méthodes de caractérisations optiques et mécaniques a été nécessaire pour l'étude de ces films sol-gel, à la fois minces et fragiles. / Main optical deposition processes, physical vapor deposition or sol-gel, exhibit difficulties of achieving thick coatings (>1 µm) and to build multilayer stacks (dielectric mirrors, polarizers). For these reasons, we have studied the conditions to enable a significative increase of deposited sol-gel films thickness. Three main parameters have been evidenced enabling the control of the stacking ability : single layer deposited thickness, chemical interactions beetween nanoparticles and coating drying time. We have shown that these parameters depend on the sol composition and on deposition conditions (process) and that the microstructure of single material stacking is influenced. Optical and mechanical properties of sol-gel films have been studied and optimized regarding these different material and process parameters. For this reason, optical and mechanical characterization techniques have been specifically developed and can now be used for fragile and thin film characterization. In controlling all these parameters, it is now possible to prepare multilayer colloidal stack with high thicknesses enabling the fabrication of high-performance mirrors and polarizers.
180

Obtenção de nanowhiskers de celulose para aplicação em revestimento polimérico

Borsoi, Cleide January 2016 (has links)
Os revestimentos poliméricos podem atuar como uma barreira física entre os íons agressivos e o substrato metálico. Porém, uma exposição prolongada pode causar danos ao revestimento polimérico, conduzir a uma redução contínua do efeito barreira e por consequência a perda da proteção contra a corrosão. A utilização de nano materiais pode atuar aumentando o efeito barreira, proporcionando um aumento no caminho de difusão dos íons agressivos e água até o substrato metálico. Nanopartículas de celulose apresentam elevada cristalinidade e razão de aspecto, excelentes propriedades mecânicas e são proveniente de fonte renovável. Por outro lado, a polianilina (PAni) vem sendo utilizada em revestimentos devido a elevação do potencial de corrosão dos aços devido o seu comportamento redox que proporciona a formação de uma camada de óxidos estável no substrato metálico. A aderência do revestimento polimérico é fundamental para que este possa atuar como revestimento protetor contra a corrosão. Com isso, um pré-tratamento superficial a base de ácido hexafluorzircônico e a utilização de organosilanos na resina epóxi, podem ser utilizados melhorando as propriedades de proteção contra a corrosão e de aderência. O objetivo deste estudo consistiu na obtenção de nanowhiskers de celulose (CNW) por moagem ultrafina através da celulose microcristalina (MCC) para posterior utilização em revestimento polimérico a base de resina epóxi. A CNW foi utilizada funcionalizada ou não com PAni SE (polianilina na forma condutora – sal de esmeraldina) em comparação a MCC nas mesmas condições. Foi avaliada a incorporação de silano aminopropiltrietoxisilano (APS) na resina epóxi e a utilização de uma camada de conversão de zircônia (Zr) aplicada ao substrato metálico. Os revestimentos poliméricos foram avaliados quanto a propriedades mecânicas e à proteção contra a corrosão. As imagens da microscopia de transmissão (TEM) mostram que é possível a obtenção da CNW por meio do processo de moagem, apresentando melhor estabilidade térmica em comparação a MCC. Os revestimentos poliméricos utilizando o silano APS e a camada de conversão de Zr apresentaram as melhores propriedades físicas e mecânicas. A interação entre a carga de reforço, a resina epóxi e a superfície metálica é um fator determinante na eficiência do revestimento polimérico, pois de acordo com a análise de migração subcutânea, a superfície do aço carbono, após 1000 h de exposição, não apresentou corrosão superficial. Com relação à proteção contra a corrosão, quando incorporado a CNW funcionalizada com PAni SE ao revestimento epóxi com APS e a camada de Zr, este apresentou os melhores resultados como constatado nas análises de névoa salina e espectroscopia de impedância eletroquímica (EIS). / Polymeric coatings can act as a physical barrier between the aggressive ions and the metal substrate. However, prolonged exposure can cause damage to the polymer coating and conduct to a continuous reduction in the barrier effect and result in the loss of protection against corrosion. The use of nanomaterials may act by increasing the barrier effect and providing an increased diffusion path of aggressive ions and water to the metal substrate. Cellulose nanoparticles have high crystallinity and aspect ratio, excellent mechanical properties and are derived from renewable sources. On the other hand polyaniline (PAni) has been used in coatings due to the increase of the corrosion potential of the steel due to redox behavior that results in the formation of a stable oxide layer on the metallic substrate. The adhesion of the polymeric coating is essential so that it can act as a protective coating against corrosion. With this, a superficial pre-treatment based on hexafluorzircônico acid and the use of organosilanes in the epoxy resin, can be used to improve the protection against corrosion properties and adhesion. The objective of this study was to obtain cellulose nanowhiskers (CNW) for ultrafine grinding through microcrystalline cellulose (MCC) for subsequent use in the polymer coating based on epoxy resin. The CNW was used functionalized or not with PAni SE (polyaniline in the conductive form - emeraldine salt) compared with MCC under the same conditions. The incorporation of silane aminopropyltriethoxysilane (APS) was evaluated in the epoxy resin and the use of a zirconia conversion layer (Zr) applied to the metal substrate. The polymeric coatings were evaluated for mechanical properties and corrosion protection. Transmission microscopy (TEM) show that obtaining the CNW through the ultrafine grinding process is possible, resulting in better thermal stability compared with MCC. Polymeric coatings using APS silane and Zr conversion coating had the best physical and mechanical properties. The interaction between the reinforcing filler, the epoxy resin and the metal surface is a determining factor in the efficiency of the polymeric coating, because according to the subcutaneous migration analysis, carbon steel surface after 1000 h of exposure, showed no corrosion superficial. With regard to protection against corrosion, when incorporated CNW functionalized with PAni SE to epoxy coating with APS and the Zr layer, showed the best results as found in salt spray tests and electrochemical impedance spectroscopy (EIS).

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