Alkaline industrial wastes are considered potential resources for the mitigation of CO2 emissions by simultaneously capturing and sequestering CO2 through mineralization. Mineralization safely and permanently stores CO2 through its reaction with alkaline earth metals. Apart from natural formations, these elements can also be found in a variety of abundantly available industrial wastes that have high reactivity with CO2, and that are generated close to the emission point-sources. Apparently, it is the applicability and marketability of the carbonated products that define to a great extent the efficiency and viability of the particular process as a point source CO2 mitigation measure. This project investigates the valorization of iron- and steel-making slags through methods incorporating the carbonation of the material, in order to achieve the sequestration of sufficient amounts of CO2 in parallel with the formation of valuable and marketable products. Iron- and steel-manufacturing slags were selected as the most suitable industrial byproducts for the purposes of this research, due to their high production amounts and notable carbonation capacities. The same criteria (production amount and carbonation capacity) were also used for the selection of the iron- and steel-making slag types that are more suitable to the scope of this work. Specifically for the determination of the slag types with the most promising carbonation capacities, the maximum carbonation conversions resulting from recent publications related to the influence of process parameters on the conversion extent of iron- and steel-manufacturing slags, were directly compared to each other using a new index, the Carbonation Weathering Rate, which normalizes the results based on particle size and reaction duration. Among the several iron- and steel-manufacturing slags, basic oxygen furnace (BOF) and blast furnace (BF) slags were found to combine both high production volumes and significant affinity to carbonation. In the context of this research, two different procedures aiming to the formation of value added materials with satisfactory CO2 uptakes were investigated as potential BF and BOF slags valorization methods. In them, carbonation was combined either with granulation and alkali activation (BOF slag), or with hydrothermal conversion (BF slag). Both treatments seemed to be effective and returned encouraging results by managing to store sufficient amounts of CO2 and generating materials with promising qualities. In particular, the performance of the granulation-carbonation of BOF slag as a method leading to the production of secondary aggregates and the sequestration of notable amounts of CO2 in a solid and stable form, was evaluated in this work. For comparison purposes, the material was also subjected to single granulation tests under ambient conditions. In an effort to improve the mechanical properties of the finally synthesized products, apart from water, a mixture of sodium hydroxide and sodium silicate was also tested as a binding agent in both of the employed processes. According to the results, the granules produced after the alkali activation of the material were characterized by remarkably greater particle sizes (from 1 to 5 mm) compared to that of the as received material (0.2 mm), and by enhanced mechanical properties, which in some cases appeared to be adequate for their use as aggregates in construction applications. The maximum CO2 uptake was 40 g CO2/kg of slag and it was achieved after 60 minutes of the combined treatment of alkali activated BOF slag. Regarding the environmental behavior of the synthesized granules, increased levels of Cr and V leaching were noticed from the granules generated by the combination of granulation-carbonation with alkali activation. Nevertheless, the combination of granulation with alkali activation or that of granulation with carbonation were found not to worsen, if not to improve, the leaching behaviour of the granules with regards to the untreated BOF slag. The formation of a zeolitic material with notable heavy metal adsorption capacity, through the hydrothermal conversion of the solid residues resulting from the calcium- extraction stage of the indirect carbonation of BF slag, was also investigated in this project. To this end, calcium was selectively extracted from the slag by leaching, using acetic acid of specific concentration (2 M) as the extraction agent. The residual solids resulting from the filtration of the generated slurry were subsequently subjected to hydrothermal conversion in caustic solution of two different compositions (NaOH of 0.5 M and 2 M). Due to the presence of calcium acetate in the composition of the solid residues, as a result of their inadequate washing, only the hydrothermal conversion attempted using the sodium hydroxide solution of higher concentration (2 M) managed to turn the amorphous slag into a crystalline material, mainly composed by a zeolitic mineral phase (detected by XRD), namely, analcime (NaAlSi2O6·H2O), and tobermorite (Ca5(OH)2Si6O16·4H2O). Finally, the heavy metal adsorption capacity of the particular material was assessed using Ni2+ as the metal for investigation. Three different adsorption models were used for the characterization of the adsorption process, namely Langmuir, Freundlich and Temkin models. Langmuir and Temkin isotherms were found to better describe the process, compared to Freundlich model. Based on the ability of the particular material to adsorb Ni2+ as reported from batch adsorption experiments and ICP-OES analysis, and the maximum monolayer adsorption capacity (Q0 = 11.51 mg/g) as determined by the Langmuir model, the finally synthesized product can potentially be used in wastewater treatment or environmental remediation applications.

