Ocorrência de fungos negros em ambientes domésticos

Black fungi are able to adapt to extreme environmental conditions, such as: high temperatures, the presence of toxic chemical substances and lack of nutrients. Besides, they are also potential pathogens to humans. The natural environment of many black fungi is still unknown and some studies are being conducted to evaluate the biodiversity of this group and their different habitats. This study aimed to isolate black fungi in domestic environments and facilities, such as toothbrushes, fridge sealing rubbers, bathroom strainers and divisions, windows, wall tiles and bath sponge. For the collection, material surfaces were scratched with a scalpel and the resulting fragments were sewed in Mycosel agar (DifcoTM), supplemented with actidione to inhibit the growth of highly-sporulating fungi. Plates were incubated at 25ºC for three weeks. The 46 isolated fungi were maintained on MA2% slants at 8ºC and cryopreserved at -80ºC. Fungal identification was performed through the analysis of macro and microscopic features and ITS rDNA sequencing. The following black fungi taxa were found: Ascomycota sp., Cladosporium spp., Dothideomycete sp., Exophiala alcalophila, Ochroconis mirabilis and Rhinocladiella atrovirens. Non-melanized fungi were also found, such as Geosmithia sp., Penicillium sp. and Rhodotorula mucilaginosa. The temperature tests showed that isolated black fungi were not able to grow at 37°C, however, this temperature proved to be fungistatic to 43% of them. According to literature, all black fungi isolated in this study are opportunistic pathogens and additional studies are necessary to evaluate the risk that these micro-organisms offer to health, once they were isolated from domestic environments

Ocorrência de fungos negros em ambientes domésticos

Black fungi are able to adapt to extreme environmental conditions, such as: high temperatures, the presence of toxic chemical substances and lack of nutrients. Besides, they are also potential pathogens to humans. The natural environment of many black fungi is still unknown and some studies are being conducted to evaluate the biodiversity of this group and their different habitats. This study aimed to isolate black fungi in domestic environments and facilities, such as toothbrushes, fridge sealing rubbers, bathroom strainers and divisions, windows, wall tiles and bath sponge. For the collection, material surfaces were scratched with a scalpel and the resulting fragments were sewed in Mycosel agar (DifcoTM), supplemented with actidione to inhibit the growth of highly-sporulating fungi. Plates were incubated at 25ºC for three weeks. The 46 isolated fungi were maintained on MA2% slants at 8ºC and cryopreserved at -80ºC. Fungal identification was performed through the analysis of macro and microscopic features and ITS rDNA sequencing. The following black fungi taxa were found: Ascomycota sp., Cladosporium spp., Dothideomycete sp., Exophiala alcalophila, Ochroconis mirabilis and Rhinocladiella atrovirens. Non-melanized fungi were also found, such as Geosmithia sp., Penicillium sp. and Rhodotorula mucilaginosa. The temperature tests showed that isolated black fungi were not able to grow at 37°C, however, this temperature proved to be fungistatic to 43% of them. According to literature, all black fungi isolated in this study are opportunistic pathogens and additional studies are necessary to evaluate the risk that these micro-organisms offer to health, once they were isolated from domestic environments

Chemical Modifications in Styrene-Butadiene Rubber after Microwave Devulcanization

Microwave devulcanization has been studied as a method for elastomer recycling, which is based on the conversion of the reticulated and infusible structure of thermosetting rubbers in free polymeric chains able to be remolded by thermomechanical processing in recycling operations for the manufacture of other products. Elastomeric wastes are often irregularly discarded in nature, producing serious environmental damage, and their mechanical recycling is still considered a challenge. Thus, the development of alternatives for elastomer recycling is directly related to the actions of sustainable development and economic benefits to companies that pay to discard their wastes. The aim of this work is to evaluate the chemical modifications occurring in styrene butadiene rubber (SBR) after microwave devulcanization. Compounds of SBR were vulcanized in the presence of vulcanization agents and variable amounts of carbon black, and then the rubbers were milled and submitted to microwave treatment. Only the SBR with high carbon black content shows some portion of devulcanized material. However, the rubber with lower content of carbon black which was devulcanized by microwave radiation shows an increase in cross-link density. The microwave treatment also causes cross-link breaks mainly in polysulfidic bonds as well as decomposition of chemical groups containing sulfur attached to the chemical structure of SBR, while. the chemical bonds of higher energy such as monosulfidic bonds remain preserved. The improvement of the microwave method for rubber devulcanization represents a way for viable recycling of thermosetting rubbers.

