O emprego de processos construtivos inovadores sem o domínio da tecnologia apropriada e sem a observância de requisitos mínimos de desempenho, conduz de maneira geral, a edifícios com sérios problemas patológicos. Por estas razões, a Alvenaria Estrutural, que tem sido empregada com prioridade na construção de edifícios habitacionais, nos últimos anos no Brasil, tem apresentado aqueles problemas com indesejável extensão e gravidade. Este trabalho procura estabelecer a tecnologia mais adequada para a construção de edifícios em Alvenaria Estrutural Não Armada, em especial, para a que utiliza o bloco sílico-calcário. Procura-se também salientar os aspectos ainda não suficientemente conhecidos e que necessitam, por isto, ser pesquisados. São apresentadas as principais características dos materiais empregados. O elemento construtivo essencial do processo - a parede resistente - é sistemicamente analisado sob diferentes abordagens. Como complemento, a análise é extendida para o edifício. No estudo, é enfatizado o mais comum e menos compreendido problema patológico da alvenaria sílico-calcária: as fissuras por retração na secagem. A tecnologia construtiva apropriada é estritamente condicionada pela necessidade de que seja evitada a ocorrência destas fissuras. Em resumo, este trabalho objetiva colaborar para o projeto e a construção de edifícios competentes e duráveis, o que, infelizmente, não tem sido a regra, quando processos inovadores são empregados. / Pathological buildings problems certainly occur when innovative constructive processes are employed without knowing their own technology and without getting to minimum performance requirements. Based on these reasons, the engineered masonry which has been mainly employed on housing constructions in Brazil during the last years, shows up severs pathological problems. This study aims to describe the most appropriate known technology for unreinforced engineered brickworks, mainly for that one employing calcium silicate bricks. Therefore, the important parameters which are not yet suitably known are pointed out, thus requiring further research. The materials main characteristics are introduced. The bearing wall which is the most important constructing element is systemically analised under different approaches. Coming at the end the concepts are extended to the whole building itself. Emphasis is given in this study to drying shrinkage cracking as the most usual problem in calcium silicate brickworks and to its mechanisms not yet fully understood. The correct building technology avoids the cracking problems by using the mentioned materials and processes. Summarising , this study intends to cooperate for the correct and durable housing buildings which unfortunately are not usual nowadays when innovative constructive processes are applied.

This dissertation presents the study of freeze-thaw resistance of carbonated, low-lime calcium silicate cement based paste, mortar, and concrete and the pore system of these materials characterized by MIP, SEM, and image J analysis.

Orientador: Renato de Mello Prado / Banca: José Carlos Barbosa / Banca: Takashi Muraoka / Resumo: A escória de siderurgia é constituída basicamente por silicato de cálcio e magnésio, sendo considerada como material corretivo da acidez do solo e como fonte de nutrientes e de silício para as plantas. Diante disso, objetivou-se avaliar os efeitos da escória de siderurgia como fonte de silício e material corretivo na presença de doses de nitrogênio nos atributos químicos do solo, no estado nutricional, no crescimento e na produção de massa seca do capim-marandu. Desenvolveu-se o estudo em casa de vegetação, na FCAV/Unesp, Campus Jaboticabal-SP, no período de dezembro/05 a julho/06, realizando dois cortes. O delineamento experimental utilizado foi o de blocos ao acaso, em esquema fatorial 2x3x3 + 1, sendo duas fontes de material corretivo, três doses de material corretivo (1,61, 3,22 e 6,44 t ha-1 de ECaCO3), três doses de nitrogênio, sendo a metade, a dose e duas vezes a dose recomendada (200 mg dm-3) aplicados nos dois cortes das plantas, e uma testemunha absoluta, com quatro repetições. A unidade experimental foi constituída por um vaso preenchido com 4 dm3 de terra de um Latossolo Vermelho distrófico textura média, e quatro plantas. Verificouse que as doses de escória aumentaram as concentrações de Si no solo e na planta, diminuindo, porém, o acúmulo de N no capim. A adubação nitrogenada associada à escória incrementou a produção de massa seca e a absorção de Si pelo capimmarandu. O uso da escória de siderurgia mostra-se adequado ao cultivo da forrageira como material corretivo da acidez do solo e fonte de silício para o capim-marandu. / Abstract: The slag