O objetivo deste trabalho é o desenvolvimento de um laser de centro de cor para aplicações em espectroscopia. O laser opera em regime CW e a cavidade óptica utilizada é do tipo X, com dois espelhos esféricos intracavidade astigmáticamente compensados. O meio ativo utilizado foi um cristal de KCl:Li+ com centros FA (II), e como fonte de bombeamento foi empregado um laser de Ar+ em 514nm. O limiar de potência de bombeamento foi de 120 mW, a eficiência energética foi de 2,8% e o intervalo de sintonia obtido vai de 2,56 a 2,82 &#956m numa potência de bombeamento de 700mW. O laser opera também com a cavidade na configuração anel. Para testar o LCC foram feitas aplicações empregando a técnica de espectroscopia intercavidade em cristais de KCl: Li+: NO-2: NO-3 e KBr:OH-. / The present work shows the development of a color Center laser for spectroscopy application. It is a CW laser which uses an X-type cavity with two astigmatically compensated intracavity spherical mirrors. The laser can be converted to a ring laser. The used active medium was a KCl:Li+ single crystal with a FA (II) centers and the pumping source was an Ar+ laser (&#955= 514nm, 700mW). Pump power at threshold was measured to be 120mW. The tuning range was 2.56&#60 &#955 &#60 2.82 &#956m and the slope efficiency was 2,8%. To test the color center laser we measured intracavity spectra of KCl: Li+: NO-2: NO-3 and KBr:OH- single crystals.

Este estudo se propôs a avaliar a influência da cristalinidade e da deformação do quartzo na ocorrência da reação álcali-agregado. A influência da cristalinidade do quartzo foi analisada através da mesóstase, material intersticial que constitui as rochas vulcânicas, que é um material composto por grãos sub-microscópicos de quartzo e feldspatos. Para tanto foram selecionadas duas rochas vulcânicas, constituídas por quartzo em diferentes quantidades e com diferentes graus de cristalinidade: um basalto, com pouca quantidade de sílica, sem quartzo livre e cuja mesóstase apresenta grãos pobremente cristalizados; e um riolito, com grande quantidade de sílica e de quartzo livre, além de uma mesóstase com grãos melhor cristalizados. A caracterização da cristalinidade do quartzo mostrou que a mesóstase, que tem aparência de material amorfo em microscopia ótica, apresenta diferentes feições quando observada através de microscopia eletrônica de varredura: mesóstase com grãos criptocristalinos de quartzo e K-feldspatos (Mm); mesóstase com grãos de quartzo e feldspato microcristalinos (Mq); mesóstase constituída predominantemente por argilominerais (Ma). Relacionando-se essas características com a reatividade das rochas verificou-se que o quartzo presente nas mesóstases Mm e Mq reage rápida e intensamente, sobressaindo-se à dissolução da mesóstase Mm, enquanto os grãos da mesóstase Ma são preservados. Através da compração dessas constatações, obtidas com o basalto e o riolito, com as características do material intersticial de um basalto inócuo, em ensaios acelerados e em campo, verificou-se que seu material intersticial da rocha inócua possui pouca quantidade de sílica livre (quartzo). Isso evidencia que a reatividade das rochas vulcânicas está relacionada à quantidade de sílica livre presente (quartzo) e a velocidade de ocorrência da reação com a cristalinidade do quartzo constituinte da mesóstase (Mm). A influência da deformação do quartzo no desencadeamento da reação álcali-agregado foi avaliada através do estudo de rochas graníticas