Children's discomfort in assessments using different methods for approximal caries detection

Because discomfort caused by different approximal caries detection methods can influence their performance, the assessment of this discomfort is important. Thus, this study aimed to evaluate the discomfort reported by children after the use of different diagnostic methods to detect approximal caries lesions in primary teeth: visual inspection, bitewing radiography, laser fluorescence (DIAGNOdent pen - LFpen) and temporary separation with orthodontic rubbers. Seventy-six children aged 4 to 12 years were examined using these methods. Their discomfort was assessed using the Wong-Baker scale and compared among the methods. Visual inspection caused less discomfort than did other methods. Radiography and the LFpen presented similar levels of discomfort. Older children reported higher discomfort using temporary separation, whereas younger children reported less discomfort with the LFpen. In conclusion, radiographic, temporary separation and LFpen methods provoke higher discomfort than visual inspection.

Industrial ecology applied to ELV management. Material and energy recovery from ASR

This PhD thesis reports on car fluff management, recycling and recovery. Car fluff is the residual waste produced by car recycling operations, particularly from hulk shredding. Car fluff is known also as Automotive Shredder Residue (ASR) and it is made of plastics, rubbers, textiles, metals and other materials, and it is very heterogeneous both in its composition and in its particle size. In fact, fines may amount to about 50%, making difficult to sort out recyclable materials or exploit ASR heat value by energy recovery. This 3 years long study started with the definition of the Italian End-of-Life Vehicles (ELVs) recycling state of the art. A national recycling trial revealed Italian recycling rate to be around 81% in 2008, while European Community recycling target are set to 85% by 2015. Consequently, according to Industrial Ecology framework, a life cycle assessment (LCA) has been conducted revealing that sorting and recycling polymers and metals contained in car fluff, followed by recovering residual energy, is the route which has the best environmental perspective. This results led the second year investigation that involved pyrolysis trials on pretreated ASR fractions aimed at investigating which processes could be suitable for an industrial scale ASR treatment plant. Sieving followed by floatation reported good result in thermochemical conversion of polymers with polyolefins giving excellent conversion rate. This factor triggered ecodesign considerations. Ecodesign, together with LCA, is one of the Industrial Ecology pillars and it consists of design for recycling and design for disassembly, both aimed at the improvement of car components dismantling speed and the substitution of non recyclable material. Finally, during the last year, innovative plants and technologies for metals recovery from car fluff have been visited and tested worldwide in order to design a new car fluff treatment plant aimed at ASR energy and material recovery.

Podredumbre parda del melocotonero (Monilinia spp.) : detección, identificación de especies y contribución a la epidemiología de la enfermedad