is constituted basically by calcium and magnesium silicate, being considered as neutralizing material of the soil acidity and as source of nutrients and of silicon for the plants. This research was carried out in greenhouse conditions with the objective to evaluate the effects of the slag plus nitrogen on the chemical attributes of the soil, nutritional state, growth and dry matter production of the marandu palisadegrass (Brachiaria brizantha). The experiment was conducted in São Paulo State University - UNESP, Brazil, during December/05 the July/06 period, when the grasses were cut twice. The experimental design was a randomized blocks with treatments organized in 2x3x3+1 in factorial scheme (two types of corrective material, tree corrective material rates, tree nitrogen rates plus a control treatment), with four replications. The experimental units were pots filled with 4 dm3 of medium texture Oxissol with four plants. The slag rates increased the soil and plant silicon contents. However, decreased the plant nitrogen contents. The nitrogen fertilization plus slag increased dry matter production and plant silicon contents. The slag was adequate as corrective material of the acidity of the soil and as silicon source to marandu palisadegrass. / Mestre

Im Rahmen dieser Arbeit wurden die Komplexierungsreaktionen von dreiwertigen Lanthaniden (Ln) und Actiniden (An) mit (α-hydroxy-)carboxylathaltigen Betonzuschlagmitteln in An- und Abwesenheit von Calciumsilikathydrat-Phasen untersucht. Die erzielten Ergebnisse erlauben eine umfassende Beschreibung der Wechselwirkungen auf thermodynamischer und molekularstruktureller Ebene.

The cement and concrete industry stand for approximately 8% of the global CO2 emissions. The demand of concrete and cement is expected to increase rapidly with the growing world population and increased urbanization. This makes it of the utmost importance for the industry to try to mitigate its emissions. One way to reduce the industry’s environmental impact is by mineral carbonation curing through which CO2 can be sequestered in the concrete. This investigation studied the CO2 uptake of wollastonite (CaSiO3) which can be used for mineral carbonation. The CO2 uptake of different brands of wollastonite powders for different temperatures, pressures and water to solid ratios were tested through carbonation, and the samples were then analyzed through XRD, SEM and particle size analysis. The results showed large differences in CO2 uptake between the brands of wollastonite powders. They also indicate that lower temperatures lead to higher CO2 uptake but also possibly slow down the reaction rate and that higher CO2 pressures seem to increase CO2 uptake though the effect is small. There was significant variation of the effects of the water to solid ratios on CO2 uptake between the tested brands. The morphology of the powders also seemed to be of little relevance as an amorphous and crystalline powder were the two best performing powders, similarly particle size is not indicated by the result to have a large effect on CO2 uptake, though further studies are required to fully determine the effect of the morphology and particle size. / Cement- och betongindustrin står för cirka 8% av de globala koldioxidutsläppen. Efterfrågan på betong och cement förväntas öka snabbt med den växande världsbefolkningen och ökad urbanisering. Detta tyder på hur viktigt det är för industrin att minska sina utsläpp. Ett sätt att minska industrins miljöpåverkan är genom härdning av betongen via mineral karbonatisering, en process som binder in koldioxid i betong. I detta arbete studerades koldioxidupptagningen av mineralen wollastonit (CaSiO3) som kan användas för mineral karbonatisering. Olika märken av wollastonitpulvers koldioxidupptag vid olika temperaturer, koldioxidtryck och vattenhalter testades genom karbonatisering och proverna analyserades därefter genom XRD-analys, SEM-analys och partikelstorleksanalys. Resultaten visade stora skillnader i koldioxidupptagning mellan varumärkena av wollastonitpulver. De visar även att lägre temperaturer leder till högre upptag av koldioxid, men att reaktionshastigheten potentiellt saktar ner vid låga temperaturer. Högre koldioxidtryck verkar öka koldioxidupptagningen men effekten är liten. Det fanns signifikant variation av effekterna av vattenhalterna på koldioxidupptagning mellan de testade varumärkena. Pulvrens morfologi verkade inte ha en stor effekt då ett av de två bäst presterande pulvren var amorft och det andra kristallint. På samma sett verkade partikelstorleken inte ha en stor påverkan på koldioxidupptaget men ytterligare studier krävs för att fullständigt kunna bestämma effekten av morfologin och partikelstorleken.

