This study examines composite materials prepared from ground recycled tires (tire crumb) and post-consumer recycled high density polyethylene (HDPE). An initial set of composites was prepared from as-received tire crumb and HDPE recyclate containing 040% tire crumb in 10% increments, using injection moulding. The elastic modulus and tensile strength were found to decrease linearly with increasing tire crumb content. Addition of tire crumb to recycled HDPE caused produced an immediate reduction in the strain to failure with a progressively more modest decrease as the tire crumb content was increased. The impact toughness decreased more linearly with increasing tire crumb fraction. Cross sections of the composites showed that the tire crumb particles were in intimate contact with the matrix but post mortem examination of the fracture surface of the impact test specimens indicated that the level of bonding had been poor. A second set of composites was a prepared from 10% tire crumb. The tire crumb was first given an oxidative treatment in hot aqueous copper chloride at concentrations from 0-5 wt% Cu Ch at 50 or 100??C for 6 or 12 hours. The composites were injection moulded with an addition of 0.5 wt% dicumyl peroxide (DCP). These composites showed good bonding between the tire crumb and the recycled HDPE even at concentrations of 0% of the Cu 2+ oxidation catalyst. The addition of DCP was found to substantially reduce the modulus of neat HDPE and this reduction was reflected in the modulus of the composites. It was found that the DCP concentration could be reduced to 0.02% without adversely affecting the composites.

Improvements to the properties of recycled rubber, by developing a more selective breakdown process, is an important issue and a global challenge. Devulcanization is the most promising way to achieve this. It is a process which aims to totally or partially cleave monosulfidic (C-S-C), disulfidic (C-S-S-C) and polysulfidic (C-Sx-C) crosslinks of vulcanized rubber. In this study, the devulcanization of sulfur-vulcanized natural rubber with a variety of diphenyldisulfides has been studied using 2,3-dimethyl-2-butene and squalene as model compounds, vulcanized by sulfur and 2-bisbenzothiazole-2,2’-disulfide. 2-aminodiphenyldisulfide; 4-amino-diphenyldisulfide; bis(2-benzamido-)diphenyldisulfide and 2,2’-bithiosalicylic acid were used as aromatic disulfides devulcanization agents. Thermal analysis was used to investigate interactions between various combinations of curatives in the vulcanization systems in the absence of model compounds. Thermogravimetric analysis was used to detect mass changes during vulcanization and whether the samples decompose/evaporate so as not to contaminate differential scanning calorimetry instrumentation. Differential scanning calorimetry was used to investigate reactions occurring between curatives. Comparison of reversing and non-reversing signals in modulated experiments are suggestive of reactions between devulcanization agents and sulfur, and accelerators Vulcanization of the model compounds were performed in 10m evacuated sealed glass ampoules placed in an oil bath at 160 °C and agitated for the duration of vulcanization. After 60 min the ampoules were removed and quenched. These were then devulcanized by exposure to a devulcanization agent in a sealed ampoule at 180 for 60 min. Crosslinked 2,3-dimethyl-2-butene species were isolated and analysed by reversed phase high performance liquid chromatography. Particular attention was paid to changes in the number of sulfur atoms in the crosslinks. Results indicate that of the devulcanization agents tested 4-amino-diphenyldisulfide was the most effective. No detrimental effect on devulcanization efficiency was caused by the substitution of a basic amino group with an acidic carboxylic acid group Gel permeation chromatography was performed on devulcanized squalene crosslinks using a tetrahydrofuran eluent. GPC investigations with squalene were less effective than HPLC experiments with 2,3-dimethyl-2-butene at evaluating the relative efficiency of individual devulcanization agents. Results were, however, consistent with 4-amino-diphenyldisulfide again being the most efficient devulcanization agent.

