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abstract: The main objective of this study is to numerically investigate: (i) the ionic transport, especially chloride ion penetration into cementitious materials under imposed electric fields, and (ii) moisture transport through cracked concretes as a function of the crack geometry. Numerical methods were implemented to simulate the ionic transport process, based on coupling the Nernst-Planck equation and Poisson's equation to account for transport dominated by electromigration. This mathematical model was also modified to account for the chloride binding mechanism (physical and chemical trapping of chlorides by the cement hydrates) and the concentration dependence of the diffusion coefficient of each ion in the transport process. To validate the numerical model, experimental data from a companion work was used in this study. The non-steady state migration test, which is one of the common accelerated chloride ion transport test, is numerically simulated. The simulation provides a linear relationship between ionic concentration and ionic flux, which indicates that the diffusion part is negligible under a strong external voltage environment. The numerical models along with adjustments for the concentration-dependent diffusion coefficients, a pore structure factor (from electrical measurements) and chloride binding considerations are found to be successful in predicting the chloride penetration depth into plain and modified concretes under imposed electrical potentials. Moisture transport through cracked concrete was examined in the second part of this thesis. To better understand the crack's influence on the permeability, modified Louis' equation was chosen to relate the permeability with crack characteristics. 3D concrete crack models were developed using a MATLAB program with distinct crack tortuosities, roughnesses and sizes. As a comparison, Navier-Stokes equation and the Lattice Boltzmann method were also applied on the 3D model of the cracked concrete to evaluate their permeability. The methodology developed here is expected to be useful in understanding the influence of cracking on moisture transport, and when properly coupled with an ionic transport model that will be further developed, helps comprehensively understand the coupling effects of moisture and ionic transport on deterioration in concrete structures. / Dissertation/Thesis / M.S. Civil and Environmental Engineering 2014

<p> The amount of chloride ion incorporated into a copper electrodeposit prepared from an aqueous copper sulphate solution has been determined at low chloride concentrations by the use of radiotracers. It has been found that the electrodeposits have a surface layer which is enriched in chloride ion. Evidence has been obtained that incorporation of chloride is preceded by the formation of cuprous chloride. The incorporation of chloride has been found to be increased by the presence of organic additives in the solution. The polarization during the first 30 seconds of electolysis has been interpreted using the knowledge obtained from the radiotracer work.</p> / Thesis / Doctor of Philosophy (PhD)

O objetivo principal deste estudo foi determinar a origem da inibição do processo foto-Fenton [Fe(II)/Fe(III), H2O2, luz UV] pelo íon cloreto. Um estudo das reações primárias da etapa fotocatalítica do processo foto-Fenton por fotólise por pulso de laser na presença de NaCl mostrou que a inibição reflete: i) fotólise competitiva dos complexos Fe(Cl)2+ e Fe(Cl)2+; ii) captura do radical hidroxila (dependente do pH) pelo íon cloreto. Esses dois processos formam o ânion radical menos reativo Cl2&#8226;- em lugar do radical HO&#8226;-, provocando uma progressiva inibição da reação de degradação com a diminuição do pH. Modelagem cinética destes resultados previa que a manutenção do pH em 3,0 durante a fotodegradação evitaria a formação do Cl2&#8226;-, o que foi confirmada através de experimentos de fotodegradação do fenol e da gasolina em meio aquoso na presença de NaCl. Por outro lado, na degradação do fenol pela reação térmica de Fenton [Fe(II)/Fe(III), H2O2], o radical hidroxila não parece ter um papel muito importante. A degradação térmica não foi inibida pela presença de íon cloreto e a cinética de mineralização do fenol pela reação térmica de Fenton é indistinguível da degradação do fenol pelo processo foto-Fenton inibido por NaCl. Isso sugere que a reação proposta por Hamilton, isto é, a redução de Fe(III) a Fe(II) por catecol (o principal intermediário inicial da oxidação do fenol) na presença de H2O2, é o mecanismo principal de catálise da reação térmica de Fenton no nosso sistema. / The principal objective of the present study was to determine the origin of the inhibition of the photo-Fenton process [Fe(II)/Fe(III), H2O2, UV light] by chloride ion. A laser flash photolysis study of the primary reactions involved in the photocatalytic step of the photo-Fenton process in the presence of NaCl demonstrated that the inhibition reflects: i) competitive photolysis of the complexes Fe(Cl)2+ and Fe(Cl)2+; ii) pH-dependent sequestration of the hydroxyl radical by chloride ion. Both processes form the less reactive radical anion Cl2&#8226;- instead of HO&#8226;, resulting in a progressive inhibition of the degradation with decreasing reaction pH. Kinetic modeling of these results predicted that maintaining the pH at 3.0 throughout the reaction should prevent the formation of Cl2&#8226;-, a prediction confirmed experimentally for the photodegradation of phenol and gasoline. In contrast, in the degradation of phenol via the thermal Fenton reaction [Fe(II)/Fe(III), H2O2], the hydroxyl radical does not appear to play a very important role. Thus, the thermal degradation is not inhibited by chloride ion and the kinetics of mineralization of phenol by the thermal Fenton reaction are indistinguishable from those for degradation of phenol in the photo-Fenton reaction inhibited by NaCl. This suggests that the reaction proposed by Hamilton, i.e., reduction of Fe(III) to Fe(II) by catechol (the major initial intermediate in the oxidation of phenol) in the presence of H2O2, is the principal catalytic mechanism operative in the thermal Fenton reaction in our system.