O experimento foi conduzido na Faculdade de Zootecnia e Engenharia de Alimentos da Universidade de São Paulo (FZEA-USP) em área pertencente à Prefeitura do Campus Administrativo da USP, no município de Pirassununga, SP de março de 2002 a junho de 2003 em uma área experimental correspondendo a 16 piquetes de 35 m de largura e 90 m de comprimento (3150 m² cada – totalizando 5,04 ha), sendo que cada piquete foi dividido em oito sub-parcelas de 8,75 m de largura e 45 m de comprimento totalizando 150 m² de área útil por tratamento. O objetivo foi avaliar os atributos químicos do solo e planta, produção de massa seca e composição bromatológica com a utilização do Silicato de Cálcio no capim – braquiarão. O delineamento experimental foi em blocos completos e ao acaso e o experimento um esquema fatorial 4 x 4 com parcelas subdivididas no tempo (45, 90 e 365 dias) compostos de quatro ofertas de forragem (5%, 10%, 15% e 20% - kg de massa seca. 100 kg-1 de peso animal.dia-1) e de quatro níveis de Silicato de Cálcio (0, 2, 4 e 6 ton.ha-1) com quatro repetições para cada oferta, sendo o fator A: Oferta de Forragem e o fator B: dose de Silicato de Cálcio. As variáveis avaliadas foram: atributos de solo (pH, K, Ca, Mg, Si, V % e H + Al), folha (N, P, K, Ca, Mg e Si), produção de massa seca (pré, pós e desaparecimento foliar) e bromatológicos (PB, FDN, FDA e LIG). Para os atributos químicos de folha, a aplicação de doses crescentes de silicato de cálcio alterou a sua composição de forma positiva em relação à testemunha para as condições do experimento. Para os atributos químicos de solo, houve resposta benéfica da aplicação de Silicato de Cálcio, quando avaliado isoladamente e, também, quando analisado em conjunto com o Calcário Magnesiano, para a correção da acidez do solo nas camadas superficiais e sub-superficiais. A produção de massa seca foi influenciada de forma benéfica pela utilização do Silicato de cálcio, onde apresentou tendência de resposta positiva para os tratamentos. A composição bromatológica foi afetada pelos níveis de ofertas utilizados, mas não respondeu de forma significativa aos tratamentos empregados. Houve um acréscimo positivo nos teores de Silício no solo e na planta com a utilização do Silicato de Cálcio. / The experiment was conducted in the FZEA-USP in an area belonging to the Administrative Campus of USP, located in Pirassununga - SP from March of 2002 to June of 2003 in an experimental area corresponding to 16 pickets of 35 m of width and 90 m of length (3150 m² each - totaling 5,04 ha), and each picket was divided in eight sub-portions of 8,75 m of width and 45 m of length totaling 150 m² of useful area for treatment. The objective was to evaluate the chemical attributes of the soil and it plants, dry matter production and nutritional quality with the use of Calcium Silicate in the signal - grass. The experimental design was in complete randomized blocks and the experiment a factorial 4 x 4 with portions subdivided in the time (45, 90 and 365 days) composed of four forage offers (5%, 10%, 15% and 20% - kg of dry matter/100 kg weight animal.day) and of four levels of Calcium Silicate (0, 2, 4 and 6 ton.ha-1) with four repetitions for each offer, being the factor A: Offer of Forage and the factor B: amount of Calcium Silicate. The evaluated responses were: soil attributes (pH, K, Ca, Mg, Si, V% and H + Al), leafs (N, P, K, Ca, Mg and Si), production of dry matter (pre, post and foliate disappearance) and nutritional qualities (CP, NDF, ADF and LIG). For the chemical attributes of leaf, the application of growing doses of calcium silicate altered its composition in a positive way in relation to the control (without calcium silicate) for the conditions of the experiment. For the chemical attributes of soil, there was a beneficial response of the application of calcium silicate, when evaluated separately and, also, when analyzed together with the lime, for the correction of the acidity of the soil in the superficial and sub-superficial layers. The production of dry matter was influenced in a beneficial way by the use of calcium silicate, where it presented tendency of positive response for the treatments. The nutritional composition was affected by the levels of offers used, but it didn't response from a significant way to the treatments applied. There was a positive increment in the tenors of Si in the soil and in the plant with the use of calcium silicate.