Este trabalho tem como objetivo o desenvolvimento de uma tecnologia para a atenuação do impacto provocado pelo passivo ambiental gerado por pneus inservíveis, conjuntamente ao desenvolvimento de novos materiais compostos para uso na construção.Os pneus têm uma estrutura física especial, com grande resistência e durabilidade, mesmo ao término de sua vida útil e, por isso, sua deposição em aterros sanitários é inadequada, já que eles não permitem compactação, tornando-se favoráveis para a criação de agentes causadores de enfermidades e oferecem grandes riscos de incêndios, o que acarreta sérios danos ao meio ambiente. A tecnologia desenvolvida utilizou a borracha de pneus inservíveis, após serem picados por processo mecânico, segundo diferentes tamanhos, para a composição de produtos de baixo custo e utilizáveis na construção civil em elementos construtivos, placas de amortecimento sonoro e de revestimento de pisos para edificações, sinalização horizontal em vias públicas, absorvedores de impacto em estradas,etc. O agente de aglomeração utilizado foi a resina poliuretânica derivada do óleo de mamona (Ricinus communis), uma fonte renovável, que também apresenta estabilidade física e química, e um excelente desempenho como aglomerante. O composto obtido foi testado com relação à durabilidade, às propriedades mecânicas como resistência à compressão e tração, módulo de elasticidade e fluência por meio da termo análise, demonstrando resultados satisfatórios e confirmada sua aplicação em vários campos da construção civil. / The objective of this work is to develop a technology for the impact attenuation caused by the passive environmental generated by scrap tires, jointly to the development of new composites for being used in construction. The tires have a special physical structure, with great resistance and durability, also in the term of their useful life, therefore, their deposit in landing fields are inadequate, once they do not allow compacting, becoming favorable for the creation of causes of diseases and they offer great fires risks, what causes serious damages to the environment. The developed technology used the rubber of useless tires, after being fragmented by mechanic process, according to different sizes, for the composition of products of low cost to be used in the civil construction in constructive elements, noise reduction plates and lining of floors for constructions, horizontal signaling in public ways, impact insulating in highways, and so on. The agent of mass used was the polyurethane resin, derived of the castor oil (Ricinus communis), a renewable source that also presents physical and chemical stability, and a good bonding behavior. The obtained composite was tested in relation to durability behavior, mechanical properties which the compression forces and tension, and also its modulus of elasticity and creep by use of thermo analisys, demonstrated satisfactory results and confirmed its application in a many fields of the civil construction.

Este trabalho tem como objetivo o desenvolvimento de uma tecnologia para a atenuação do impacto provocado pelo passivo ambiental gerado por pneus inservíveis, conjuntamente ao desenvolvimento de novos materiais compostos para uso na construção.Os pneus têm uma estrutura física especial, com grande resistência e durabilidade, mesmo ao término de sua vida útil e, por isso, sua deposição em aterros sanitários é inadequada, já que eles não permitem compactação, tornando-se favoráveis para a criação de agentes causadores de enfermidades e oferecem grandes riscos de incêndios, o que acarreta sérios danos ao meio ambiente. A tecnologia desenvolvida utilizou a borracha de pneus inservíveis, após serem picados por processo mecânico, segundo diferentes tamanhos, para a composição de produtos de baixo custo e utilizáveis na construção civil em elementos construtivos, placas de amortecimento sonoro e de revestimento de pisos para edificações, sinalização horizontal em vias públicas, absorvedores de impacto em estradas,etc. O agente de aglomeração utilizado foi a resina poliuretânica derivada do óleo de mamona (Ricinus communis), uma fonte renovável, que também apresenta estabilidade física e química, e um excelente desempenho como aglomerante. O composto obtido foi testado com relação à durabilidade, às propriedades mecânicas como resistência à compressão e tração, módulo de elasticidade e fluência por meio da termo análise, demonstrando resultados satisfatórios e confirmada sua aplicação em vários campos da construção civil. / The objective of this work is to develop a technology for the impact attenuation caused by the passive environmental generated by scrap tires, jointly to the development of new composites for being used in construction. The tires have a special physical structure, with great resistance and durability, also in the term of their useful life, therefore, their deposit in landing fields are inadequate, once they do not allow compacting, becoming favorable for the creation of causes of diseases and they offer great fires risks, what causes serious damages to the environment. The developed technology used the rubber of useless tires, after being fragmented by mechanic process, according to different sizes, for the composition of products of low cost to be used in the civil construction in constructive elements, noise reduction plates and lining of floors for constructions, horizontal signaling in public ways, impact insulating in highways, and so on. The agent of mass used was the polyurethane resin, derived of the castor oil (Ricinus communis), a renewable source that also presents physical and chemical stability, and a good bonding behavior. The obtained composite was tested in relation to durability behavior, mechanical properties which the compression forces and tension, and also its modulus of elasticity and creep by use of thermo analisys, demonstrated satisfactory results and confirmed its application in a many fields of the civil construction.

