A geração de passivos ambientais após o término da vida útil dos materiais poliméricos é uma realidade que está sendo mudada devido a reciclagem desses materiais. A obtenção de novos materiais a partir do seu reuso traz vantagens com a diminuição de custos no produto final, já que reduz a produção da matéria prima virgem, além de minimizar a quantidade de rejeitos. Neste trabalho, a borracha EPDM vulcanizada foi reprocessada termicamente por irradiação e envelhecimento para que ocorresse a sua desvulcanização, visando obter melhor desempenho no processo de reciclagem; o polietileno de alta densidade (PEAD) foi reprocessado vinte vezes de modo a obter um termoplástico reciclado. Com esses componentes foram obtidos compósitos extrudados contendo 1 % e 5 % da borracha (com e sem tratamento térmico) dispersa na matriz reprocessada de PEAD. A compatibilização entre os componentes foi obtida testando alguns tipos de substâncias e nesse sentido, o metacrilato de glicidila (GMA) foi o que promoveu o melhor resultado. Os compósitos também foram submetidos ao processo de irradiação por feixe de elétrons nas doses de 50 kGy e 100 kGy e a comparação entre os materiais irradiados e não irradiados foi realizada a partir de análises por FTIR, TG, DSC, MEV e testes mecânicos (tração, impacto e dureza). Os compósitos apresentaram-se homogêneos e a interface entre a borracha e a matriz polimérica apresentou-se contínua. Observou-se que tanto o reprocessamento termocisalhante quanto a irradiação promovem alterações em nível molecular de modo que a reticulação e a degradação ocorrem simultaneamente. A adição de EPDM nas concentrações estudadas foi fundamental na promoção da reticulação do material. Com processo de irradiação, os compósitos apresentaram melhoria nas propriedades mecânicas. / The generation of waste after service end-life of polymeric materials is a reality that is being changed because of the recycling of these materials. Obtaining new materials from its reuse brings benefits to the reduction of costs in the final product, since it reduces the production of virgin raw material, while minimizing the amount of waste. In this work, the vulcanized EPDM rubber was thermally reprocessed by both simultaneous irradiation and oven aging to perform its devulcanization to improve performance in the recycling process; high density polyethylene (HDPE) was reprocessed twenty times so as to obtain a recycled thermoplastic. These both components were extruded to obtain composites containing 1% and 5% of rubber (with or without heat treatment) dispersed in reprocessed HDPE matrix. The compatibility between the components was obtained testing some kinds of substances and accordingly, the glycidyl methacrylate (GMA) promoted the best result. The composites were also subjected to irradiation process by electron beam at doses of 50 kGy to 100 kGy and analysis by FTIR, TG, DSC, SEM and mechanical tests (traction, impact and hardness) were carried out to compare irradiated and non-irradiated materials. The composites had become homogenous and the rubber and the polymeric matrix interface presented to be continuous. It was observed that both processes thermal-shearing and irradiation promote changes at the molecular level so that crosslinking and degradation occur simultaneously. The addition of EPDM in the studied concentrations was important to promote the material crosslinking. The composites showed improvement in mechanical properties with the irradiation process.