Monilinia spp. (M. laxa, M. fructigena y M. fructicola) causa marchitez en brotes y flores, chancros en ramas y podredumbre de la fruta de hueso provocando pérdidas económicas importantes en años con climatología favorable para el desarrollo de la enfermedad, particularmente en variedades tardías de melocotonero y nectarino. En estos huéspedes en España, hasta el momento, la especie predominante es M. laxa y, en menor proporción, M. fructigena. La reciente introducción en Europa de la especie de cuarentena M. fructicola hace necesaria una detección e identificación rápida de cada una de las especies. Además, hay diversos aspectos de la etiología y epidemiología de la enfermedad que no se conocen en las condiciones de cultivo españolas. En un primer objetivo de esta Tesis se ha abordado la detección e identificación de las especies de Monilinia spp. causantes de podredumbre parda. El estudio de las bases epidemiológicas para el control de la enfermedad constituye el fin del segundo objetivo. Para la detección del género Monilinia en material vegetal por PCR, diferenciándolo de otros hongos presentes en la superficie del melocotonero, se diseñaron una pareja de cebadores siguiendo un análisis del ADN ribosomal. La discriminación entre especies de Monilinia se consiguió utilizando marcadores SCAR (región amplificada de secuencia caracterizada), obtenidos después de un estudio de marcadores polimórficos de ADN amplificados al azar (RAPDs). También fue diseñado un control interno de amplificación (CI) basado en la utilización de un plásmido con secuencias de los cebadores diferenciadores del género, para ser utilizado en el protocolo de diagnóstico de la podredumbre parda con el fin de reconocer falsos negativos debidos a la inhibición de PCR por componentes celulares del material vegetal. Se disponía de un kit comercial que permitía distinguir Monilinia de otros géneros y M. fructicola del resto de especies mediante anticuerpos monoclonales utilizando la técnica DAS-ELISA. En esta Tesis se probaron diferentes fuentes de material como micelio ó conidias procedentes de cultivos en APD, o el micelio de la superficie de frutas o de momias frescas, como formas de antígeno. Los resultados obtenidos con ELISA se compararon con la identificación por métodos morfológico-culturales y por PCR con los cebadores desarrollados en esta Tesis. Los resultados demostraron la posibilidad de una detección temprana en frutas frescas por este método, realzando las posibilidades de una diagnosis temprana para una prevención más eficaz de M. fructicola en fruta de hueso. El estudio epidemiológico de la enfermedad comenzó con la determinación de las principales fuentes de inóculo primario y su importancia relativa en melocotoneros y nectarinos del valle del Ebro. Para ello se muestrearon 9 huertos durante los años 2003 a 2005 recogiendo todas las momias, frutos abortados, gomas, chancros, y brotes necróticos en los árboles. También se recogieron brotes aparentemente sanos y muestras de material vegetal situados en el suelo. En estas muestras se determinó la presencia de Monilinia spp. Los resultados mostraron que la fuente principal de inóculo son las momias que se quedan en los árboles en las que la supervivencia del hongo tras el invierno es muy alta. También son fuentes de inóculo las momias del suelo y los brotes necróticos. De aquí se deriva que una recomendación importante para los agricultores es que deben eliminar este material de los huertos. Un aspecto no estudiado en melocotonero o nectarino en España es la posible relación que puede darse entre la incidencia de infecciones latentes en los frutos inmaduros a lo largo del cultivo y la incidencia de podredumbre en los frutos en el momento de la recolección y en postcosecha. Esta relación se había observado previamente en otros frutales de hueso infectados con M. fructicola en diversos países del mundo. Para estudiar esta relación se realizaron ensayos en cinco huertos comerciales de melocotonero y nectarino situados en el Valle del Ebro en cuatro estados fenológicos durante los años 2000-2002. No se observaron infecciones latentes en botón rosa, dándose la máxima incidencia en precosecha, aunque en algunos huertos se daba otro pico en el endurecimiento del embrión. La especie prevaleciente fue M. laxa. Se obtuvo una correlación positiva significativa entre la incidencia de infecciones latentes y la incidencia de podredumbre en postcosecha. Se desarrolló también un modelo de predicción de las infecciones latentes en función de la temperatura (T) y el periodo de humectación (W). Este modelo indicaba que T y W explicaban el 83% de la variación en la incidencia de infecciones latentes causadas por Monilinia spp. Por debajo de 8ºC no se predecían latentes, necesitándose más de 22h de W para predecir la ocurrencia de latentes con T = 8ºC, mientras que solo se necesitaban 5h de W a 25ºC. Se hicieron también ensayos en condiciones controladas para determinar la relación entre la incidencia de las infecciones latentes, las condiciones ambientales (T y W), la concentración de inóculo del patógeno (I) y el estado de desarrollo del huésped (S) y para validar el modelo de predicción desarrollado con los experimentos de campo. Estos ensayos se llevaron cabo con flores y frutos de nectarino procedentes de un huerto