The rapid growth of population and climate change has subjected our civil infrastructures to high load demands and fast aging or degradation over time. Temperature plays a key role in the performance of the aging infrastructure in form of thermal stress and cracking, temperature-induced material aging and degradation, temperature-dependent deformation, and softening. Thus, the importance of predicting the consequent behavior of the infrastructures under environmental conditions becomes imperative. This research characterizes three infrastructure surface materials, namely asphalt pavement, solar panels, and phase change materials (PCM), models the efficacy of modifiers and novel methods to improve their performance and uses these materials in the design and testing of thermal management systems for different applications. The connection between these materials is the thermal management in pavement overlays, which can be extended to other infrastructure surfaces. Asphalt pavement modified with recycled crumb rubber (CR) is a sustainable way to reuse the millions of tires that used to end in landfills. However, the ultraviolet (UV) rays from the sun have been shown to adversely affect the asphalt’s performance in the long run. The severe photo-oxidation can cause changes in the volatile components of the asphalt and result in hardening, aging, and thermal cracks in it. The effect of UV rays on the rubber-modified asphalt may be even more complex due to the presence of crumb rubber particles and their chemical/physical incompatibility and changes in the glass transition. In order to examine these effects, a PG 64-22 is modified with two percentages of 16.6 wt.% and 20.0 wt.% crumb rubber. Results show the specific heat capacities increase with UV aging with 16.6% having the highest value. The addition of the rubber particles does not change the chemical composition of the binder as confirmed by the elemental analysis. However, after UV exposure, peaks associated with carbonyl and sulfoxide are observed, proving that the rubber-modified binder is subject to photo-oxidation as well. The 16.6. wt.% shows the best performance against aging with the lowest sulfoxide index and the highest aliphatic index. Another advantage of adding crumb rubber particles is the formation of a matrix due to the crosslinking of the rubber particles with the binder after being heated, as approved by microscopic images. The carbon nanotubes (CNT) are used to modify the asphalt binder to improve its rheological characteristics while also enhancing the thermal conductivity of the mixture to facilitate the transfer of heat to the surface. In this study, two samples of 3% and 6% multi walled carbon nanotubes (MWCNTs) are prepared using a foaming technology. Foaming the asphalt via water lowers its viscosity and temperature resulting in the saving of the base material and consumed energy while increasing the coating of the aggregates. The results show the CNTs can improve the thermal conductivity of the foamed binder by almost 2X while not negatively affect its rheology. For the other end of the thermal management system, a new hydronic system is introduced for the building integrated photovoltaics and thermal (BIPVT) silicon module that acts for the dual objectives of collecting heat to be used for the thermal management of the pavement and controlling the surface temperature of the solar module itself for the optimal efficiency under different operating conditions. The BIPVT panel with different flow rates of 100 to 600 ml/min were tested for the effectiveness of the cooling design. The results from experiments and simulations show that at 200 ml/min, an optimal balance for the performance of the panel is achieved to not only reduce the temperature of the panel from 88°C to 65°C, but also generate a partially heated water outlet of 37°C (compared with the 23°C inlet) that can be used for the hot water system of the building, or as the inlet feed to the hydronic cooling/heating pavement system. In addition, the BIPVT design proves to restore the power of the solar module by 24.6% at a 200 ml/min flow rate, as confirmed from the I-V curves. Finally, the feasibility study of converting the waste animal fat to a phase change material (PCM) is explored. In PCMs, the high latent heat characteristics are used to store or release energy during the phase change. The use of PCMs can significantly lower the temperature variation of buildings and the consequent energy use. While most common PCMs are paraffin-based and too expensive for large scale applications, a bio-based and more economic alternative could be the key to its vast use in infrastructure systems. However, more research is needed to achieve an animal fat PCM with high latent heat values. In this study, characterizing the raw fat shows a ~20% saturated content. After hydrolysis, the saturated portion has been increased to 65%, but the improvement in the latent is not significant. However, after separation of the fatty acids by use of crystallization, the resulting fully saturated fatty acids (palmitic and stearic acids) show a 3.5X increase in the value of the latent heat, increasing it from ~55 J/g for free fatty acids to ~195 J/g for saturated fatty acids. The promising results of the high latent heat values make the current bio-based PCM a good alternative that needs to be further explored in the future to be used for applications in buildings and BIPVT panels. Overall, the results of this PhD study provide a comprehensive understanding of materials and systems for thermal management of asphalt pavements and enable the design and development of durable self-heated pavements, which can be immediately extended to other infrastructure applications such as wall panels, net-zero buildings, and solar panels.