Submitted by (lucia.rodrigues@ufrpe.br) on 2017-03-17T14:39:22Z No. of bitstreams: 1 Janaina Cortez de Oliveira.pdf: 616667 bytes, checksum: 9d56953508b1cd4518224b8966b15c92 (MD5) / Made available in DSpace on 2017-03-17T14:39:22Z (GMT). No. of bitstreams: 1 Janaina Cortez de Oliveira.pdf: 616667 bytes, checksum: 9d56953508b1cd4518224b8966b15c92 (MD5) Previous issue date: 2010-10-22 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / The bacterial blight caused by Xanthomonas citri subsp. malvacearum (Xcm) is the most important bacterial disease of cotton in the Middle-West and Northeast Regions of Brazil. The variability of a population formed by 100 Xcm strains obtained from commercial fields in the states of Goiás, Mato Grosso, Mato Grosso do Sul and Bahia, Brazil, was analyzed based upon genetic and phenotypic characteristics. The enzymes amylase, lipase, cellulase and the polysaccharide levan were produced by all Xcm isolates while the caseinase was only produced by 20 strains. All strains induced hipersensitivity reaction in tomato leaves. The 100 strains were sensitive to copper oxychloride (1500 mg L-1), copper hidroxide (1614 mg L-1), oxytetracicline (600 mg L-1), oxytetracicline (90 mg L-1) + tribasic copper sulfate (1500 mg L-1) and oxytetracicline (76.6 mg L-1) + streptomycin sulfate (367.2 mg L-1), but resistant to kasugamycin (60 mg L-1). Among the eighteen tested antibiotics the strains presented variable reaction in relation to: nalidixic acid, amoxicillin, azithromycin, bacitracin, eritromicin, kanamycin, pefloxacin, tobramycin e vancomycin. Rep-PCR (REP, ERIC and BOX) showed the formation of five groups at 70% similarity level. Group I contained 98 strains, including the reference strain Xcm IBSBF1733, group II contained only two strains from Bahia and the other three groups included strains of Xanthomonas citri pv. anacardii, X. citri pv. mangiferaeindicae e X. axonopodis pv. spondiae used for comparison. This work also evaluated the effect of silicon (Si) on the bacterial blight of cotton control and the putative mechanisms involved in the resistance potentialized by this element were evaluated. Calcium silicate (CaSiO3) was incorporated into the soil at concentrations of 0.00, 0.25, 0.50, 1.50 and 3.00 g of SiO2 kg-1 soil 25 days before planting. Leaves of 33-day-old-plants were inoculated by infiltration with 0.5 mL suspension of Xcm (108 CFU ml-1). Components of resistance were evaluated every two days until 10 days after inoculation, at which point plant development and the accumulation of Si and Calcium (Ca) were also determined. H2O2 production and the activity of enzymes related to plant defenses were analyzed at 6, 12 and 24 hours after inoculation in plants +/-Si. In vitro inhibition of pathogen growth due to Si was also assessed. No significant difference was seen among the treatments regarding incubation period, disease incidence or inhibition of bacterial growth. However, with the application of 1.50 g of SiO2 kg-1 of soil, a reduction in severity (54.9%) was observed along with a reduction in the area under the disease progression curve (35.76%) and an increase in plant height (7.04%). There was no observable accumulation of Si in the cotton leaves. Levels of soluble proteins and H2O2 and activity of the enzymes SOD, APX, guaiacol peroxidase, PAL and b Glu were altered in the presence of Si (1.80 g SiO2 kg-1). Thus based on the genetic and phenotypic characteristics studied we conclude that the population of 100 Xcm strains