comercial en seis estados fenológicos en los años 2004 y 2005, demostrándose que la incidencia de podredumbre en postcosecha y de infecciones latentes estaba afectada por T, W, I y S. En los frutos se producían infecciones latentes cuando la T no era adecuada para el desarrollo de podredumbre. Una vez desarrollado el embrión eran necesarias más de 4-5h de W al día y un inóculo superior a 104 conidias ml-1 para que se desarrollase o podredumbre o infección latente. La ecuación del modelo obtenido con los datos de campo era capaz de predecir los datos observados en estos experimentos. Para evaluar el efecto del inóculo de Monilinia spp. en la incidencia de infecciones latentes y de podredumbre de frutos en postcosecha se hicieron 11 experimentos en huertos comerciales de melocotonero y nectarino del Valle del Ebro durante 2002 a 2005. Se observó una correlación positiva entre los números de conidias de Monilinia spp. en la superficie de los frutos y la incidencia de infecciones latentes De los estudios anteriores se deducen otras dos recomendaciones importantes para los agricultores: las estrategias de control deben tener en cuenta las infecciones latentes y estimar el riesgo potencial de las mismas basándose en la T y W. Deben tener también en cuenta la concentración de esporas de Monilinia spp. en la superficie de los frutos para disminuir el riesgo de podredumbre parda. El conocimiento de la estructura poblacional de los patógenos sienta las bases para establecer métodos más eficaces de manejo de las enfermedades. Por ello en esta Tesis se ha estudiado el grado de diversidad genética entre distintas poblaciones de M. laxa en diferentes localidades españolas utilizando 144 marcadores RAPDs (59 polimórficos y 85 monomórficos) y 21 aislados. El análisis de la estructura de la población reveló que la diversidad genética dentro de las subpoblaciones (huertos) (HS) representaba el 97% de la diversidad genética (HT), mientras que la diversidad genética entre subpoblaciones (DST) sólo representaba un 3% del total de esta diversidad. La magnitud relativa de la diferenciación génica entre subpoblaciones (GST) alcanzaba 0,032 y el número estimado de migrantes por generación (Nm) fue de 15,1. Los resultados obtenidos en los dendrogramas estaban de acuerdo con el análisis de diversidad génica. Las agrupaciones obtenidas eran independientes del huerto de procedencia, año o huésped. En la Tesis se discute la importancia relativa de las diferentes fuentes evolutivas en las poblaciones de M. laxa. Finalmente se realizó un muestreo en distintos huertos de melocotonero y nectarino del Valle del Ebro para determinar la existencia o no de aislados resistentes a los fungicidas del grupo de los benzimidazoles y las dicarboximidas, fungicidas utilizados habitualmente para el control de la podredumbre parda y con alto riesgo de desarrollar resistencia en las poblaciones patógenas. El análisis de 114 aislados de M. laxa con los fungicidas Benomilo (bencimidazol) (1Bg m.a ml-1), e Iprodiona (dicarboximida) (5Bg m.a ml-1), mostró que ninguno era resistente en las dosis ensayadas. Monilinia spp. (M. laxa, M. fructigena and M. fructicola) cause bud and flower wilt, canker in branches and stone fruit rot giving rise important economic losses in years with appropriate environmental conditions, it is particularly important in late varieties of peach and nectarine. Right now, M. laxa is the major species for peach and nectarine in Spain followed by M. fructigena, in a smaller proportion. The recent introduction of the quarantine organism M. fructicola in Europe makes detection and identification of each one of the species necessary. In addition, there are different aspects of disease etiology and epidemiology that are not well known in Spain conditions. The first goal of this Thesis was the detection and identification of Monilinia spp. causing brown rot. Study of the epidemiology basis for disease control was the second objective. A pair of primers for PCR detection was designed based on the ribosomal DNA sequence in order to detect Monilinia spp. in plant material and to discriminate it from other fungi colonizing peach tree surface. Discrimination among Monilinia spp. was successful by SCAR markers (Sequence Characterized Amplified Region), obtained after a random amplified polymorphic DNA markers (RAPDs) study. An internal control for the PCR (CI) based on the use of a mimic plasmid designed on the primers specific for Monilinia was constructed to be used in diagnosis protocol for brown rot in order to avoid false negatives due to the inhibition of PCR as consequence of remained plant material. A commercial kit based on DAS-ELISA and monoclonals antibodies was successfully tested to distinguish Monilinia from other fungus genera and M. fructicola from other Monilinia species. Different materials such as micelium or conidias from APD cultures, or micelium from fresh fruit surfaces or mummies were tested in this Thesis, as antigens. Results obtained by ELISA were compared to classical identification by morphologic methods and PCR with the primers developed in this Thesis. Results demonstrated the possibility of an early detection in fresh fruits by this method for a more effective prevention of M. fructicola in stone fruit. The epidemiology study of the disease started