The goal of service life prediction is to accurately predict the useful lifetime of a coating system in a typical service environment. Field testing is the most true-to-life form of service life testing but requires long exposure times, often not quick enough to readily aid redesign in the product development cycle. As an alternative, accelerated weathering chambers are used to speed up coating failure in a laboratory setting. These devices do indeed accelerate failure but often produce failure modes that are not seen in actual service or produce material rankings that are not reproducible. This work explores the principle of cumulative stressor damage for an exterior architectural coating being exposed to outdoor conditions in San Luis Obispo, California, as well as an accelerated UV/moisture protocol. The accelerated UV/moisture protocol is executed first by ASTM D4587, and then by creating a custom exposure test cycle based on locally observed weather. Comparison of failure mode and quantification of failure is determined by gloss and spectral reflectance measurements. Finally, acceleration factor determination for the new SLO-in-a-box protocol is outlined, with a discussion of preliminary results.

É conhecido que, atualmente, o Brasil possui uma demanda substancial de obras de engenharia, como por exemplo, o Trem de Alta Velocidade (TAV) entre as cidades do Rio de Janeiro e de Campinas, necessárias para suportar as presentes e futuras demandas para o desenvolvimento do país. Este projeto governamental do TAV deverá requerer produção elevada de agregados de alta qualidade para emprego como lastro e também para concreto. No tocante ao uso como lastro, o agregado fica exposto e sujeito à ação constante das intempéries, fazendo com que estudos envolvendo alterabilidade sejam tão importantes quanto os de caracterização geomecânica dos materiais pétreos, levando-se em conta as condições intempéricas típicas de uma zona tropical que estarão submetidos. Estas constatações motivaram investigar as relações entre as propriedades tecnológicas de nove tipos de rochas cristalinas (micro-gabro, gnaisse e variedades de granitos) e suas utilizações como lastro do trecho Campinas/São Paulo do traçado do TAV. Em termo práticos, estas rochas foram submetidas a ensaios físicos, mecânicos e de alterabilidade acelerada, sendo que os testes de ciclagem água-estufa foram conjugados aos ensaios de abrasão Los Angeles, choque Treton e esmagamento. Os resultados indicaram que alguns materiais apresentaram valores de resistência inferiores ou próximos aos limites normatizados para lastros de ferrovia, além da perda de qualidade verificada nos ensaios de resistência à intempérie, inviabilizando ou restringindo a utilização de três dos materiais estudados para lastro. De modo geral, tais informações poderão servir de subsídio aos órgãos governamentais para tomada de decisões, quanto ao emprego dos materiais disponíveis na área onde será construído o TAV brasileiro, uma vez que os custos de manutenção da camada de lastro da ferrovia são críticos quando se opta por uma via lastrada ou em laje. / It is well known that Brazil currently shows a high number of engineering projects that are necessary to the development of the country. The projects include the High-Speed Rail (HSR) that will connect Rio de Janeiro and Campinas cities and requires a great production of high-quality construction aggregates to be used in track ballast and also in concrete. In the case of the track ballast, previous studies about the weathering of the aggregates together with a mechanical characterization are important and have to take in consideration that the material will be submitted to weathering conditions typical of a tropical environment. These assumptions motivated the investigation of the technological properties of nine types of crystalline rocks (microgabbro, gneiss and varied granitic rocks) considering their potential to be used as track ballast in the HSR between Campinas and São Paulo. The rock samples were submitted to physical, mechanical and accelerated weathering tests. The soundness by artificial weathering, drying water were conjugated to the Los Angeles abrasion tests, Treton shock and crushing. The results indicate that some materials present resistance values bellow or near the limit normalized for track ballast, besides the loss of the quality verified in weathering resistance tests, making it impossible or restricting the use of the three studied materials as track ballast. In general, such information can be used by government agencies to make decisions about the materials available in the area where the brazilian HSR will be built once the maintenance costs of the track ballast are critical to the choice between a track ballast or slab track.