presents low variability, and that the reduction of cotton bacterial blight severity mediated by Si is probably associated to the characteristic events of induced resistance observed. / A mancha-angular, causada por Xanthomonas citri subsp. malvacearum (Xcm), é a principal doença bacteriana do algodoeiro no Centro-Oeste e Nordeste do Brasil. A variabilidade de uma população de 100 isolados de Xcm, oriundos de plantas com sintomas típicos de mancha-angular em áreas produtoras de algodoeiro dos estados de Goiás, Mato Grosso, Mato Grosso do Sul e Bahia, Brasil, foi analisada com base em características fenotípicas e genéticas. As enzimas amilase, lipase e celulase e o polissacarídeo levana foram produzidos por todos os isolados de Xcm, enquanto a caseinase foi produzida apenas por 20 isolados. Todos os isolados induziram reação de hipersensibilidade em folhas de tomateiro. Os 100 isolados foram sensíveis a oxicloreto de cobre (1500 mg l-1), hidróxido de cobre (1614 mg l-1), oxitetraciclina (600 mg l-1), oxitetraciclina (90 mg l-1) + sulfato tribásico de cobre (1500 mg l-1) e oxitetraciclina (76,6 mg l-1) + sulfato de estreptomicina (367,2 mg l-1), e resistentes a casugamicina (60 mg l-1). Dentre os 18 antibióticos testados, os isolados bacterianos apresentaram reação variável a nove: ácido nalidíxico, amoxicilina, azitromicina, bacitracina, eritromicina, kanamicina, pefloxacina, tobramicina e vancomicina. Rep-PCR (REP, ERIC e BOX) revelou a formação de cinco grupos ao nível de 70% de similaridade, sendo o grupo I constituído de 98 isolados, incluindo o isolado referência de Xcm IBSBF1733, o grupo II, formado apenas por dois isolados oriundos da Bahia e os três outros grupos por isolados de X. citri pv. anacardii, X. citri pv. mangiferaeindicae e X. axonopodis pv. spondiae utilizados para comparação. Neste trabalho também foi avaliado o efeito do silício (Si) no controle da mancha-angular do algodoeiro, e os possíveis mecanismos envolvidos na resistência potencializada por este elemento. O silicato de cálcio (CaSiO3) foi incorporado ao solo nas doses de 0,00; 0,25; 0,50; 1,50 e 3,00 g de SiO2 kg-1 de solo 25 dias antes do plantio. Plantas com 33 dias tiveram as folhas inoculadas por infiltração com 0,5 mL de suspensão de Xcm (108 UFC ml-1). Os componentes da resistência foram avaliados a cada dois dias até 10 dias após a inoculação, quando o desenvolvimento da planta e o acúmulo de Si e Ca foram também determinados. Foram ainda analisadas a atividade de enzimas relacionadas à defesa vegetal e a produção de H2O2 às 6, 12 e 24 h após a inoculação em plantas +/-Si e a inibição in vitro do crescimento do patógeno. Não foi verificada diferença significativa entre os tratamentos quanto ao período de incubação, incidência da mancha-angular e inibição do crescimento da bactéria. Com a aplicação da dose 1,50 g SiO2 kg-1 de solo, observou-se redução da severidade (54,9%), da área abaixo da curva de progresso da doença (35,76%) e aumento na altura das plantas (7,04%). Não foi verificado acúmulo de Si nas folhas de algodoeiro. Níveis de proteínas solúveis e H2O2 e atividade das enzimas SOD, APX, POX, PAL e GLU foram alterados na presença do Si (1,80 g SiO2 kg-1). Com base nas características fenotípicas e genéticas analisadas, conclui-se que a população de 100 isolados de Xcm estudada apresenta baixa variabilidade e que a redução da severidade da mancha-angular do algodoeiro mediada por Si está provavelmente associada aos eventos característicos de indução de resistência observados.