with the determination of the main sources of primary inoculum and its relative importance in peach trees and nectarines in the Ebro valley. Nine orchards were evaluated during years 2003 to 2005 collecting all mummies, aborted fruits, rubbers, cankers, and necrotic buds from the trees. Apparently healthy buds and plant material located in the ground were also collected. In these samples presence of Monilinia spp. was determined. Results showed that the main inoculum sources are mummies that stay in the trees and where fungus survival after the winter is very high. Mummies on the ground and the necrotics buds are also sources of inoculum. As consequence of this an important recommendation for the growers is the removal of this material of the orchards. An important issue not well studied in peach or nectarine in Spain is the possible relationship between the incidence of latent infections in the immature fruits and the incidence of fruit rot at harvesting and postharvesting. This relationship had been previously shown in other stone fruit trees infected with M. fructicola in different countries over the world. In order to study this relationship experiments were run in five commercial peach and nectarine orchards located in the Ebro Valley in four phenologic states from 2000 to 2002. Latent infections were not observed in pink button, the maxima incidence arise in preharvest, although in some orchards another increase occurred in the embryo hardening. The most prevalence species was M. laxa. A significant positive correlation between the incidence of latent infections and the incidence of rot in postharvest was obtained. A prediction model of the latent infections based on the temperature (T) and the wetness duration (W) was also developed. This model showed that T and W explained 83% of the variation in latent infection incidence caused by Monilinia spp. Below 8ºC latent infection was not predicted, more than 22h of W with T = 8ºC were needed to predict latent infection occurrence of, whereas at 25ºC just 5h of W were enough. Tests under controlled conditions were also made to determine the relationship among latent infections incidence, environmental conditions (T and W), inoculum concentration of the pathogen (I) and development state of the host (S) to validate the prediction model developed on the field experiments. These tests were made with flowers and fruits of nectarine coming from a commercial orchard, in six phenologic states in 2004 and 2005, showing that incidence of rot in postharvest and latent infections were affected by T, W, I and S. In fruits latent infections took place when the T was not suitable for rot development. Once developed the embryo, more than 4-5h of W per day and higher inoculums (104 conidia ml-1) were necessary for rot or latent infection development. The equation of the model obtained with the field data was able to predict the data observed in these experiments. In order to evaluate the effect of inoculum of Monilinia spp. in the incidence of latent infections and of rot of fruits in postharvest, 11 experiments in commercial orchards of peach and nectarine of the Ebro Valley were performed from 2002 to 2005. A positive correlation between the conidial numbers of Monilinia spp. in the surface of the fruits and the incidence of latent infections was observed. Based on those studies other two important recommendations for the agriculturists are deduced: control strategies must consider the latent infections and potential risk based on the T and W. Spores concentration of Monilinia spp. in the surface of fruits must be also taken in concern to reduce the brown rot risk. The knowledge of the population structure of the pathogens determines the bases to establish more effective methods of diseases handling. For that reason in this Thesis the degree of genetic diversity among different M. laxa populations has been studied in different Spanish locations using 144 RAPDs markers (59 polymorphic and 85 monomorphics) on 21 fungal isolates. The analysis of the structure of the population revealed that the genetic diversity within the subpopulations (orchards) (HS) represented 97% of the genetic diversity (HT), whereas the genetic diversity between subpopulations (DST) only represented a 3% of the total of this diversity. The relative magnitude of the genic differentiation between subpopulations (GST) reached 0.032 and the considered number of migrantes by generation (Nm) was of 15.1. The results obtained in dendrograms were in agreement with the analysis of genic diversity. The obtained groupings were independent of the orchard of origin, year or host. In the Thesis the relative importance of the different evolutionary sources in the populations from M. laxa is discussed. Finally a sampling of resistant isolates in different orchards from peach and nectarine of Ebro Valley was made to determine the existence of fungicide resistance of the group of benzimidazoles and the dicarboximidas, fungicides used habitually for the control of rot brown and with high risk of resistance developing in the pathogenic populations. The analysis of 114 isolated ones of M. laxa with the fungicides Benomilo (bencimidazol) (1Bg m.a ml-1), and Iprodiona (dicarboximida) (5Bg m.a ml-1), showed no resistant in the doses evaluated.