The currently accepted method for assessing the resistance of concrete to penetration of chloride ions is ASTM C1202, commonly known as the “Rapid Chloride Permeability (RCP) Test.” The test is time-consuming, laborious, has rather high variability, and, is to a degree, user sensitive, making it problematic for inclusion in a performance-based specification. A potential alternative to the RCP test is the “Surface Resistivity (SR) Test”, a method which is dramatically easier, faster, and has less variability than the RCP test. The research reported herein was directed toward determining a correlation between RCP and SR test measurements for Tennessee bridge deck concrete, based on cylinders collected from concrete bridge decks being constructed across the state, and evaluating the appropriateness of the SR test as an alternative to the RCP test for inclusion in a performance-based specification. Results of the testing showed a clear correlation between the two methods and identified potential limits for possible inclusion in a performance-based specification.

Background: Sex and stress steroids are metabolized to 3a-hydroxy-pregnane-steroid metabolites such as allopregnanolone (Allo) and tetrahydrodeoxycorticosterone (THDOC). Allo and THDOC are neuroactive steroids that are metabolized in the brain and act in brain as potent positive GABAA receptor function modulators. Allo as well as THDOC levels increase during stress. Allo has been associated with a number of symptoms and malfunctions such as impaired memory function and negative mood symptoms in a subgroup of individuals both for animals and humans. Pregnane steroids with 3b-hydroxy-configuration (3b-steroids) have been shown to reduce the Allo enhanced GABA effect. Aims: The aims for the present thesis were to investigate the effect of 3b-steroids on the GABA mediated GABAA receptor function in presence of positive GABAA receptor modulators. Further, the regional variances between the 3b-steroids as well as the mechanism of the effect were studied. Finally, the effect of stress steroid metabolites on the GABAA receptor function was investigated. Results: 3b-OH-5a-pregnane-20-one reduced the Allo enhanced GABA mediated chloride ion uptake into cortical microsacs. The 3b-isomer reduced the efficacy of Allo without shift the concentration response curve. It is therefore suggested that the 3b-isomer has a non-competitive effect. Further, it was shown that the 3b-isomer reduced the Allo effect in a selective way since the 3b-isomer did not interact with other positive modulators or with GABA itself. Five tested 3b-steroids reduced the Allo enhanced GABA mediated chloride ion uptake in cerebral cortex and hippocampus as well as the Allo prolongation on spontaneous inhibitory postsynaptic currents (sIPSCs) in preoptic nucleus. In cerebellum on the other hand the 3b-steroids showed to have weaker or no effect compared to the other tested regions. Interestingly, in absence of Allo, two of the 3b-steroids positively modulated the GABA stimulated GABAA receptor function. In absence of Allo, 5b-pregnane-3b,20(R)-diol increased the desensitization rate of current response. In contrast to the reducing effect on the Allo induced prolongation on sIPSCs, the effect of the 3b-steroid on GABA application, was not altered in presence of Allo. The mechanism of the 3b-steroid is therefore suggested being desensitization dependent in contrast to Allo, which has been suggested to decrease the GABA unbinding rate. In contrast to the enhanced effect of Allo, glucocorticoid metabolites reduced the GABA mediated chloride ion uptake in a concentration dependent way. The results in present thesis indicate that both sex and stress steroid metabolites interact with the GABAA receptor function. The knowledge that diversity of endogenous steroids interact with the GABAA receptor function is of importance for further understanding of different sex and stress steroid related symptoms and syndromes.