O polietileno surgiu em 1898 e logo já começou a ser utilizado como conduíte e isolante. Desde então este material vem ganhando muito espaço no mercado de tubulações, seja no saneamento, mineração, indústrias ou no segmento de petróleo e gás. Seu tipo mais usado é o Polietileno de Alta Densidade (PEAD), que apesar de já ser comumente encontrado em adutoras, emissários e ramais prediais, somente nos últimos anos passou a ser utilizado de maneira mais abrangente nas redes de distribuição de água, se tornando um aliado importante no combate aos altos índices de perdas reais. No Brasil, somente nos últimos anos que a presença de tubulações de PEAD em redes de distribuição de água potável se tornou mais comum. Contudo, é possível identificar cenários de aplicação do PEAD em sistemas de abastecimento de água já relativamente consolidados, como é o caso do Departamento Municipal de Água e Esgotos (DMAE) de Porto Alegre, que utiliza o material há 25 anos, a Companhia de Saneamento Básico do Estado de São Paulo (Sabesp), onde desde 2009 a Diretoria Metropolitana vem utilizando o PEAD em novas aplicações em redes e a Odebrecht Ambiental da cidade de Limeira, que utiliza tubos deste material desde 2007. Através de análises de custos de implantação, operação e manutenção, de amostragens da condição de tubulações em operação, da evolução de índice de perdas e de entrevistas com as equipes de operação e planejamento, é possível verificar que realmente as tubulações de PEAD auxiliam no combate às perdas reais e na otimização da operação e eficiência das prestadoras de serviços de distribuição de água potável, no sentido de diminuir o tempo de intervenção de redes, os custos de manutenção e a frequência de arrebentamento e vazamentos nas redes de abastecimento. / Polyethylene appeared in 1898 and soon started been used as conduit and insulating material. Since then, the material has been gaining a lot of space in the pipes market in sanitation, mining, industries and oil & gas production. The most used type is High Density Polyethylene (HDPE), which despite being commonly found in water mains, emissaries and communication pipes, only in recent years began to be used more widely in water distribution networks, becoming an important ally in the fight against high rates of real water losses. In Brazil, only in recent years the use of HDPE pipes has become more common in public water distribution networks. However, it is possible to identify HDPE application cases in relatively consolidated water supply distribution networks, such as the Departamento Municipal de Água e Esgotos (DMAE) of Porto Alegre, which have used the material for 25 years; the Companhia de Saneamento Básico do Estado de São Paulo (Sabesp), where since 2009 the Metropolitan Unit has been using HDPE in new applications in network pipes and Odebrecht Ambiental, in Limeira city, which uses this material in water pipelines since 2007. Through research of implementation, operation and maintenance costs, sampling the condition of pipes in operation, analysis the real losses indicators and interviews with the operations and planning teams, it is possible to conclude HDPE pipes contribute to reduction of real losses and optimization of the operation and efficiency of the providers of drinking water distribution services, decreasing maintenance time and costs.

A geração de passivos ambientais após o término da vida útil dos materiais poliméricos é uma realidade que está sendo mudada devido a reciclagem desses materiais. A obtenção de novos materiais a partir do seu reuso traz vantagens com a diminuição de custos no produto final, já que reduz a produção da matéria prima virgem, além de minimizar a quantidade de rejeitos. Neste trabalho, a borracha EPDM vulcanizada foi reprocessada termicamente por irradiação e envelhecimento para que ocorresse a sua desvulcanização, visando obter melhor desempenho no processo de reciclagem; o polietileno de alta densidade (PEAD) foi reprocessado vinte vezes de modo a obter um termoplástico reciclado. Com esses componentes foram obtidos compósitos extrudados contendo 1 % e 5 % da borracha (com e sem tratamento térmico) dispersa na matriz reprocessada de PEAD. A compatibilização entre os componentes foi obtida testando alguns tipos de substâncias e nesse sentido, o metacrilato de glicidila (GMA) foi o que promoveu o melhor resultado. Os compósitos também foram submetidos ao processo de irradiação por feixe de elétrons nas doses de 50 kGy e 100 kGy e a comparação entre os materiais irradiados e não irradiados foi realizada a partir de análises por FTIR, TG, DSC, MEV e testes mecânicos (tração, impacto e dureza). Os compósitos apresentaram-se homogêneos e a interface entre a borracha e a matriz polimérica apresentou-se contínua. Observou-se que tanto o reprocessamento termocisalhante quanto a irradiação promovem alterações em nível molecular de modo que a reticulação e a degradação ocorrem simultaneamente. A adição de EPDM nas concentrações estudadas foi fundamental na promoção da reticulação do material. Com processo de irradiação, os compósitos apresentaram melhoria nas propriedades mecânicas. / The generation of waste after service end-life of polymeric materials is a reality that is being changed because of the recycling of these materials. Obtaining new materials from its reuse brings benefits to the reduction of costs in the final product, since it reduces the production of virgin raw material, while minimizing the amount of waste. In this work, the vulcanized EPDM rubber was thermally reprocessed by both simultaneous irradiation and oven aging to perform its devulcanization to improve performance in the recycling process; high density polyethylene (HDPE) was reprocessed twenty times so as to obtain a recycled thermoplastic. These both components were extruded to obtain composites containing 1% and 5% of rubber (with or without heat treatment) dispersed in reprocessed HDPE matrix. The compatibility between the components was obtained testing some kinds of substances and accordingly, the glycidyl methacrylate (GMA) promoted the best result. The composites were also subjected to irradiation process by electron beam at doses of 50 kGy to 100 kGy and analysis by FTIR, TG, DSC, SEM and mechanical tests (traction, impact and hardness) were carried out to compare irradiated and non-irradiated materials. The composites had become homogenous and the rubber and the polymeric matrix interface presented to be continuous. It was observed that both processes thermal-shearing and irradiation promote changes at the molecular level so that crosslinking and degradation occur simultaneously. The addition of EPDM in the studied concentrations was important to promote the material crosslinking. The composites showed improvement in mechanical properties with the irradiation process.