One of the most stunning works of art on the Scripps College campus is the mural Flower Vendors(1946). The artist,Alfredo Ramos Martínez, an influential figure in Mexican Modernism, executed the work using a variety of traditional and non-traditional techniques. Prior analysis of the work indicated the use of a wax emulsion medium and established the range of pigments used. Ramos Martínez’s use of lead chromate (chrome yellow, Pb(CrO4)) was unusual in wall painting, and the pigment itself has been shown to photodegrade and darken over time in oil paintings, due to the reduction of Cr(VI) to Cr(III). The Pb(CrO4) in Flower Vendorsdoes not appear to have darkened, raising questions about the stability of lead chromate in a wax-emulsion medium relative to that of oil-based mediums. To better understand the behavior of lead chromate in wax-based mediums, a historical synthesis of lead chromate was recreated, and the pigment was suspended in four different binder matrices: a wax-water emulsion, refined linseed oil, cold-pressed linseed oil, and poppy oil. Each of these paint-binder mixtures wasaged beneath full-spectrum 6500 K LED lights. The relative darkening of the pigments was measured using UV-Vis reflectance colorimetry, and comparisons were made between the mediums.

É conhecido que, atualmente, o Brasil possui uma demanda substancial de obras de engenharia, como por exemplo, o Trem de Alta Velocidade (TAV) entre as cidades do Rio de Janeiro e de Campinas, necessárias para suportar as presentes e futuras demandas para o desenvolvimento do país. Este projeto governamental do TAV deverá requerer produção elevada de agregados de alta qualidade para emprego como lastro e também para concreto. No tocante ao uso como lastro, o agregado fica exposto e sujeito à ação constante das intempéries, fazendo com que estudos envolvendo alterabilidade sejam tão importantes quanto os de caracterização geomecânica dos materiais pétreos, levando-se em conta as condições intempéricas típicas de uma zona tropical que estarão submetidos. Estas constatações motivaram investigar as relações entre as propriedades tecnológicas de nove tipos de rochas cristalinas (micro-gabro, gnaisse e variedades de granitos) e suas utilizações como lastro do trecho Campinas/São Paulo do traçado do TAV. Em termo práticos, estas rochas foram submetidas a ensaios físicos, mecânicos e de alterabilidade acelerada, sendo que os testes de ciclagem água-estufa foram conjugados aos ensaios de abrasão Los Angeles, choque Treton e esmagamento. Os resultados indicaram que alguns materiais apresentaram valores de resistência inferiores ou próximos aos limites normatizados para lastros de ferrovia, além da perda de qualidade verificada nos ensaios de resistência à intempérie, inviabilizando ou restringindo a utilização de três dos materiais estudados para lastro. De modo geral, tais informações poderão servir de subsídio aos órgãos governamentais para tomada de decisões, quanto ao emprego dos materiais disponíveis na área onde será construído o TAV brasileiro, uma vez que os custos de manutenção da camada de lastro da ferrovia são críticos quando se opta por uma via lastrada ou em laje. / It is well known that Brazil currently shows a high number of engineering projects that are necessary to the development of the country. The projects include the High-Speed Rail (HSR) that will connect Rio de Janeiro and Campinas cities and requires a great production of high-quality construction aggregates to be used in track ballast and also in concrete. In the case of the track ballast, previous studies about the weathering of the aggregates together with a mechanical characterization are important and have to take in consideration that the material will be submitted to weathering conditions typical of a tropical environment. These assumptions motivated the investigation of the technological properties of nine types of crystalline rocks (microgabbro, gneiss and varied granitic rocks) considering their potential to be used as track ballast in the HSR between Campinas and São Paulo. The rock samples were submitted to physical, mechanical and accelerated weathering tests. The soundness by artificial weathering, drying water were conjugated to the Los Angeles abrasion tests, Treton shock and crushing. The results indicate that some materials present resistance values bellow or near the limit normalized for track ballast, besides the loss of the quality verified in weathering resistance tests, making it impossible or restricting the use of the three studied materials as track ballast. In general, such information can be used by government agencies to make decisions about the materials available in the area where the brazilian HSR will be built once the maintenance costs of the track ballast are critical to the choice between a track ballast or slab track.

