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Crushed or recycled concrete aggregates (CCA/RCA) is an increasingly popular material as a replacement for natural aggregates in concrete due to industry demands for more recycled, lower carbon and responsibly sourced materials. In the UK, the majority of CCA is utilised in non-structural applications such as: a general fill material, road base/subbase or in low-grade concrete. Recycled aggregate producers however, are seeking new ways to incorporate CCA into higher value applications such as structural concrete to increase profits. Opportunities to incorporate CCA into structural concrete may also arise because of project demands for sustainability or in situations where natural aggregates are in short supply. Limited research has been published regarding the effect of coarse CCA on the durability of structural concrete, particularly in respect to water and chloride ion ingress and possibility of corrosion initiation. The aim of this EngD research programme was to investigate the effect of coarse CCA and supplementary cementitious materials (SCMs) on the durability performance of structural concrete, with particular emphasis on the key liquid transport mechanisms within concrete, namely absorption by capillary action, diffusion and migration. This addressed an industry concern regarding the detrimental effect of coarse CCA which has resulted in a limit on replacement levels of coarse natural aggregates in structural concrete, as defined in Eurocodes and local national standards for concrete. In this study, structural concrete was produced with varying levels of coarse CCA replacement (up to 100%), from five different sources and/or structural elements across the UK, with various combinations of SCMs to replace in part the Portland cement. Petrographic analysis was used as an innovative technique to characterise the coarse CCA sources to determine suitability which yielded positive results. The durability performance of the resultant concrete was analysed by exposing the concrete to aggressive chloride environments. The results indicate that the inclusion of coarse CCA, even as low as 20%, had a detrimental effect on the durability performance of structural concrete, in relation to absorption by capillary action, diffusion and migration. This effect however, can be offset through the use of SCMs, which have been shown to outperform control Portland cement concrete with 100% natural aggregates in durability performance tests. The results also suggest that cementitious materials had a greater influence on durability performance than the type and source of coarse aggregates used. It is recommended that the replacement of natural aggregate with coarse CCA be limited to 30% in cases where compliance with the 28 day characteristic strength is of particular importance. If the criterion for compliance at 28 days can be relaxed and the compressive cube strength of concretes with SCMs tested at later ages for conformity (56 or 90 days), then higher quantities of coarse CCA may be incorporated up to 60% to produce a more sustainable structural concrete. It is recommended that Portland cement is partially replaced with 50% ground granulated blast-furnace slag (GGBS) to produce a CEM III/A concrete. This is a significant step towards the potential wider implementation of coarse CCA in structural concrete, provided a suitable quantity of SCM is adopted along with a reliable and consistent source of coarse CCA.