O experimento foi conduzido na Faculdade de Zootecnia e Engenharia de Alimentos da Universidade de São Paulo (FZEA-USP) em área pertencente à Prefeitura do Campus Administrativo da USP, no município de Pirassununga, SP de março de 2002 a junho de 2003 em uma área experimental correspondendo a 16 piquetes de 35 m de largura e 90 m de comprimento (3150 m² cada – totalizando 5,04 ha), sendo que cada piquete foi dividido em oito sub-parcelas de 8,75 m de largura e 45 m de comprimento totalizando 150 m² de área útil por tratamento. O objetivo foi avaliar os atributos químicos do solo e planta, produção de massa seca e composição bromatológica com a utilização do Silicato de Cálcio no capim – braquiarão. O delineamento experimental foi em blocos completos e ao acaso e o experimento um esquema fatorial 4 x 4 com parcelas subdivididas no tempo (45, 90 e 365 dias) compostos de quatro ofertas de forragem (5%, 10%, 15% e 20% - kg de massa seca. 100 kg-1 de peso animal.dia-1) e de quatro níveis de Silicato de Cálcio (0, 2, 4 e 6 ton.ha-1) com quatro repetições para cada oferta, sendo o fator A: Oferta de Forragem e o fator B: dose de Silicato de Cálcio. As variáveis avaliadas foram: atributos de solo (pH, K, Ca, Mg, Si, V % e H + Al), folha (N, P, K, Ca, Mg e Si), produção de massa seca (pré, pós e desaparecimento foliar) e bromatológicos (PB, FDN, FDA e LIG). Para os atributos químicos de folha, a aplicação de doses crescentes de silicato de cálcio alterou a sua composição de forma positiva em relação à testemunha para as condições do experimento. Para os atributos químicos de solo, houve resposta benéfica da aplicação de Silicato de Cálcio, quando avaliado isoladamente e, também, quando analisado em conjunto com o Calcário Magnesiano, para a correção da acidez do solo nas camadas superficiais e sub-superficiais. A produção de massa seca foi influenciada de forma benéfica pela utilização do Silicato de cálcio, onde apresentou tendência de resposta positiva para os tratamentos. A composição bromatológica foi afetada pelos níveis de ofertas utilizados, mas não respondeu de forma significativa aos tratamentos empregados. Houve um acréscimo positivo nos teores de Silício no solo e na planta com a utilização do Silicato de Cálcio. / The experiment was conducted in the FZEA-USP in an area belonging to the Administrative Campus of USP, located in Pirassununga - SP from March of 2002 to June of 2003 in an experimental area corresponding to 16 pickets of 35 m of width and 90 m of length (3150 m² each - totaling 5,04 ha), and each picket was divided in eight sub-portions of 8,75 m of width and 45 m of length totaling 150 m² of useful area for treatment. The objective was to evaluate the chemical attributes of the soil and it plants, dry matter production and nutritional quality with the use of Calcium Silicate in the signal - grass. The experimental design was in complete randomized blocks and the experiment a factorial 4 x 4 with portions subdivided in the time (45, 90 and 365 days) composed of four forage offers (5%, 10%, 15% and 20% - kg of dry matter/100 kg weight animal.day) and of four levels of Calcium Silicate (0, 2, 4 and 6 ton.ha-1) with four repetitions for each offer, being the factor A: Offer of Forage and the factor B: amount of Calcium Silicate. The evaluated responses were: soil attributes (pH, K, Ca, Mg, Si, V% and H + Al), leafs (N, P, K, Ca, Mg and Si), production of dry matter (pre, post and foliate disappearance) and nutritional qualities (CP, NDF, ADF and LIG). For the chemical attributes of leaf, the application of growing doses of calcium silicate altered its composition in a positive way in relation to the control (without calcium silicate) for the conditions of the experiment. For the chemical attributes of soil, there was a beneficial response of the application of calcium silicate, when evaluated separately and, also, when analyzed together with the lime, for the correction of the acidity of the soil in the superficial and sub-superficial layers. The production of dry matter was influenced in a beneficial way by the use of calcium silicate, where it presented tendency of positive response for the treatments. The nutritional composition was affected by the levels of offers used, but it didn't response from a significant way to the treatments applied. There was a positive increment in the tenors of Si in the soil and in the plant with the use of calcium silicate.