Investigación de mezclas de caucho, con bajo contenido en cloro, para bandas transportadoras con características ignífugas

El objeto de la tesis doctoral se centra en la obtención de una banda transportadora de minería exenta de halógenos o al menos con el menor contenido posible, es por ello que se ha realizado un estudio de diferentes matrices poliméricas sin halógenos y se han evaluado diferentes sistemas ignifugantes. Se ha partido de mezclas con base polimérica de caucho natural y de estireno butadieno ya que son cauchos sin halógenos y con los que se pueden obtener mezclas de buenas propiedades mecánicas. Los resultados obtenidos durante el desarrollo de la tesis han sido muy satisfactorios, ya que se fabricaron bandas a gran escala para poder realizar los ensayos descritos en la normativa UNE EN 14973. La clasificación adquirida, categoría B1, alcanza dos de los objetivos marcados al inicio de los trabajos de investigación, y por tanto puede dar lugar a: - La fabricación a nivel industrial - La comercialización de una banda retardante de llama para minería y obra subterránea, formulada con un nuevo aditivo que reduce notablemente el contenido en cloro. - Disminución de la contaminación derivada de los humos tóxicos producidos cuando una banda transportadora arde accidentalmente. Los aditivos retardantes de llama sin halógenos, son muy efectivos en dosis elevadas, para la obtención de mezclas con propiedades ignífugas, pero las propiedades mecánicas de las mezclas se debilitan. Se ha buscado un compromiso entre las propiedades ignífugas y mecánicas, por lo que resulta adecuado obtener aditivos que posean un tamaño de partícula tal que actúen como cargas semi-reforzantes para poder utilizarlos en mayor proporción y así poder conseguir las propiedades ignífugas deseadas sin alterar de forma significativa las demás propiedades de la mezcla. ABSTRACT The purpose of this thesis is to obtain a mining conveyor belt with minimal halogen content, with the final objective of being halogen-free. Several polymer matrices without halogen and as well as fireproof systems have been analyzed to achieve this goal. The polymer mixtures studied are based on natural rubber and styrene butadiene, due to the fact that are rubbers without halogens and which their mixtures have good mechanical properties. The outcome of the thesis research is satisfactory, since the results are manufactured conveyor belts that comply with the tests described in the UNE EN 14973. The obtained B1 classification achieves two objectives set at the beginning of the research, and therefore can lead to: - Manufacturing at industrial level - Marketing of a flame retardant conveyor belt for mining and underground works formulated with a new additive that significantly reduces the chlorine content - Reduce pollution produced of the toxic fumes generated when a conveyor accidentally burns Additive flame retardant halogen-free are very effective in high doses to obtain blends with flame retardant properties, but the mechanical properties of the blends are below standards. A compromise between the fire retardant and mechanical properties has been successfully obtained, making possible to obtain additives that show a particle size that act as semi-reinforcing load in order to use a greater extent and thus be able to achieve the pursued fire retardant properties without altering significant other properties of mixture.