In present study, high energy electrons were used to modify blends based on RP and PP under two conditions: stationary and in-stationary conditions. Modification of blend under stationary condition is a process which is established in industrial application and where required absorbed dose is applied to form parts (after molding) at room temperature and in solid state. On the contrary, the modification of blend with high energy electrons under in-stationary condition is a new process (electron induced reactive processing) where required absorbed dose is applied to a molten state during melt mixing process. The modification of blend based on RP and PP under stationary condition resulted in slightly enhancement of tensile properties while the modification of this blend under in-stationary condition resulted in deterioration of tensile properties due to degradation of the PP matrix. Thus, special grafting agent (GA) is required for improving the tensile properties. The effect of different GAs on tensile, thermal, dynamic mechanical as well as morphological properties and melt flow properties of blends based on RP and PP were determined. The optimum absorbed dose for modification of blend based on RP and PP under both conditions was evaluated. In addition, the effect of treatment parameters of electron induced reactive processing was investigated.

M. Tech. (Civil Engineering, Faculty of Engineering and Technology), Vaal University of Technology) / Modified asphalt concrete is one of the important construction materials for flexible pavements. The addition of polymers and natural hydrocarbon modifiers to enhance the properties of asphalt concrete over a wide temperature range in paving applications has been the common practice. Currently these modified asphalt mixtures are relatively expensive. However, recycled polymers and rubber added to asphalt have also shown similar results in improving the performance of road pavements. In this study, an attempt has been made to use low density polyethylene (LDPE) obtained from plastic waste and crumb rubber obtained from worn out vehicle tyres. The aim was to optimise the proportions of LDPE in the bitumen binder using the ‘wet process’ and crumb rubber aggregates in the hot mix asphalt (HMA) using the ‘dry process’. The Marshall method of bituminous mix design was carried out for varying percentages of LDPE namely 2%, 4%, 6%, 8% and 10% by weight of bitumen binder and 1%, 2%, 3%, 4% and 5% crumb rubber by volume of the mineral aggregates. The characteristics of bitumen modified with LDPE were evaluated. The modified asphalt mix was also evaluated to determine the different mix characteristics. The results from laboratory studies in terms of the rheological properties of the LDPE modified bitumen binder showed an increase in viscosity, softening point and stiffness of the binder. The optimum Marshall stability values for HMA mixtures containing 2% crumb rubber tyre and 4% LDPE were found to be 30% higher than the conventional asphalt concrete mix. The wheel tracking test done at 50ºC was 9.81mm rut depth showing a good rutting resistance of the optimized mixture compared to the conventional asphalt mixes. The Modified Lottman test gave a Tensile Strength Ratio value of 0.979 which indicates a low degree of moisture susceptibility of the modified asphalt mix. The above results showed improved properties of the asphalt mixture. The economic assessment done using the present worth of costs indicated a reduction in maintenance cost due to the extended service life of the modified asphalt pavement.

In present study, high energy electrons were used to modify blends based on RP and PP under two conditions: stationary and in-stationary conditions. Modification of blend under stationary condition is a process which is established in industrial application and where required absorbed dose is applied to form parts (after molding) at room temperature and in solid state. On the contrary, the modification of blend with high energy electrons under in-stationary condition is a new process (electron induced reactive processing) where required absorbed dose is applied to a molten state during melt mixing process. The modification of blend based on RP and PP under stationary condition resulted in slightly enhancement of tensile properties while the modification of this blend under in-stationary condition resulted in deterioration of tensile properties due to degradation of the PP matrix. Thus, special grafting agent (GA) is required for improving the tensile properties. The effect of different GAs on tensile, thermal, dynamic mechanical as well as morphological properties and melt flow properties of blends based on RP and PP were determined. The optimum absorbed dose for modification of blend based on RP and PP under both conditions was evaluated. In addition, the effect of treatment parameters of electron induced reactive processing was investigated.