com diferentes graus de deformação: uma rocha pouco deformada (granito), uma rocha com deformação intermediária (proto-milonito) e uma rocha muito deformada (orto-milonito). Os graus de deformação do quartzo foram caracterizados, através de microscopia ótica, como: grau 0= ausência de deformação; grau 1= grãos pouco deformados, com extinção ondulante leve; grau 2= quartzo muito deformado, com forte extinção ondulante, chegando a formar bandas de deformação; grau 3= forte deformação, com formação de subgrãos; grau 4= grãos recristalizados. O estudo mostrou que a presença preponderante de quartzo com grau 2 nas rochas denota uma maior velocidade de desencadeamento da reação álcali-agregado. A partir dessa constatação efetuou-se a avaliação das características texturais dos grãos de quartzo de rochas reativas em campo, verificando-se que quanto maior a quantidade de grãos com grau 2 mais rápida a ocorrência da reação em campo. / This research aims to study the influence of crystallinity and deformation of quartz to the occurrence of alkali-aggregate reaction. The influence of the cristallinitiy of quartz was analyzed through the interstitial material (volcanic glass/mesostase) into volcanic rocks. This material is composing by sub-microscopic grains of quartz and feldspars, thus it was selected a basaltic rock, with poor crystallized interstitial material and low silica content; and a rhyolitic rock, with better crystallized interstitial material and high silica content. The characterization of the crystallinity of the quartz showed that interstitial mesostase has appearance of amorphous material on the optical microscopy, but, at scanning electron microscopy it was observe the following features: mesostase with microcrystalline grains of quartz and K-feldspar (Mm); mesostase with better crystallized grains of quartz and K-feldspar (Mq); mesostase with clay predominantly (Ma). Reactivity potential tests showed that quartz in Mm and Mq react quickly and intensely, especially Mm, while quartz in Ma was preserved. Comparing these evidences, obtained with basalt and rhyolite, with interstitial material into innocuous basalt, it was found that interstitial material in innocuous rock has smaller amount of free silica (quartz). It proof that reactivity of volcanic rocks is related to the amount of free silica present into the rocks and poor cristalinity of quartz into mesostase make alkali-aggregate reaction quickness (Mm). The influence of the deformation of quartz on alkali-aggregate reaction was analyzed through granitic rocks with different degrees of deformation: a rock with very little deformation (granite), a medium deformed rock (proto-mylonite), a very deformed rock (orto-mylonite). Deformation degree of quartz was characterized through optical microscopy as follows: order 0= absence of the deformation; order 1= slightly deformed grain (weak ondulatory extinction); order 2= very deformed quartz, with strong ondulatory extinction and forming deformation bands; order 3= very deformed quartz, with formation of sub-grains, order 4= recrystallized quartz. The study showed that rocks with most quartz „order 2‟ denotes the development of alkali-aggregate reaction faster than rocks with other „orders‟ deformation of the quartz. From this conclusion it was obseve the textural characteristics of quartz grains in reative rocks on the field, confirming that quartz with deformation bands cause alkali-aggregate reaction quickly.