The field of organic electronics has received considerable attention over the past several years due to the promise of novel electronic materials that are cheap, flexible and light weight. While some devices based on organic materials have already emerged on the market (e.g. organic light emitting diodes), a deeper understanding of the excited states within the condensed phase is necessary both to improve current commercial products and to develop new materials for applications that are currently in the commercial pipeline (e.g. organic photovoltaics, wearable displays, and field effect transistors). To this end, a model for pi-conjugated molecular aggregates and crystals is developed and analyzed. The model considers two types of electronic excitations, namely Frenkel and charge-transfer excitons, both of which play a prominent role in determining the nature of the excited states within tightly-packed organic systems. The former consist of an electron-hole pair bound to the same molecule while in the later the electron and hole are located on different molecules. The model also considers the important nuclear reorganization that occurs when the system switches between electronic states. This is achieved using a Holstein-style Hamiltonian that includes linear vibronic coupling of the electronic states to the nuclear motion associated with the high frequency vinyl-stretching and ring-breathing modes. Analysis of the model reveals spectroscopic signatures of charge-transfer mediated J- and H-aggregation in systems where the photophysical properties are determined primarily by charge-transfer interactions. Importantly, such signatures are found to be sensitive to the relative phase of the intermolecular electron and hole transfer integrals, and the relative energy of the Frenkel and charge-transfer states. When the charge-transfer integrals are in phase and the energy of the charge-transfer state is higher than the Frenkel state, the system exhibits J-aggregate characteristics including a positive band curvature, a red shifted main absorption peak, and an increase in the ratio of the first two vibronic peaks relative to the monomer. On the other hand, when the charge-transfer integrals are out of phase and the energy of the charge-transfer state is higher than the Frenkel state, the system exhibits H-aggregate characteristics including a negative band curvature, a blue shifted main absorption peak, and a decrease in the ratio of the first two vibronic peaks relative to the monomer. Notably, these signatures are consistent with those exhibited by Coulombically coupled J- and H-aggregates. Additional signatures of charge-transfer J- and H-aggregation are also discovered, the most notable of which is the appearance of a second absorption band when the charge-transfer integrals are in phase and the charge-transfer and Frenkel excitons are near resonance. In such instances, the peak-to-peak spacing is found to be proportional to the sum of the electron and hole transfer integrals. Further analysis of the charge-transfer interactions within the context of an effective Frenkel exciton coupling reveals that the charge-transfer interactions interfere directly with the intermolecular Coulombic coupling. The interference can be either constructive or destructive resulting in either enhanced or suppressed J- or H- aggregate behavior relative to what is expected based on Coulombic coupling alone. Such interferences result in four new aggregate types, namely HH-, HJ-, JH-, and JJ-aggregates, where the first letter indicates the nature of the Coulombic coupling and the second indicates the nature of the charge-transfer coupling. Vibronic signatures of such aggregates are developed and provide a means by which to rapidly screen materials for certain electronic characteristics. Notably, a large total (Coulombic plus charge-transfer) exciton coupling is associated with an absorption spectrum in which the ratio of the first two vibronic peaks deviates significantly from that of the unaggregated monomer. Hence, strongly coupled, high exciton mobility aggregates can be readily distinguished from low mobility aggregates by the ratio of their first two vibronic peaks. Analysis of the spatial dependence of the intermolecular interactions reveals that all four aggregate types (HH-, HJ-, JH-, JJ-) can be achieved by enforcing the appropriate crystalline packing arrangement. Such tunability is possible due of the different length scales over which the natures of the two coupling sources interconvert from J-like to H-like; whereas the nature of the Coulombic coupling is known to be sensitive to displacements on the order of half the molecular length, the nature of the charge-transfer mediated exciton coupling is sensitive to geometric displacements of approximately a carbon-carbon bond length. It is proposed that such sensitivity should allow for fine tuning of the total excitonic coupling via modifications in the packing structure, as determined, for example, by the side chains. Several examples of the different aggregate types are provided throughout this dissertation as the model is used to probe the excited state character of several relevant conjugated organic systems. Such examples include pentacene and 7,8,15,16-tetraazaterrylene (TAT) along with several derivatives from the perylene family. / Chemistry

Στην παρούσα διατριβή ελέγχθηκε η καταλληλότητα των υπερβασικών και βασικών πετρωμάτων ως αδρανή υλικά υψηλής ποιότητας σε διάφορες κατασκευαστικές εφαρμογές. Ενώ παράλληλα πραγματοποιήθηκε συσχέτιση των φυσικομηχανικών παραμέτρων των πετρωμάτων με τα ορυκτολιγικά και δομικά χαρακτηριστικά τους. Επιπροσθέτως, ιδιαίτερη έμφαση δόθηκε στην περιεκτικότητα των υπο εξέταση αδρανών υλικών σε αμιαντικά ορυκτά, καθώς αυτή πρέπει να διερευνάται προ της χρήσης τους ως αδρανή υλικά. Ομοίως, επιβλαβή συστατικά, τα οποία και εξετάστηκαν, αποτελούν και οι ενώσεις του Cr και του Ni που απαντώνται σε μεγάλο βαθμό στους υπερβασικούς λιθότυπους. / -