The aim of this study was to arrive at a fundamental understanding of kimberlite weathering and of factors which affect the rate and extent of weathering. Weathering was evaluated by measuring the change in size distribution after immersing crushed kimberlite in solutions of various compositions. Reproducibility of the measurements was found to be good, with the cumulative mass passing a given size differing by 7% or less, as tested for various weathering conditions. Kimberlite mineralogy, specifically the swelling clay content, was found to play a central role: kimberlite ores containing no swelling clay were not prone to weathering under any of the conditions tested. The cation exchange capacity (CEC) correlates well with the swelling clay content and with the weathering behaviour. The cation exchange capacity may be used in conjunction with the swelling clay content, as a predictor of possible kimberlite behaviour; however, given the relative complexity and cost of measuring swelling clay content (by X-ray diffraction), the CEC is the preferred parameter for practical use. Cations in the weathering solution have a strong effect on kimberlite weathering; the strength of the effect followed the series Cu2+ > Li+ > Fe2+ > Ca2+ > Fe3+ > Mg2+, whereas K+ and NH4+ stabilised the kimberlite somewhat against weathering. This sequence was in reasonable correlation with the ionic potential (ratio of valency to ionic radius), but with exceptionally strong weathering effects of Cu2+, and (to a lesser extent) of Li+ and Fe2+. The strong effect of the latter group of cations may be related to their tendency to adsorb onto other crystal sites in addition to the interlayer – the associated change in surface energy can change the fracture behaviour of the kimberlite. Measurement of the layer spacing of the swelling clay (by X-ray diffraction) showed no correlation between the weathering effect of a cation and the associated thickness of the interlayer. For solutions of cupric ions, the identity of the anion (chloride or sulphate) has little effect on weathering. The size of the crushed kimberlite ore similarly has little effect on the relative extent of size degradation by weathering. The concentration of cupric ions affects weathering, as does the weathering time – although 85% of the weathering caused by 30 days' exposure was found to occur within the first 24 hours. Increasing the temperature to 40°C (in a magnesium chloride solution) also increased weathering strongly. The kinetics of exchange of cuprous and potassium ions was measured (for two different kimberlites); the apparent reaction order (with respect to the concentration of exchanging cations in solution) varied between 1 and 3.5, and exchange of potassium was more rapid. This work has practical implications for in-plant processing of kimberlite, possible alternative kimberlite processing routes which eliminate one or more crushing steps, and for the stability of mine tunnels which pass through kimberlite. / Thesis (PhD (Metallurgical Engineering))--University of Pretoria, 2006. / Materials Science and Metallurgical Engineering / PhD / unrestricted

No description available.