Neste trabalho foram sintetizados catalisadores Ziegler-Natta heterogêneos obtidos a partir de TiCl4 e etilato de magnésio com geração de MgCl2 in situ. Foi verificado que o tempo e a temperatura de têmpera da preparação do catalisador influenciam significativamente a atividade catalítica destes. O catalisador não submetido ao processo de têmpera (ZNST), e o catalisador temperado em condições mais rigorosas (ZNT), apresentaram, respectivamente, a maior e a menor atividade catalítica entre vários catalisadores submetidos a diferentes condições de têmpera. Os catalisadores ZNST e ZNT tratam-se de sólidos amorfos, com área superficial e dimensão de partículas semelhantes. Pela análise da composição química dos catalisadores, por diferentes técnicas analíticas, verificouse que o tratamento térmico do catalisador favorece a fixação de TiCl4 e de compostos de Ti oxigenados, diferentes daqueles depositados na reação do MgCl2 com TiCl4. Nesta Tese foi proposta uma estrutura para os sítios ativos formados à base de compostos de Ti oxigenados ou titanoxanos. Estes resultados permitiram a proposição do modelo físico-químico, denominado núcleo-superfície, segundo o qual o catalisador ZNT é constituído de partículas primárias contendo no núcleo predominantemente sítios de Ti do tipo clorotitanatos, entre outros, e na superfície majoritariamente sítios titanoxano (-Ti-O-Ti-). O catalisador ZNST tem majoritariamente sítios de Ti do tipo clorotitanato. O modelo foi válido para explicar o comportamento dos catalisadores na polimerização de eteno, em processo em suspensão, na obtenção do polietileno de alta densidade (PEAD) e também para explicar as propriedades diferenciadas dos polímeros obtidos. O sistema catalítico ZNST-TEA apresentou maior atividade catalítica e produziu o PEAD de menor massa molar e menor polidispersão. Com o sistema catalítico ZNT-IPRA se verificou atividade catalítica intermediária e PEAD com maior massa molar e maior polidispersão. / In this work, Ziegler-Natta heterogeneous supported catalysts were synthesized from TiCl4 and magnesium ethylate with MgCl2 in situ generation. It was observed that both catalyst tempering time and temperature influenced significantly the catalytic activity. The non tempered catalyst (ZNST) and the tempered catalyst (ZNT) presented the highest and the lowest catalyst activity, respectively, among other ones prepared in different tempering conditions. The catalysts ZNST and ZNT are amorphous solids and both have approximately the same surface area and particle size. By the catalyst chemical compositions, determined through different techniques, it was possible to conclude that thermal treatment (tempering) increases the Ti content and new oxygenated Ti sites in the catalyst. In this work was proposed a structure to the new site titanoxane different of that one obtained in the MgCl2 chloration of with TiCl4. These results allow proposing a core-shell model. The core of ZNT catalyst particle has mainly Ti site as chloridetitanate, and others, and the shell has primary particles that have mainly titanoxane sites. The ZNST catalyst has mainly Ti sites as chloridetitanate. The model was valid to explain HDPE properties produced by slurry process. The ZNST-TEA catalytic system showed the highest catalytic activity and the HDPE obtained with this system had the lower molecular weight and the lower polidispersity. The ZNT-IPRA catalytic system showed an intermediate activity and the HDPE obtained had the highest molecular weight and broader polidispersity.