Adesivo de contato de policloropreno base aquosa nanoaditivado e condicionado magneticamente.

Atualmente, os adesivos de contato de policloropreno base aquosa, possuem capacidade de adesão, variando entre 1,15 até 2,75 kgf/cm2. Em contrapartida, os adesivos de policloropreno base solvente, suportam tensões médias de cisalhamento de 3,8 kgf/cm2. Esta pesquisa apresenta uma proposta inovadora de condicionamento magnético do adesivo de contato de policloropreno base aquosa com o objetivo de aumentar a capacidade de aderência entre o adesivo e o substrato. Para promover um incremento na capacidade de adesão do adesivo de policloropreno base aquosa, formulou-se um adesivo utilizando um nanoaditivo, o gás carbônico como catalisador e um processo de condicionamento magnético precedente à etapa de aplicação sobre os substratos. Os resultados obtidos demonstraram aumento médio de 292 % na tensão de cisalhamento do adesivo condicionado magneticamente quando comparado com o adesivo de mesma formulação sem o condicionamento magnético, e quando comparado com um adesivo comercial de policloropreno base aquosa, o aumento foi de 122 %.

Mechanics of pneumatic tires.

Mode of access: Internet.

The science of plastics : a comprehensive source book based on the original literature for 1942-1946 /

A systematic collection of abstracts from the monthly abstract service Resins, rubbers, plastics.

Short-term guidelines to improve crumb rubber modified asphalt concrete pavements. Final report.

Texas Department of Transportation, Austin

Temperature rise-times in pneumatic tires. Interim report.

Transportation Systems Center, Cambridge, Mass.

Reactive processing methods for functionalisation of polymers and in-situ compatibilisation of poly(ethylene terephthalate)-based blends

One of the main objectives of this study was to functionalise various rubbers (i.e. ethylene propylene copolymer (EP), ethylene propylene diene terpolymer (EPDM), and natural rubber (NR)) using functional monomers, maleic anhydride (MA) and glycidyl methacrylate (GMA), via reactive processing routes. The functionalisation of the rubber was carried out via different reactive processing methods in an internal mixer. GMA was free-radically grafted onto EP and EPDM in the melt state in the absence and presence of a comonomer, trimethylolpropane triacrylate (TRlS). To optinuse the grafting conditions and the compositions, the effects of various paranleters on the grafting yields and the extent of side reactions were investigated. Precipitation method and Soxhlet extraction method was established to purifY the GMA modified rubbers and the grafting degree was determined by FTIR and titration. It was found that without TRlS the grafting degree of GMA increased with increasing peroxide concentration. However, grafting was low and the homopolymerisation of GMA and crosslinking of the polymers were identified as the main side reactions competing with the desired grafting reaction for EP and EPDM, respectively. The use of the tri-functional comonomer, TRlS, was shown to greatly enhance the GMA grafting and reduce the side reactions in terms of the higher GMA grafting degree, less alteration of the rheological properties of the polymer substrates and very little formation of polyGMA. The grafting mechanisms were investigated. MA was grafted onto NR using both thermal initiation and peroxide initiation. The results showed clearly that the reaction of MA with NR could be thermally initiated above 140°C in the absence of peroxide. At a preferable temperature of 200°C, the grafting degree was increased with increasing MA concentration. The grafting reaction could also be initiated with peroxide. It was found that 2,5-dimethyl-2,5-bis(ter-butylproxy) hexane (TIOI) was a suitable peroxide to initiate the reaction efficiently above I50°C. The second objective of the work was to utilize the functionalised rubbers in a second step to achieve an in-situ compatibilisation of blends based on poly(ethylene terephthalate) (PET), in particular, with GMA-grafted-EP and -EPDM and the reactive blending was carried out in an internal mixer. The effects of GMA grafting degree, viscosities of GMAgrafted- EP and -EPDM and the presence of polyGMA in the rubber samples on the compatibilisation of PET blends in terms of morphology, dynamical mechanical properties and tensile properties were investigated. It was found that the GMA modified rubbers were very efficient in compatibilising the PET blends and this was supported by the much finer morphology and the better tensile properties. The evidence obtained from the analysis of the PET blends strongly supports the existence of the copolymers through the interfacial reactions between the grafted epoxy group in the GMA modified rubber and the terminal groups of PET in the blends.