Os revestimentos curáveis por radiação ultravioleta (UV) ou feixe de elétrons (EB) são sistemas líquidos reativos compostos por resinas, diluentes (monômero) e aditivos, capazes de formar compostos poliméricos termorrígidos por reações de polimerização e reticulação induzidas por radiação. Esta tecnologia tem sido empregada como alternativa aos processos convencionais no desenvolvimento de uma variada gama de produtos. Um dos grandes desafios da aplicação da tecnologia de cura UV/EB em produtos a serem submetidos ao intemperismo é a manutenção de suas propriedades físicas e de sua aparência. Este trabalho apresenta informações sobre o comportamento de quatro vernizes com e sem aditivos estabilizantes à luz-curados por radiação UV ou EB quando submetidos ao processo de envelhecimento acelerado. Os vernizes foram caracterizados por técnicas termoanalíticas como termogravimetria (TG), calorimetria exploratória diferencial (DSC) e fotocalorimetria diferencial (foto-DSC); espectroscopia de absorção no infravermelho e no ultravioleta, e propriedades mecânicas. Os vernizes sob a forma de filmes de 50 µm de espessura foram curados com diferentes doses de radiação UV ou EB. A cura por radiação UV foi conduzida em túnel de luz, provido de uma lâmpada de mercúrio de média pressão e esteira rolante com velocidade variável. As diferentes doses de radiação UV de 50 a 1500 mJ cm-2 foram obtidas variando-se a velocidade da esteira. A cura por EB foi realizada utilizando-se acelerador de elétrons de energia de 1,5 MeV, sob atmosfera de nitrogênio, aplicando-se doses no intervalo de 1,6 a 300 kGy. O grau de cura dos diferentes filmes foi calculado por meio dos valores das entalpias de reação da cura residual obtidos por DSC. Os testes de envelhecimento acelerado dos filmes curados foram feitos em câmara de envelhecimento do tipo Weather-Ometer por períodos de exposição de 100 a 3000 horas. Os dados obtidos experimentalmente foram avaliados em função da composição dos vernizes, da dose e do tipo de radiação empregada na cura e do tempo de permanência na câmara de envelhecimento. Os resultados indicam que os filmes curados por EB apresentam maior durabilidade frente ao intemperismo do que os seus pares curados por radiação UV. Os filmes não estabilizados (sem aditivos) apresentam grande instabilidade nas condições do teste de envelhecimento. O efeito do envelhecimento foi observado por meio de dados de dureza, brilho, rugosidade, índice de amarelecimento e alteração das bandas de absorção dos espectros FTIR. / The materials curable by ultraviolet (UV) or electron beam (EB) radiation such as inks, adhesives and coatings are reactive compounds made up of resin, monomer, photoinitiator and additives which undergo polymerization and crosslinking under irradiation producing thermoset products. This technology has been used in a great variety of industrial applications, replacing the conventional curing process in the development of new products. One of the challenging applications has been to design weatherable radiation cured coating which maintain their desirable physical properties and aesthetic appearance. This research reports information about the behavior of four UV and EB curable clear coatings -with or without light stabilizer additives- under accelerated weathering. Thermogravinietry, differential scanning calorimetry, differential photocalorimetry, infrared and ultraviolet spectroscopy and tensile properties were used to evaluate these formulations. Clear coating 50 µm thick films were cured with UV and EB radiation at different doses. The UV curing process was carried out at room temperature using an UV tunnel, with a medium pressure mercury lamp and a transport belt with variable speed. The ultraviolet radiation doses were in the range of 50 to 1500 mJ cm-2. The EB curing process was performed under N2 atmosphere, with doses in the range from 1,6 to 300 kGy using the IPEN-CNEN/SP Dynamitron electron beam accelerator with energy of 1.5 MeV. The cure degree was determined by means of the residual reaction heat of the undercured samples obtained from photo-DSC or DSC measurements. The accelerated aging tests were carried out using a Weather-Ometer chamber with exposition times in the range of 100 to 3000 hours. The experimental data obtained from the photo-aged samples were evaluated and correlated to the formulation composition, type of radiation - UV or EB, radiation dose and residence time in the aging chamber. The results have shown that the EB cured films have a better resistance to photoinduced weathering effects than UV cured ones. UV/EB films with light stabilizers have shown larger stability than those counterparts with no additives. The aging effects were evaluated by parameters such as hardness, gloss, surface roughness, yellowness index and changes in the FTIR absorption bands.