This work investigates the interactions of carbonaceous materials (metallurgical coke, natural graphite and HDPE/coke blends) with three EAF slags [FeO: 24% to 32%]. Experiments were conducted using the sessile drop technique (1500??C-1600??C) with off-gases (CO, CO2) measured using an IR analyzer; the wetting behaviour was determined from contact angle measurements. Estimation of slag foaming behaviour was determined from the droplet volume changes calculated using specialized software. At 1550??C, all slags were non-wetting with coke due to increased surface tension due to sulphur. At 1550??C, slag 1 was initially non-wetting on natural graphite due to gas entrapment in the slag droplet; the wetting improved after that. Other slags showed comparatively better wetting. At 1600??C, all slags were non-wetting with coke. Slags showed a shift from non-wetting to wetting behaviour with natural graphite. Slag/coke reactions produced high off-gases levels causing extensive FeO reduction; gas entrapment in the slag was poor (small volume droplets). Slag/natural graphite interactions revealed both slow gas generation rates and FeO reduction, and excellent gas entrapment (higher droplet volumes) with minor changes in slag properties due to low ash levels. The iron oxide reduction rates were determined to be 1.54x10-5 and 4.2x10-6 mol.cm-2/sec (Slag 1, 1550??C) for metallurgical coke and natural graphite respectively. Slag interactions with coke/HDPE blends showed increasing off-gas levels with increasing HDPE levels. Blend#3 produced the highest off-gas levels, extensive FeO reduction and displayed significantly higher slag foaming and better wetting compared to coke. Our line on trends compared well for slag/carbon interactions and resulted in deceased specific energy consumption and carbon usage and increased productivity. These findings have enhanced the possibility of utilizing polymeric wastes in blends with coke in EAF steelmaking for slag/carbon interactions.

Different methods for quality assessment of separated andcommingled plastics from household and electronic waste havebeen developed. Especial attention has been given tospectroscopic methods since they are non-destructive andrequire little or no sample preparation at all. A wide variety of low molecular weight compounds have beenidentified in recycled polyethylene (HDPE) and polypropylenefrom hard packaging waste by gas chromatography- massspectroscopy (GC-MS) after microwave assisted extraction (MAE).Low molecular weight substances such as alcohols, esters,ketones and fragrance and flavour compounds were detected inthe recycled resins. The major category of compounds identifiedin the virgin resins is conformed by aliphatic hydrocarbonssuch as alkanes and alkenes. It was found that theconcentration of aromatic hydrocarbons without functionalgroups, e.g. ethylbenzene and xylenes in recycled HDPE wasapprox. 5 times higher and equal to 120 and 35 ppb,respectively. The potential of near infrared (NIR) and Fourier transformRaman (FT-Raman) spectroscopy in combination with multivariateanalysis as a rapid, non-destructive and accurate analyticalmethod has been studied and the feasibility of these methodsfor at/in line characterisation of several properties ofrecyclates has also been explored. NIR in diffuse reflectance mode has been successfully usedfor quantification of antioxidants in polyethylene, thestandard error of prediction is almost comparable to the errorof wet methods, i.e., extraction plus liquid chromatography.The error of prediction of this method is 35 ppm for Irganox1010 and 68 ppm for Irgafos 168. The inaccuracy in thequantification of Irgafos 168 is due to the fact that thisantioxidant degrades during polymer processing. NIR and Mid-infrared (Mid-IR) worked well for fastdetermination of molecular weight and crystallinity of therecycled HDPE and acceptable errors of prediction, comparableto that of the reference methods, i.e. size exclusionchromatography (SEC) and differential scanning calorimetry(DSC) have been obtained. The present thesis also shows that NIR and Raman are goodcandidates for in/on line compositional analysis of mixedpolymer fractions from recycled plastic waste. Diffusereflectance NIR allows a rapid and reliable measurement ofpellets and requires no previous sample preparation. Thecomposition of binary blends can be determined with highaccuracy. The PP content in the PP/HDPE blends was predictedwith a RMSEP equal to 0.46 %w in the 0-15 %wt region and theRMSEP for PP in the PP/ABS blends was 0.3 %wt. The thermal and thermoxidative stability of recycled PP,HDPE and a 20/80 PP/HDPE blend subjected to multiple extrusionhave been studied by DSC, thermal analysis (TGA) andchemiluminiscence (CL). A decrease in Toxand OIT was observed after each extrusion step.The drop in OIT was sharper after the first two extrusions. TheOIT values produced by DSC and CL were in good agreement.However, CL provided more information about the oxidationprocess taking place in the blends. The moisture content in recycled polyamide 6,6 was readilydetermined by NIR in transmission mode and it could bepredicted with a RMSEP = 0.05 %wt. The accuracy of the methodappeared to be as good as that of the more time consumingthermal methods such as TGA, DSC and loss on dry (LOD), whichwere used as reference methods. The influence of differentamounts of water on the viscoelastic properties of nylon hasbeen investigated. <b>Keywords:</b>Recycling, HDPE, PP, blends, nylon 6,6, ABS,water content, MAE, GC-MS, NIR, FT-Raman, chemiluminiscence,low molecular weight compounds, antioxidant content,crystallinity, molecular weight, thermal stability,characterisation methods, analysis of polymers, blends.