A reação álcali-silica (RAS) ocorre entre certas formas de sílica, estruturalmente distorcidas ou amorfas, e soluções de hidróxido alcalino, como KOH e NaOH. O produto da RAS é um gel de silicato e álcalis, susceptível de expansão pela absorção de água. Quando a RAS ocorre nos agregados minerais utilizados no concreto, o processo de reação e expansão do gel compromete a resistência mecânica da estrutura. Neste trabalho, foram estudados os efeitos sobre o gel de dois processos propostos respectivamente para mitigar a expansão e prevenir a ocorrência da RAS: o tratamento do gel com LiNO3 e a aplicação de metiltrimetoxisilano (MTMS, Si(OCH3)3CH3). Também foi analisada a reatividade de minerais utilizados como agregados (basalto, granito e quartzito), simulando a RAS em condições de laboratório. Utilizando técnicas de ressonância Magnética Nuclear (RMN) de 29Si, 7Li, 23Na, 13C e 1H, foi analisada a estrutura do gel, dos minerais e dos produtos resultantes dos tratamentos e de ataques com soluções alcalinas. Os resultados mostram que a estrutura de silicatos no gel é lamelar formada principalmente por silicatos do tipo Q3 e a aplicação de soluções de LiNO3 provoca uma transformação para um silicato de tipo linear. Esta alteração, eliminado os espaços interlamelares capazes de absorver água e causar expansão coletiva da estrutura, explica o efeito observado de redução da expansão pelos tratamentos com Li. Por outro lado, após exposição ao MTMS não foi detectada interação dos silicatos pertencentes ao gel com os grupos SiCH3, indicando autocondensaçao dos silanos. Com relação ao ataque dos minerais reativos, foram detectadas mudanças na distribuição de espécie de silicatos Qn nas três rochas. No basalto e no granito existe um aumento da fração de espécies Q1 e Q4 com relação ao mineral original. No quartzito as diferenças são maiores em magnitude e dependem dos parâmetros do ataque: temperatura e tempo de ataque. O aumento da temperatura dissolve os silicatos amorfos de conectividade baixa e média (Q0, Q1 e Q2) e produz um silicato altamente conexo formado por espécies Q3 e Q4. O aumento do tempo de ataque à temperatura ambiente não produz transformações apreciáveis na parte amorfa, mas sim dissolução de silicatos Q4 pertencentes a grãos de quartzo de maior tamanho. / The alkali-silica reaction (ASR) occurs between structurally distorted or disordered silica and aqueous solutions of alkaline hydroxides, as KOH or NaOH. The product of the ASR is an alkali-silicate gel, which may expand upon water absorption. When the ASR occurs in mineral aggregate used in concrete, the process of reaction and expansion cause the decrease in the mechanical resistance of the structure. In this work, a structural study was carried out to analyze the effect on the gel of two processes proposed respectively to mitigate the expansion and prevent the ASR: the treatment with LiNO3 and the application of methyltrimethoxysilane (MTSM, Si(OCH3)3CH3). Also, the reactivity of three minerals (basalt, granite and quartzite) commonly used as aggregates was analyzed, simulating the ASR in laboratory conditions. Nuclear Magnetic Resonance (NMR) techniques of 29Si, 7Li, 23Na, 13C e 1H in the solid state were applied to analyze the structure of the gel, the minerals and the products resulting from treatments and the attack with alkaline solutions (KOH). The results show that the silicate network in the gel is a lamellar structure, composed mainly by Q3 silicates, which is transformed into a linear structure upon the treatment with LiNO3 solutions. This modification, eliminating the inter-lamellar spaces capable to host water and cause the collective expansion of the structure, explain the reduction in the expansion observed in mortar or concrete structures treated with Li. On the other hand, after exposing gel samples to MTMS aqueous solutions, no interaction of the silicate groups in the gel with SiCH3 groups were detected, indicating auto-condensation of silane in these samples. With respect to the attack of the reactive minerals, some changes were detected in the distribution of Qn silicate species in the three rocks. In attacked basalt and granite there is an increase in the fraction of Q1 and Q4with respect to the original minerals. In attacked quartzite the differences are mores strong and depend on the reaction parameters: temperature and time of attack. The increment in temperature dissolve the amorphous silicates of low and medium connectivity (Q0, Q1 and Q2) resulting in a highly connected silicate with Q3 and Q4. Conversely, no appreciable transformation in the amorphous silicates were observed during longer attack times at room temperature, but the dissolution of bigger silica particles with well defined Q4 species was observed.