Os revestimentos curáveis por radiação ultravioleta (UV) ou feixe de elétrons (EB) são sistemas líquidos reativos compostos por resinas, diluentes (monômero) e aditivos, capazes de formar compostos poliméricos termorrígidos por reações de polimerização e reticulação induzidas por radiação. Esta tecnologia tem sido empregada como alternativa aos processos convencionais no desenvolvimento de uma variada gama de produtos. Um dos grandes desafios da aplicação da tecnologia de cura UV/EB em produtos a serem submetidos ao intemperismo é a manutenção de suas propriedades físicas e de sua aparência. Este trabalho apresenta informações sobre o comportamento de quatro vernizes com e sem aditivos estabilizantes à luz-curados por radiação UV ou EB quando submetidos ao processo de envelhecimento acelerado. Os vernizes foram caracterizados por técnicas termoanalíticas como termogravimetria (TG), calorimetria exploratória diferencial (DSC) e fotocalorimetria diferencial (foto-DSC); espectroscopia de absorção no infravermelho e no ultravioleta, e propriedades mecânicas. Os vernizes sob a forma de filmes de 50 µm de espessura foram curados com diferentes doses de radiação UV ou EB. A cura por radiação UV foi conduzida em túnel de luz, provido de uma lâmpada de mercúrio de média pressão e esteira rolante com velocidade variável. As diferentes doses de radiação UV de 50 a 1500 mJ cm-2 foram obtidas variando-se a velocidade da esteira. A cura por EB foi realizada utilizando-se acelerador de elétrons de energia de 1,5 MeV, sob atmosfera de nitrogênio, aplicando-se doses no intervalo de 1,6 a 300 kGy. O grau de cura dos diferentes filmes foi calculado por meio dos valores das entalpias de reação da cura residual obtidos por DSC. Os testes de envelhecimento acelerado dos filmes curados foram feitos em câmara de envelhecimento do tipo Weather-Ometer por períodos de exposição de 100 a 3000 horas. Os dados obtidos experimentalmente foram avaliados em função da composição dos vernizes, da dose e do tipo de radiação empregada na cura e do tempo de permanência na câmara de envelhecimento. Os resultados indicam que os filmes curados por EB apresentam maior durabilidade frente ao intemperismo do que os seus pares curados por radiação UV. Os filmes não estabilizados (sem aditivos) apresentam grande instabilidade nas condições do teste de envelhecimento. O efeito do envelhecimento foi observado por meio de dados de dureza, brilho, rugosidade, índice de amarelecimento e alteração das bandas de absorção dos espectros FTIR. / The materials curable by ultraviolet (UV) or electron beam (EB) radiation such as inks, adhesives and coatings are reactive compounds made up of resin, monomer, photoinitiator and additives which undergo polymerization and crosslinking under irradiation producing thermoset products. This technology has been used in a great variety of industrial applications, replacing the conventional curing process in the development of new products. One of the challenging applications has been to design weatherable radiation cured coating which maintain their desirable physical properties and aesthetic appearance. This research reports information about the behavior of four UV and EB curable clear coatings -with or without light stabilizer additives- under accelerated weathering. Thermogravinietry, differential scanning calorimetry, differential photocalorimetry, infrared and ultraviolet spectroscopy and tensile properties were used to evaluate these formulations. Clear coating 50 µm thick films were cured with UV and EB radiation at different doses. The UV curing process was carried out at room temperature using an UV tunnel, with a medium pressure mercury lamp and a transport belt with variable speed. The ultraviolet radiation doses were in the range of 50 to 1500 mJ cm-2. The EB curing process was performed under N2 atmosphere, with doses in the range from 1,6 to 300 kGy using the IPEN-CNEN/SP Dynamitron electron beam accelerator with energy of 1.5 MeV. The cure degree was determined by means of the residual reaction heat of the undercured samples obtained from photo-DSC or DSC measurements. The accelerated aging tests were carried out using a Weather-Ometer chamber with exposition times in the range of 100 to 3000 hours. The experimental data obtained from the photo-aged samples were evaluated and correlated to the formulation composition, type of radiation - UV or EB, radiation dose and residence time in the aging chamber. The results have shown that the EB cured films have a better resistance to photoinduced weathering effects than UV cured ones. UV/EB films with light stabilizers have shown larger stability than those counterparts with no additives. The aging effects were evaluated by parameters such as hardness, gloss, surface roughness, yellowness index and changes in the FTIR absorption bands.

No description available.