<p>Different methods for quality assessment of separated andcommingled plastics from household and electronic waste havebeen developed. Especial attention has been given tospectroscopic methods since they are non-destructive andrequire little or no sample preparation at all.</p><p>A wide variety of low molecular weight compounds have beenidentified in recycled polyethylene (HDPE) and polypropylenefrom hard packaging waste by gas chromatography- massspectroscopy (GC-MS) after microwave assisted extraction (MAE).Low molecular weight substances such as alcohols, esters,ketones and fragrance and flavour compounds were detected inthe recycled resins. The major category of compounds identifiedin the virgin resins is conformed by aliphatic hydrocarbonssuch as alkanes and alkenes. It was found that theconcentration of aromatic hydrocarbons without functionalgroups, e.g. ethylbenzene and xylenes in recycled HDPE wasapprox. 5 times higher and equal to 120 and 35 ppb,respectively.</p><p>The potential of near infrared (NIR) and Fourier transformRaman (FT-Raman) spectroscopy in combination with multivariateanalysis as a rapid, non-destructive and accurate analyticalmethod has been studied and the feasibility of these methodsfor at/in line characterisation of several properties ofrecyclates has also been explored.</p><p>NIR in diffuse reflectance mode has been successfully usedfor quantification of antioxidants in polyethylene, thestandard error of prediction is almost comparable to the errorof wet methods, i.e., extraction plus liquid chromatography.The error of prediction of this method is 35 ppm for Irganox1010 and 68 ppm for Irgafos 168. The inaccuracy in thequantification of Irgafos 168 is due to the fact that thisantioxidant degrades during polymer processing.</p><p>NIR and Mid-infrared (Mid-IR) worked well for fastdetermination of molecular weight and crystallinity of therecycled HDPE and acceptable errors of prediction, comparableto that of the reference methods, i.e. size exclusionchromatography (SEC) and differential scanning calorimetry(DSC) have been obtained.</p><p>The present thesis also shows that NIR and Raman are goodcandidates for in/on line compositional analysis of mixedpolymer fractions from recycled plastic waste. Diffusereflectance NIR allows a rapid and reliable measurement ofpellets and requires no previous sample preparation. Thecomposition of binary blends can be determined with highaccuracy. The PP content in the PP/HDPE blends was predictedwith a RMSEP equal to 0.46 %w in the 0-15 %wt region and theRMSEP for PP in the PP/ABS blends was 0.3 %wt.</p><p>The thermal and thermoxidative stability of recycled PP,HDPE and a 20/80 PP/HDPE blend subjected to multiple extrusionhave been studied by DSC, thermal analysis (TGA) andchemiluminiscence (CL). A decrease in T_oxand OIT was observed after each extrusion step.The drop in OIT was sharper after the first two extrusions. TheOIT values produced by DSC and CL were in good agreement.However, CL provided more information about the oxidationprocess taking place in the blends.</p><p>The moisture content in recycled polyamide 6,6 was readilydetermined by NIR in transmission mode and it could bepredicted with a RMSEP = 0.05 %wt. The accuracy of the methodappeared to be as good as that of the more time consumingthermal methods such as TGA, DSC and loss on dry (LOD), whichwere used as reference methods. The influence of differentamounts of water on the viscoelastic properties of nylon hasbeen investigated.</p><p><b>Keywords:</b>Recycling, HDPE, PP, blends, nylon 6,6, ABS,water content, MAE, GC-MS, NIR, FT-Raman, chemiluminiscence,low molecular weight compounds, antioxidant content,crystallinity, molecular weight, thermal stability,characterisation methods, analysis of polymers, blends.</p>