The Bayer process for the production of alumina (A1203) from bauxite involves a perennial gibbsite (y-Al(OH)3) precipitation step, relating to an inherently slow crystal growth from supersaturated sodium aluminate solutions (pregnant Bayer liquors). The kinetics and mechanisms involved in the transformation of the tetrahydroxo, Al(III)-containing species in solution into octahedrally-coordinated Al(OH)3 crystals in the presence of NA+ and excess of ions, are as yet not fully known. To gain further knowledge and better understanding of the nature of solution species, their specific interaction and participation in the gibbsite crystallization mechanisms, the role alkali ions play in the kinetic behaviour and mechanisms of nucleation, growth and aggregation/agglomeration from caustic aluminate solutions of industrial strength has been investigated.

Adsorption of monolayers and multilayers of metal-free and metal phthalocyanines molecules on metal surfaces has been investigated using complementary microscopic and synchrotron-based spectroscopic techniques. It was observed by STM measurements that at monolayer coverage the adsorption direction of the metal-free phthalocyanine molecules with respect to the gold surface vary as a function of temperature, i.e. at room temperature (RT) and low temperature (LT). It was explained by the difference in strength of intermolecular and adsorbate-substrate interactions at room and low temperatures. Nature of the interaction between adsorbed species and the surfaces as a function of coverage has been further characterized by XPS measurements. Binding energy shifts as a function of coverage have been attributed to initial- and final-state effects, the latter being due to different core-hole screening for the different molecular coverage. The alignment of molecular films at both monolayer and multilayer coverages, which has been determined by XAS measurements in several cases, is also dependent upon the relative strength of molecule-molecule versus molecule-substrate interaction. Parallel alignment of the molecular film with respect to the surface is the result of significant interaction between the adsorbate and the substrate, whilst standing geometry of the molecular film is due to more significant intermolecular interactions. DFT simulations have provided further information on the nature of the adsorbate-substrate interaction as well as contribution of different molecular orbitals in XPS and XAS spectra. Moreover, investigation of alkali interaction with the phthalocyanine films revealed a significant modification in their geometric and electronic structures due to charge transfer from the alkali metal to the molecular film. However, no sign of metallization of the molecules has been observed by spectroscopic and microscopic studies.

No description available.

Cantilevered reinforced concrete columns with a lap splice of the longitudinal reinforcement near the base can induce high moment demands on the splice region when lateral loads are present on the structure. Code design specifications typically require a conservative splice length to account for these high moment demands and their consequences of bond failure. The required splice length is calculated as a function of required development length, which is a function of the bond between the reinforcement and the surrounding concrete, and a factor depending on the section detailing. However, the effects of concrete deterioration due to alkali silica reaction (ASR) and/or delayed ettringite formation (DEF) may weaken the bond of the splice region enough to overcome the conservative splice length, potentially resulting in brittle failure of the column during lateral loading. This thesis presents the following results obtained from an experimental and analytical program. * Fabrication of large-scale specimens of typical column splice regions with concrete that is susceptible to ASR/DEF deterioration * Measurement of the large-scale specimen deterioration due to ASR/DEF accelerated deterioration * Analytical model of the column splice region based on flexure theory as a function of the development length of the reinforcement and a factor to account for deterioration of the bond due to ASR/DEF * Experimental behavior of two large-scale specimens that are not influenced by premature concrete deterioration due to ASR/DEF (control specimens). This experimental data is also used to calibrate the analytical model. The conclusions of the research are that the analytical model correlates well with the experimental behavior of the large-scale control specimens not influenced by ASR/DEF. The lap splice region behaved as expected and an over-strength in the splice region is evident. To account for ASR/DEF damage, the analytical model proposes a reduction factor to decrease the bond strength of the splice region to predict ultimate performance of the region with different levels of premature concrete deterioration.