published_or_final_version / Civil Engineering / Doctoral / Doctor of Philosophy

A RESEARCH REPORT SUBMITIED TO THE FACULTY OF ARCHITECTURE. UNIVERSITY OF THE WITWATERSRAND, JOHANNESBURG, FOR THE DEGREE OF MASTER OF SCIENCE IN BUILDING / This research project is an investigation into the effect of the grading of perlite lightweight aggregates on the resultant concrete strengths. Lightweight concretes are reviewed. Perlite, as a lightweight aggregate, is assessed. Grading theory for aggregates and in particular lightweight aggregate is analysed. A series of mix designs are proposed with manipulation of the grading of the perlite as the only variable. This is so that variations in compressive strength and density may be assessed in terms of the grading of the perlite. Those mixes are undertaken and tested for compressive strength and dry density. In this research project compressive strength is considered a benefit, while mass is considered a disadvantage. The performance of a lightweight concrete is assessed firstly in terms of the Power Factor. The Power Factor is the compressive strength divided by the dry density of a concrete. The performance of lightweight concretes produced with Perlite aggregate is assessed secondly in terms of the Cement Content factor. The Cement Content Factor is the Power Factor divided by the Cement Content. This factor has the effect of creating a common denominator of the cement content. An evaluation of the results yields the conclusions detailed in chapter Eight, the principal two being: • The optimal perlite grading tested was a monodisperse, single size fraction, of between 600 and 1180 microns. • The most practical measure for manufacturers to improve the performance of lightweight / Andrew Chakane 2019

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O estudo da reciclagem de pavimentos de concreto para utilização em novos pavimentos tem se mostrado de grande importância haja vista a quantidade de materiais necessários para a reconstrução dessas vias. Além do ganho ambiental, devido a uma menor extração de agregados, obtém-se um ganho econômico, com menor custo de transporte e de aquisição de materiais. O agregado proveniente da britagem de antigas placas de concreto se mostrou, historicamente, apto a ser utilizado para a produção de um novo pavimento de concreto. Entretanto, existem certas limitações, pois o seu uso não resulta em um concreto com características totalmente idênticas àquelas do concreto convencional. O presente trabalho apresenta resultados da análise das características dos agregados produzidos através da britagem de antigas placas de pavimentos de concreto do Rodoanel Metropolitano Mário Covas em britador de mandíbula e em britador de impacto, bem como a influência do uso de agregados reciclados nas propriedades mecânicas do concreto. No estudo comparativo entre os tipos de britador foi verificado que agregados obtidos por britador de mandíbula e por britador de impacto possuem características muito semelhantes. No estudo das características mecânicas dos concretos a resistência à tração na flexão, a resistência à tração na compressão e o módulo de elasticidade diminuíram conforme se aumentou a absorção de água ponderada dos agregados. No que se refere à resistência à compressão, contudo, não foi observada queda ao se substituir somente a fração de agregados graúdos na mistura. Quando se procedeu com a substituição da fração miúda, porém, a resistência ficou abaixo daquela do concreto de convencional. / The study of concrete pavement recycling for its use in new pavements has shown to be of great importance considering the quantity of materials that are necessary to reconstruct these roads. Besides the environmental gain, due to a lesser extraction of aggregates, there is also an economic gain, with smaller transportation and material purchasing costs. The aggregate originated from the crushing of old concrete slabs has historically been shown to be able to be employed in the construction of a new concrete pavement. However, there are limitations, since its utilization does not result in a concrete with the exact same properties of the conventional concrete. The present work presents the results from the analysis of the characteristics from the aggregates produced through the crushing of old concrete slabs using a jaw crusher and an impact crusher, as well as the influence of the use of recycled aggregates on the concrete mechanical properties. The crusher type comparative study has shown that aggregates obtained from a jaw crusher and from an impact crusher have very similar characteristics. The concrete mechanical characteristic study reveals that flexural strength, indirect tensile strength and modulus of elasticity decrease as the aggregates water absorption increase. Concerning compressive strength, however, there was no observed decrease when only coarse recycled aggregates were used. Nevertheless, when fine recycled aggregates were employed besides coarse recycled aggregates, there was a decrease in compressive strength.