The ageing of high density polyethylene geomembrane (GM) liners used to minimize advection and diffusion of contaminants in municipal solid waste landfill leachate and in hydrocarbon spills to the environment is examined. The evaluation of the ageing of GMs used in landfills involved four components. First, a laboratory-accelerated ageing investigation of a GM exposed to air, water and leachate at elevated temperatures. Service life of a GM (Stage I: Antioxidant depletion, Stage II: Induction, and Stage III: Polymer degradation) is examined. The results demonstrate the critical role of antioxidants in protecting against oxidative degradation. The service life of the GM is predicted. Second, a study was conducted to provide an estimate of Stage I for a GM in a composite liner. The results indicated that immersion tests are too severe and the service life is substantially greater for a GM in composite liner than implied by leachate immersion tests. Third, a comparison of ageing with three different “protection” layers between the GM and overlying gravel and leachate is reported. A slower antioxidant depletion rate is observed when geotextile-geosynthetic clay liner and geotextile-sand-geotextile are applied than with a typical geotextile alone. This could be partially attributed to the attenuation of leachate constituents by the protection layer as well as the buildup of antioxidant concentration on either side of GM thereby reducing the concentration gradient and outward diffusive flux of antioxidants. Fourth, diffusion modelling is used to evaluate the results from immersion and composite liner simulation tests. Diffusion modelling provided a means for predicting the performance of the GMs in conditions other than the typical test conditions. The evaluation of the ageing of GM used in barrier system for hydrocarbon involved two components. First, untreated and fluorinated GMs immersed in jet fuel were tested. Results show that antioxidants depleted at slower rate from fluorinated GM than untreated GM. This suggested a significant beneficial effect of fluorination. Antioxidant depletion time is predicted at field temperatures. Second, the time dependant change in GM samples used at jet fuel containment site constructed in 2001 is reported. The GM is shown to be performing very well. / Thesis (Ph.D, Civil Engineering) -- Queen's University, 2009-01-14 10:46:31.089

This work investigates the interactions of carbonaceous materials (metallurgical coke, natural graphite and HDPE/coke blends) with three EAF slags [FeO: 24% to 32%]. Experiments were conducted using the sessile drop technique (1500??C-1600??C) with off-gases (CO, CO2) measured using an IR analyzer; the wetting behaviour was determined from contact angle measurements. Estimation of slag foaming behaviour was determined from the droplet volume changes calculated using specialized software. At 1550??C, all slags were non-wetting with coke due to increased surface tension due to sulphur. At 1550??C, slag 1 was initially non-wetting on natural graphite due to gas entrapment in the slag droplet; the wetting improved after that. Other slags showed comparatively better wetting. At 1600??C, all slags were non-wetting with coke. Slags showed a shift from non-wetting to wetting behaviour with natural graphite. Slag/coke reactions produced high off-gases levels causing extensive FeO reduction; gas entrapment in the slag was poor (small volume droplets). Slag/natural graphite interactions revealed both slow gas generation rates and FeO reduction, and excellent gas entrapment (higher droplet volumes) with minor changes in slag properties due to low ash levels. The iron oxide reduction rates were determined to be 1.54x10-5 and 4.2x10-6 mol.cm-2/sec (Slag 1, 1550??C) for metallurgical coke and natural graphite respectively. Slag interactions with coke/HDPE blends showed increasing off-gas levels with increasing HDPE levels. Blend#3 produced the highest off-gas levels, extensive FeO reduction and displayed significantly higher slag foaming and better wetting compared to coke. Our line on trends compared well for slag/carbon interactions and resulted in deceased specific energy consumption and carbon usage and increased productivity. These findings have enhanced the possibility of utilizing polymeric wastes in blends with coke in EAF steelmaking for slag/carbon interactions.

Universiẗat, Diss., 2004--Düsseldorf.