Reinforced concrete bridge columns can deteriorate prematurely due to the alkali-silica reaction (ASR) and/or delayed ettringite formation (DEF), causing internal expansion and cracking on the surface of the concrete. The performance of the longitudinal reinforcement lap splice in deteriorated concrete columns is the focus in this research. This thesis presents the results from the deterioration of large-scale specimens constructed and placed in an environment susceptible to ASR/DEF deterioration, the experimental results from four-point and three-point structural load tests, and an analytical model based on bending theory characterizing the specimen behavior during the structural load tests. Fourteen large-scale specimens were constructed, placed in an environment to accelerate the ASR/DEF deterioration mechanisms, and instrumented both internally and externally to measure the internal concrete expansions, and surface expansions and crack widths. In addition, two control specimens were constructed and kept in a laboratory, preventing ASR/DEF deterioration. Post-tensioning was used to simulate axial load on a bridge column. Structural load tests were performed on eight specimens with no ASR/DEF damage to late stage ASR and minimal DEF damage. Comparing the specimen behaviors during the loading testing, it was found that the yield strength increased about 5-15%, and post-cracking stiffness up to first yielding of the deteriorated specimens was about 25-35% stiffer than the control specimens. The increased specimen strength and stiffness likely occurred from volumetric expansion due to ASR/DEF damage which engaged the reinforcement, further confining the concrete and causing a beneficial increase in the axial post-tensioning load. The analytical model matched the control specimens well and matched the non-control specimens when the axial load was increased.

The objectives of this study were to investigate the difference and interaction of mercury (Hg) and selenium (Se) among fish species and tissues. In addition, by comparing with the detected concentrations in other regions, it would be possible to evaluate the pollution status. In the meanwhile, this study analyzed the edibility of the fish, the interaction between Hg and Se as well as their impacts on fish growth. Ten species of fish, including tenpounder (Elops machnata), fourlined terapon (Pelates quadrilineatus), whipfin silverbiddy (Gerres filamentosus), common ponyfish (Leiognathus equulus), Hamilton's thryssa (Thryssa hamiltonii), tilapia (Orechromis niloticus), western Pacific gizzard shad (Nematalosa come), large-scaled mullet (Liza macrolepis), flathead mullet (Mugil cephalus) and milkfish (Chanos chanos), and 20 sediment samples were collected from September to October of 2003 at the reservoir adjacent to a chlor-alkali plant, which had been abandoned for 22 years in Tainan City. Total mercury (THg) and organic mercury (OHg) concentrations were determined in fish muscles, livers, kidneys, gonads, gills and sediment samples. Besides, Se concentrations were also analyzed in fish muscles and livers. Concentrations (mg/kg dry wt.) of THg and OHg in sediment were 43.2¡Ó23.4(mean¡Ósd) and 0.013¡Ó0.008, respectively. THg, OHg and Se concentrations (mg/kg wet wt.) in fish muscles were 0.432¡Ó0.360, 0.305¡Ó0.206 and 0.126¡Ó0.030, similar to the concentrations in other chlor-alkali polluted regions. With the diet habit of Taiwanese, the Hg concentrations of muscles in the seven fish species exceeded the limit of Hg which was allowed to be consumed by humans. THg and OHg concentrations in the fish muscles showed significant species difference. Obviously, the concentrations in carnivorous fishes were higher than those in omnivorous and herbivorous fishes. The OHg concentrations of fish livers and kidneys were highest in carnivorous fishes, but the THg concentrations were higher in omnivorous fishes than in that of carnivorous and herbivorous fishes. Besides, Se concentrations in fish muscles and livers also showed significant species difference, but did not show relation with the feeding habit of fishes. The Hg levels among fish tissues were highest in livers or kidneys, followed by gonads and muscles, lowest in gills. Generally speaking, Se levels were higher in livers than in muscles. The liver THg concentrations of tilapia reached 10 mg/kg wet wt. Their muscle THg concentrations decreased suddenly and maintained at a level about 0.4 mg/kg wet wt. Meanwhile, the liver inorganic Hg and Se concentrations increased with fish weight, while the liver OHg concentrations did not show such a trend but stay at a low level. High Hg concentrations in the fish tissues resulted in adverse effects on fish health. High Hg concentrations in muscles and livers caused heptasomatic index to decrease in western Pacific gizzard shad and milkfish, and condition factor declined in tilipia. Moreover, gonasomatic index remained low while the Hg concentrations of muscles, livers and gonads reached a threshold, which suggested that the growth of those fishes was likely inhibited in Hg polluted environment.