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.

O objetivo principal deste estudo foi determinar a origem da inibição do processo foto-Fenton [Fe(II)/Fe(III), H2O2, luz UV] pelo íon cloreto. Um estudo das reações primárias da etapa fotocatalítica do processo foto-Fenton por fotólise por pulso de laser na presença de NaCl mostrou que a inibição reflete: i) fotólise competitiva dos complexos Fe(Cl)2+ e Fe(Cl)2+; ii) captura do radical hidroxila (dependente do pH) pelo íon cloreto. Esses dois processos formam o ânion radical menos reativo Cl2&#8226;- em lugar do radical HO&#8226;-, provocando uma progressiva inibição da reação de degradação com a diminuição do pH. Modelagem cinética destes resultados previa que a manutenção do pH em 3,0 durante a fotodegradação evitaria a formação do Cl2&#8226;-, o que foi confirmada através de experimentos de fotodegradação do fenol e da gasolina em meio aquoso na presença de NaCl. Por outro lado, na degradação do fenol pela reação térmica de Fenton [Fe(II)/Fe(III), H2O2], o radical hidroxila não parece ter um papel muito importante. A degradação térmica não foi inibida pela presença de íon cloreto e a cinética de mineralização do fenol pela reação térmica de Fenton é indistinguível da degradação do fenol pelo processo foto-Fenton inibido por NaCl. Isso sugere que a reação proposta por Hamilton, isto é, a redução de Fe(III) a Fe(II) por catecol (o principal intermediário inicial da oxidação do fenol) na presença de H2O2, é o mecanismo principal de catálise da reação térmica de Fenton no nosso sistema. / The principal objective of the present study was to determine the origin of the inhibition of the photo-Fenton process [Fe(II)/Fe(III), H2O2, UV light] by chloride ion. A laser flash photolysis study of the primary reactions involved in the photocatalytic step of the photo-Fenton process in the presence of NaCl demonstrated that the inhibition reflects: i) competitive photolysis of the complexes Fe(Cl)2+ and Fe(Cl)2+; ii) pH-dependent sequestration of the hydroxyl radical by chloride ion. Both processes form the less reactive radical anion Cl2&#8226;- instead of HO&#8226;, resulting in a progressive inhibition of the degradation with decreasing reaction pH. Kinetic modeling of these results predicted that maintaining the pH at 3.0 throughout the reaction should prevent the formation of Cl2&#8226;-, a prediction confirmed experimentally for the photodegradation of phenol and gasoline. In contrast, in the degradation of phenol via the thermal Fenton reaction [Fe(II)/Fe(III), H2O2], the hydroxyl radical does not appear to play a very important role. Thus, the thermal degradation is not inhibited by chloride ion and the kinetics of mineralization of phenol by the thermal Fenton reaction are indistinguishable from those for degradation of phenol in the photo-Fenton reaction inhibited by NaCl. This suggests that the reaction proposed by Hamilton, i.e., reduction of Fe(III) to Fe(II) by catechol (the major initial intermediate in the oxidation of phenol) in the presence of H2O2, is the principal catalytic mechanism operative in the thermal Fenton reaction in our system.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第19740号 / 工博第4195号 / 新制||工||1647(附属図書館) / 32776 / 京都大学大学院工学研究科分子工学専攻 / (主査)教授 田中 庸裕, 教授 阿部 竜, 教授 陰山 洋 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM