Premature concrete deterioration due to alkali-silica reaction (ASR) and delayed ettringite formation (DEF) is a significant problem all over the world. In cases where these mechanisms were not initially prevented, mitigation is critical to halt expansion and cracking. The main objectives of the research presented herein were to study the effect of ambient relative humidity (RH) on rates of concrete expansion, to determine RH thresholds below which expansion due to ASR and/or DEF may be suppressed, and to evaluate coatings intended to lower the internal RH of concrete and thus minimize future potential for damage. Results from testing showed that the RH threshold for ASR was below 82%, the RH threshold for DEF was below 92%, and the RH threshold for combined ASR and DEF could be about 83% for the materials tested. Furthermore, it was shown that some coatings are effective in reducing ASR- and DEF-related expansion by lowering the internal RH of concrete. / text

No description available.

A large amount of information concerning interatomic distances in the solid state is available, but little has been done in recent times to comprehensively filter, summarize and analyze this information. Here, I examine the distribution of bond lengths for 135 ions bonded to oxygen, using 180,331 bond lengths extracted from 9367 refined crystal structures collected from the Inorganic Crystal Structure Database (ICSD). The data are used to evaluate the parameterization of the bond-length—bond-valence relation of the bond-valence model. Published bond-valence parameters for 135 cations bonded to oxygen, and the various methods used in their derivation, are evaluated. New equations to model the relation are tested and the common form of the equation is found to be satisfactory. A new method (the Generalized Reduced Gradient Method, GRG method) is used to derive new bond-valence parameters for 135 cations bonded to oxygen, leading to significant improvements in fit for many of the ions. The improved parameterization is used to gain crystal-chemical insight into the milarite structure. A literature review of 350+ published compositions is done to review the end-members of the milarite group and to identify compositions that should have been described as distinct minerals species. The a priori bond-valences are calculated for minerals of this structure, and are used to examine the controls of bond topology on site occupancy, notably by localizing the major source of strain of the structure (the B site). Examination of the compositions of all known milarite-group minerals shows that compositions with a fully occupied B site are less common than those with a vacant B site, in accord with the idea that the B site is a local region of high strain in the structure. The bond-length distributions for the ions of the alkali and alkaline-earth metal families are examined. Variations in mean bond-lengths are only partly explained by the distortion theorem of the bond-valence model. I have found that bond length also correlates with the amount of vibrational displacement of the constituent ions. The validity of some uncommon coordination numbers, e.g., [3]-coordinated Li+, [3]-coordinated Be2+, is confirmed. / October 2016

No description available.

3 Abstract Yeast Saccharomyces cerevisiae belongs to important models for alkali-metal-cation homeostasis research. As other cells, certain intracellular content of K+ is necessary for S. cerevisiae, but Na+ or other alkali metal cations (Li+ , Rb+ ) are toxic for yeast cells. Uniporters Trk1 and Trk2 are responsible for K+ accumulation, while efflux of Na+ , Li+ , Rb+ and K+ is ensured by Ena ATPases, Na+ (K+ )/H+ antiporter Nha1 and K+ specific channel Tok1. Several regulators of K+ (Na+ ) transporters are already known, but reciprocal regulation between transporters and overall picture of the maintenance of alkali-metal-cation homeostasis is still unclear. In this work, K+ circulation (simultaneous uptake and export of K+ ) was shown to be important in alkali-metal-cation homeostasis maintenance. K+ circulation is maintained using reciprocal regulation and interactions between K+ exporters and importers. Though obtained results showed that the alkali-metal-cation homeostasis and associated physiological parameters (e.g. membrane potential, cell size, salt sensitivity) are strain specific, Nha1p was verified to be important for cell survival in ever-changing natural environment. Furthermore, two novel positive regulators of Nha1p activity were found, 14-3-3 proteins and Cka1 kinase. 14-3-3 proteins...

Essa tese de Doutorado tem por objetivo apresentar uma discussão sobre a evolução do manto litosférico subcontinental na região nordeste da Província Borborema, desde o Mesozóico até Cenozóico. Para isso foram obtidos dados de geoquímica elementar e isotópica de dois importantes eventos magmáticos expostos na região: (i) o enxame de diques toleíticos Ceará-Mirim (Cretáceo Inferior) e (ii) o vulcanismo alcalino Macau representado por plugs, necks e lavas com idades distribuídas desde o Oligoceno ao Mioceno.O enxame de diques de Ceará Mirim é composto de (i) olivina toleítos de alto-Ti, (ii) toleítos evoluídos de alto-Ti (TiO2>1,5 wt.%; Ti/Y>360), e (iii) toleítos de baixo-Ti (TiO2<1,5wt%; Ti/Y<360), todos com forte enriquecimento em elementos incompatíveis relativo ao manto primitivo. Os olivina toleitos exibem teores em Nb-Ta semelhante àqueles de magmas do tipo OIB. Ao contrário, os toleitos evoluídos de alto-Ti e os toleítos a baixo-Ti mostram anomalias negativas em Nb-Ta, as quais são mais pronunciadas nos basaltos de baixo-Ti. Os olivina toleítos mostram a razões iniciais 87 Sr/86Sr uniformes (0,7034-0,7037), enquanto que as composições isotópicas de Nd e Pb são variáveis, parte delas moderadamente radiogênicas(0,512518- 0,512699; 19,13-19,25). As composições isotópicas de Pb sugerem a contribuição de um componente FOZO na gênese desses olivina toleitos. Os outros toleítos apresentam valores muito mais variáveis, com 87Sr/86Sr radiogênicas (em comparação ao BSEt=127) e valores subcondríticos para Nd (<0,512442 ou \'épsilon\'Nd< -0,6). Quando combinadas com razões 206Pb/204Pb entre 17,08 e 18,41, os toleitos evoluídos de alto-Ti e os toleitos de baixo-Ti mostram afinidade com o componente EMI, sendo as características enriquecidas dos toleitos de baixo-Ti mais acentuadas devido a contaminação crustal durante ascensão. As similaridades com EMI, as anomalia de Nb e idades modelo TDM> 1 Ga, são evidências composicionais para atribuir a origem dos toleítos evoluídos de altoe baixo-Ti à fusão do manto litosférico subcontinental proterozóico, metasomatizado por um componente de subducção. Os dados de termometria aliados aos padrões fracionados de elementos terras raras indicam que a fusão deve ter acontecido a ~60 km,na região de transição granada-espinélio assumindo uma litosfera afinada durante o Cretáceo. Os olivina toleitos, por sua vez, teriam fundido em profundidades de ~75 km a partir da astenosfera tipo-FOZO, passivamente soerguida em decorrência de afinamento litosférico relacionado a esforços distensivos duranteo Cretáceo. O vulcanismo cenozóico Macau é representado por alcali-basaltos, basanitos e nefelinitos. Basaltos toleíticos são menos comuns. Em geral, os basaltos Macau guardam alguma semelhança com os olivina toleitos cretáceos. São enriquecidos em elementos incompatíveis e 6 em Nb-Ta, mas com características mais primitivas como10<MgO<15wt.% e 200<Ni<500ppm. Todos experimentaram fracionamento de olivina e clinopiroxênio, enquanto plagioclásio contribuiu em menor importância. O modelamento feito a partir de razões entre elementos terras raras combinado a dados termométricos indicam que os basanitos e alcali-basaltos teriam fundido a partir de lherzolitos a profundidade entre 80-90 km, na região de transição espinéliogranada, enquanto que os nefelinitos seriam produto da fusão (<0,1%) mais profunda,a ~120 km de profundidade (~1470ºC). As composições isotópicas Sr-Nd-Pb são semelhantes a magmas OIB gerados pela mistura de dois reservatórios, odelados como FOZO e EM. A identificação de FOZO no Cenozóico da Província Borborema aliada à ausência de um cenário tectônico compatível com afinamento litosférico/ascensão passiva da astenosfera e/ou presença de plumas,nos leva a propor que a astenosfera tipo-FOZO teria se re-equilibrado termalmente com o manto litosférico subcontinental desde o Cretáceo. Ao contrário, o componente EM nos basaltos Macau não pode ser correlacionado ao mesmo manto litosférico enriquecido identificado nos toleitos. Embora ainda não muito clara, sua origem é por ora atribuída a metassomatismo potássico provavelmente relacionado ao impacto da pluma de Fernando de Noronha sob o continente. As similaridades isotópicas entre esses basaltos oceânicos e os basaltos continentais sugerem que alguma ligação genética deve ser considerada. Por fim, composições isotópicas de Os e idades modelo TRD obtidos de xenólitos peridotíticos nos basaltos cenozóicos, registram a recorrência de múltiplos eventos de extração de magmas (1,3 a 0,1 Ga) e metassomatismo, confirmando a evolução química complexa experimentada pelo manto litosférico subcontinental no extremo nordeste da Província Borborema. / The objective of this doctoral thesis is to present a discussion on the evolution of the subcontinental lithospheric mantle in the northeast of the Borborema Province from the Mesozoic to the Cenozoic. For this reason, element and isotope geochemical data were obtained from two important magmatic events in the region: (i) the Lower Cretaceous Ceará-Mirim dyke swarm and (ii) the Macau alkaline volcanism characterized by plugs, necks and flows of Oligocene to Miocene ages. The Ceará-Mirim dyke swarm is composed of (i) high-Ti olivine tholeiites, (ii) evolved high-Ti tholeiites (TiO2>1.5 wt.%; Ti/Y>360), and (iii) low-Ti tholeiites (TiO2<1.5 wt.%; Ti/Y<360), all exhibiting strong enrichment in incompatible elements relative to the primitive mantle. The Nb-Ta abundance in the olivine tholeiites is of OIB affinity, while the evolved high-Ti and the low-Ti tholeiites demonstrate Nb-Ta negative anomalies, more accentuated in the low-Ti basalts. Initial 87Sr/86Sr ratios in the olivine tholeiites are less variable (0.7034-0.7037), but have variable Nd and Pb isotopic compositions with some moderately radiogenic (0.512518-0.512699; 19.13-19.25). The Pb isotopic compositions suggest the contribution of a FOZO component in the genesis of the olivine tholeiites. The other tholeiites exhibit more variable values, with radiogenic 87Sr/86Sr (relative to BSEt=127) and subchondritic Nd <;0.512442 or \'èpsilon\'Nd < -0.6). When combined with the 206Pb/204Pb ratios of 17.08 to 18.41, the evolve high-Ti tholeiites demonstrate EM1 affinity, with the enriched nature of the low-Ti tholeiites more enhanced due to crustal assimilation during ascent. The similarities with EM1, the Nb anomaly and the TDM model age> 1 Ga, are compositional evidence that suggest the magmas of the evolved high-Ti and low-Ti tholeiites were generated from the melting of the Proterozoic subcontinental lithospheric mantle, metasomatized by a subduction component. A combination of the inferred temperature data with the fractionated rare earth element patterns indicate that melting might have occurred at ~60km, at the garnet-spinel lherzolites transition zone in a thinned lithosphere during the Cretaceous. On the other hand, the olivine tholeiite magma might have been generated at ~75 km depth, in a FOZO-type asthenosphere that passively welled up due to the lithospheric extension and thinning in the Cretaceous. The Macau volcanism is composed of alkali basalts, basanites and nephelinites, and rare tholeiitic basalts. Generally, the Macau basalts and the Cretaceous olivine tholeiites share some similarities. They are enriched in incompatible elements and in Nb-Ta, but with more primitive characteristics like 10<MgO<15 wt.% and 200<Ni<500 ppm. All experienced fractionation of olivine and clinopyroxene, but less important for plagioclase. Rare earth element modeling and inferred temperature data indicate that the basanitic and the alkaline basaltic magmas melted from lherzolites at 80-90 km depth, at the spinel-garnet transition, while the nephelinitic magmas were generated from melting (<0.1%) at deeper levels, at ~120 km of depth (~1470°C). The Sr-Nd-Pb isotopic compositions have affinity to OIB magmas generated from the mixing of two reservoirs, modeled as FOZO and EM. The identification of FOZO in the Borborema Province in the Cenozoic with the absence of a compatible tectonic scenario such as lithospheric thinning/passive asthenospheric upwelling and/or the presence of plumes, make us to propose that a FOZO-type asthenosphere might have thermally re-equilibrated as a subcontinental lithospheric mantle since the Cretaceous. On the other hand, the EM component in the Macau basalts cannot be linked to the same enriched lithospheric mantle identified with the tholeiites. However, their origin, though not very clear, is attributed to potassic metasomatism probably linked to the impact of the Fernando de Noronha plume on the continent. The similarities in isotopic signatures between the oceanic and continental basalts suggest a genetic link between both. Lastly, the Os isotopic compositions and TRD model ages contrained from the peridotite xenoliths in the Cenozoic basalts, record the occurrence of multiple magma extraction (1.3 to 0.1 Ga) and metasomatism events, confirming a complex chemical evolution in the subcontinental lithosphere in the far northeast of the Borborema Province.

<p>Sorghum [<i>Sorghum bicolor</i> (L.) Moench] is a staple food for millions of people in Africa and South Asia. It is mainly consumed for its starch. The starch composition and structure in the seed endosperm determines cooking properties, processing quality, and starch digestibility. </p> <p>An assay to measure the alkali spreading value (ASV) of sorghum is described. The assay was used to identify sorghum EMS mutants with variation in starch composition. The ASV mutants (ASV+) exhibited a range of starch thermal properties with starch gelatinization temperatures (GT) being lower or higher than samples from Tx623 or Sepon82. The ASV+ phenotypes were found to be correlated with starch related traits such as enthalpy (r = −0.53) and range of starch GT (T_c-T_o) (r = 0.60). </p> <p>Genes controling the ASV phenotype of sorghum and their impact on starch quality traits are described. Whole genome re-sequencing of sorghum EMS mutants exhibiting an ASV+ phenotype was used to identify single nucleotide polymorphisms (SNPs) in candidate genes <i>Sobic.004G163700</i> and <i>Sobic.010G093400</i>. The two genes were identified as a <i>SbeIIb</i>, a putative sorghum homolog of <i>amylose extender,</i> and as a <i>SSIIa</i>, respectively. Linkage analysis showed that the mutations in <i>Sobic.010G093400</i> and <i>Sobic.004G163700</i> co-segregated with the ASV phenotype. The <i>ssIIa</i>-mutants exhibited normal amylose values, lower starch GT and lower final viscosity than the wild type. The <i>sbeIIb</i>-mutants exhibited higher amylose content, higher starch GT and lower peak and final viscosity with poor gel consistency compared to the wild type and <i>ssIIa</i>-mutants. An allele dosage test indicated that the <i>sbeIIb</i>-mutants had an allele dosage dependent effect on amylose content. Double mutants of <i>sbeIIb</i> and <i>ssIIa</i> showed that amylose content, starch thermal properties and paste viscosity profiles resemble the <i>sbeIIb</i> parent. </p> <p>A study of ASV phenotypes in a panel of more than 750 sorghum conversion lines revealed genetic variation for the ASV phenotype. A few SC-lines exhibiting stable expression of the ASV+ phenotype over two growing seasons. Most of these lines were described as belonging to the working group Nandyal, durra types from India described as producing ‘glutinous grains’. Whole genome resequencing discovered common SNPs in genes associated with starch biosynthesis. A genome wide association study (GWAS) identified a significant SNP that could be associated with the starch biosynthesis gene <i>Sobic.010G273800</i>, and with candidate genes <i>Sobic.010G274800</i> and <i>Sobic.010G275001</i> both annotated as glucosyltransferases. Grain samples from SC489, SC491, SC587 and SC589 exhibited a consistent ASV+ phenotype with lower or similar starch GT, similar amylose content, and similar high viscosity and gel consistency compared to controls.</p> <p> </p>

A reação álcali-sílica é uma patologia de origem química que ocorre em estruturas de concreto. A partir desta reação há a formação de um gel de álcali-sílica que em contato com a água provoca expansão e deformação da estrutura. Esta patologia traz muitos transtornos e prejuízos, principalmente em obras que estão em contato direto com a água (barragens, pontes, piers, etc) e a possibilidade de prever o comportamento e deformações em uma estrutura desse porte é de grande valia. Neste trabalho é feita a modelagem da percolação d\'água em meio poroso por meio do método dos elementos finitos, sem movimentação de malha e fazendo uso de função Heaviside contínua para a percolação. A modelagem da reação álcali-sílica é feita por meio de um modelo paramétrico, com alteração para contemplar regimes não uniformes de umidade e sua interferência na taxa de expansão. A modelagem do campo mecânico é feita pelo Método dos Elementos Finitos Posicional. / The alkali-silica reaction (ASR) is a pathology that occurs in concrete structures. Such pathology creates an alkali-silica gel that when in contact to water promotes expansion and strain on a affected structure. Most buildings that are susceptible to this fenomena are the ones in contact with water, such as dams, piers and bridges. The possibility to predict the ASR behavior and total strain developed would be helpful. In this work, finite element method with fixed mesh is employed to model seepage in a porous media. Also, it\'s used a Heaviside function for the percolation coefficient. The modeling of the alkali-silica reaction is done by a parametric model, modified to non-uniform humidity conditions and it\'s interference on the expansion rate. The modeling of the mechanical field is done by the Positional Finite Element method.

Neste trabalho, descrevemos um espectrômetro ótico para medidas de Dicroismo Circular Magnético (DCM), utilizado nas seguintes experiências: 1) Medidas de tempo de relaxação spin-rede (T1) para centros F em NaCl, NaBr, CsBr e CsCl, a temperatura de 1,8&#176K em campos magnéticos até 17000Gs. Verificamos a validade da teoria da referência (8) para explicar as diferenças observadas, no comportamento de \'T IND.1\', para halogenetos com diferentes íons alcalinos, bem como diferentes estruturas. Comprovamos que a interação hiperfina ainda continua a ser o mecanismo mais importante para esses centros. Verificamos também que, para temperaturas entre 6&#176K e l5&#176K, os valores de experimentais para T1, em KBr, concordam razoavelmente com a teoria da referência (21). Esta terapia é uma extensão daquela da referência (8). 2) Espectros de DCM para KCl: Co++ e CaF2: Co++ foram obtidos para campos magnéticos ate 56KGs e temperaturas entre 1,8&#176K e 4,2 &#176K. Os resultados obtidos mostraram ser concordantes com a hipótese dos centros Co++ ocuparem sítios intersticiais na rede de KCl. / In this work we describe a Magnetic Circular Dicroism Spectrometer wich was used in the following experiments: 1) We measured the spin-lattice relaxation time (T1) for F centers in NaCl, NaBr, CsBr and CsCl, at 1,8&#176K in magnetic fields up to 15000Gs. We verified the suitability of the theory of ref.(O8) to explain the differences observed for halides of differents alkali ions as well as for different structures. This proves that the hyperfine interaction is the most important mechanism for this kind of centers. We also verified that, for temperatures between 6&#176K and l5&#176K, T1, the T1 experimental values fits the theory of ref.(21) reasonably well ,for F centers in KBr. This theory is an extension of that of ref.(8). 2) We obtained the MCD spectra for KCl: Co++ and CaF2: Co++ in different magnetic fields up to 56KGs, and in temperature range between 1,8 &#176K and 4,2&#176K. Our results are consistent with the assumption that Co++ centers are intersticial in KCl lattice.

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.