A study of fatigue failure in vulcanized rubber

Some aspects of fatigue failure in rubbers have been examined. Scanning electron micrographs of the surface exposed by the failure confirm the incremental, crack-propagation nature, of the fatigue process. Many other features of the failure surface have been identified and related to this process. The complicating effect of a reinforcing filler has also been investigated. The fatigue resistance of rubber test-pieces deformed in simple tension was measured as a function of frequency and temperature. This showed that an increase in frequency was equivalent to a decrease in temperature; for an amorphous unfilled rubber the time and temperature effects of crystallisation and fillers on the validity of this transformation is considered. This transformation indicates that hysteresis plays an important part in the fatigue process. Torsional pendulum measurements were used to demonstrate the dependence of the fatigue life on the mechanical damping. An apparatus was developed to measure the hysteresial energy loss directly at deformations, rates of deformation and temperatures consistent with a typical fatigue test. Measurements made with this apparatus are compared with fatigue values and a quantitative relationship is suggested describing fatigue, in terms of the energy lost per unit energy input in a cycle of a fatigue test.

Desenvolvimento de pastas cimentantes contendo nanossílica como material estendedor para aplicação em fases iniciais, de poços petrolíferos, submetidas à baixa temperatura (5°c ± 3ºc)

The improved performance of hydraulic binders, the base of Portland cement, consists in the careful selection and application of materials that promote greater durability and reduced maintenance costs There is a wide variety of chemical additives used in Portland cement slurries for cementing oil wells. These are designed to work in temperatures below 0 ° C (frozen areas of land) to 300 ° C (thermal recovery wells and geothermal); pressure ranges near ambient pressure (in shallow wells) to greater than 200 MPa (in deep wells). Thus, additives make possible the adaptation of the cement slurries for application under various conditions. Among the materials used in Portland cement slurry, for oil wells, the materials with nanometer scale have been applied with good results. The nanossílica, formed by a dispersion of SiO2 particles, in the nanometer scale, when used in cement systems improves the plastic characteristics and mechanical properties of the hardened material. This dispersion is used commercially as filler material, modifier of rheological properties and / or in recovery processes construction. It is also used in many product formulations such as paints, plastics, synthetic rubbers, adhesives, sealants and insulating materials Based on the above, this study aims to evaluate the performance of nanossílica as extender additive and improver of the performance of cement slurries subjected to low temperatures (5 ° C ± 3 ° C) for application to early stages of marine oil wells. Cement slurries were formulated, with densities 11.0;12.0 and 13.0 ppg, and concentrations of 0; 0.5, 1.0 and 1.5%. The cement slurries were subjected to cold temperatures (5 ° C ± 3 ° C), and its evaluation performed by tests rheological stability, free water and compressive strength in accordance with the procedures set by API SPEC 10A. Thermal characterization tests (TG / DTA) and crystallographic (XRD) were also performed. The use of nanossílica promoted reduction of 30% of the volume of free water and increased compression resistance value of 54.2% with respect to the default cement slurry. Therefore, nanossílica presented as a promising material for use in cement slurries used in the early stages of low-temperature oil wells