Η παρουσία αυξημένων συγκεντρώσεων πυριτικών ιόντων στα φυσικά νερά, σε συνδυασμό με την παρουσία δισθενών μεταλλοϊόντων τα οποία βρίσκονται σε σχετικά αυξημένες συγκεντρώσεις στα υπόγεια νερά έχει ως αποτέλεσμα σε συνδυασμό με την αύξηση του pH ή της θερμοκρασίας, να συντελεί στην εναπόθεση του πυριτίου με τη μορφή είτε αλάτων του με μέταλλα όπως το ασβέστιο και το μαγνήσιο είτε με την μορφή κάποιας από τις οξειδικές φάσεις (κρυσταλλικές ή μη). Οι εναποθέσεις αυτές σε μεταλλικές επιφάνειες, (σωληνώσεις, εναλλάκτες θερμότητας, αγωγούς, λέβητες κ.τ.λ.), σε βιομηχανικές μονάδες που χρησιμοποιούν νερό σε διάφορες διεργασίες και οι οποίες επιβάλλεται, για περιβαλλοντικούς λόγους, να χρησιμοποιούν ανακυκλωμένο νερό είναι και ανεπιθύμητες και επικίνδυνες. Ανεπιθύμητες επειδή μειώνουν τη θερμική αγωγιμότητα και επικίνδυνες λόγω αδυναμίας ελέγχου παραμέτρων όπως η θερμοκρασία. Βασικός στόχος της παρούσας εργασίας είναι η διερεύνηση του μηχανισμού σχηματισμού πυριτικών εναποθέσεων παρουσία ασβεστίου σε υδατικά διαλύματα. Κατά την επαφή υδατικών διαλυμάτων με ξένες επιφάνειες και υπό την προϋπόθεση ότι τα υδατικά διαλύματα είναι υπέρκορα ως προς τον σχηματισμό δυσδιάλυτων πυριτικών αλάτων, σχηματίζονται πυριτικές επικαθίσεις. Η διερεύνηση του μηχανισμού πραγματοποιήθηκε με μετρήσεις του ρυθμού σχηματισμού ιζημάτων σε διαλύματα υπέρκορα τόσο ως προς άλατα του πυριτικού ασβεστίου όσο και ως προς σειρά οξειδίων του πυριτίου. Η μέτρηση των ρυθμών έγινε βάσει της μεταβολής της οπτικής πυκνότητας των υπέρκορων διαλυμάτων συναρτήσει του χρόνου αλλά και από μετρήσεις της μεταβολής των ιόντων ασβεστίου και των πυριτικών ιόντων συναρτήσει του χρόνου, σε pH 9.0 και θερμοκρασία 25C. Μετρήθηκαν οι χρόνοι επαγωγής οι οποίοι προηγούνται της εμφανίσεως στερεών στα υπέρκορα διαλύματα, οι οποίοι ήταν αντιστρόφως ανάλογοι των αντιστοίχων υπερκορεσμών. Βάσει των μετρήσεων κατασκευάσθηκαν τα διαγράμματα σταθερότητας για το σύστημα CaO-SiO2-H2O. Ο χαρακτηρισμός των στερεών που σχηματίσθηκαν στην περιοχή υπερκορεσμού που μελετήθηκε, με περιθλασιµετρία ακτίνων Χ (XRD) και με ηλεκτρονική μικροσκοπία σάρωσης (SEM), έδειξε ότι κατά κύριο λόγο αποτελούνται από άμορφη σίλικα και σε πολύ μικρή περιεκτικότητα από πυριτικό ασβέστιο. Από την εξάρτηση του ρυθμού καταβύθισης από τον υπερκορεσμό των διαλυμάτων, προέκυψε ότι ο σχηματισμός της στερεάς φάσης οφείλεται σε επιφανειακή διάχυση των δομικών μονάδων στους αναπτυσσόμενους ως κρύσταλλοι, υπερκρίσιμους πυρήνες. Ως εκ τούτου, ως μέθοδος αναστολής του σχηματισμού των καταβυθιζόμενων στερεών προκρίθηκε η χρήση οργανικών ενώσεων με δραστικές ομάδες, οι οποίες λόγω του ιονισμού τους σε υδατικά διαλύματα, μπορούν να δηλητηριάσουν τα ενεργά κέντρα κρυσταλλικής ανάπτυξης των σχηματιζόμενων στερεών. Συγκεκριμένα, χρησιμοποιήθηκαν υδατοδιαλυτά ομο-πολυμερή τα οποία περιείχαν καρβοξυλομάδες και συμπολυμερή στα οποία συμπεριλαμβάνονταν και σουλφονομάδες. Η παρουσία των ενώσεων αυτών στα υπέρκορα διαλύματα και σε συγκεντρώσεις που δεν ξεπερνούσαν τα 20ppm, έδειξαν σημαντική αύξηση αφενός του χρόνου επαγωγής και μείωση του ρυθμού σχηματισμού των ιζημάτων. / Natural waters containing elevated levels of silicate concentration, in combination with the presence alkaline earth metal ions at relatively high concentrations, (present especially in ground water), result to the formation of tenaciously adhering solid precipitates consisting of calcium and/or magnesium silicate or even of an oxidized phase (crystalline or amorphous). Increased pH values or elevated temperatures enhance deposition. Deposition of silicates on metal surfaces, including tubing, heat inverters, conductors and boilers used in water intensive industrial processes, are very common. These depositions result to energy losses because of their low thermal conductivity and raise safety issues especially in processes involving high temperatures and pressures. The main task of the present work was the investigation of silicate deposition mechanism in aqueous media in the presence of calcium. The investigation of the deposition mechanism was accomplished through measurements of the rate of solid formation in aqueous supersaturated solutions both with respect to calcium silicates and to silica. The rate measurements were based on the optical density variation of the solutions, as a function of time and on the concomitant variation of the involved ions concentrations. All measurements were carried at 25oC and at initial pH value of 9.0. Induction times were measured and were found to be inversely proportional to the solution super saturation. The stability diagrams for the system CaO-SiO2-H2O, were constructed from these measurements. The solids characterization, was done by Powder X – Ray Diffraction (XRD) and by Scanning Electron Microscopy (SEM). It was found that at the experimental conditions of the present work amorphous silica was the main component of the precipitates rather than calcium silicate. The deposition mechanism was surface diffusion controlled. Water soluble polymers, with carboxylic and sulfonic groups, were tested as inhibitors to the deposition. The presence of these compounds at concentration levels as low as 20ppm showed significant extension of the induction times preceding the spontaneous precipitation and reduction of the precipitation rates reaching 40%.

Η ευρύτατη χρήση του τσιμέντου οφείλεται στην χρήση του ως βασικού δομικού υλικού σε σύγχρονες κατασκευές περιλαμβανομένου και του εγκιβωτισμού επικίνδυνων στερεών ή υγρών αποβλήτων. Οι υψηλές τιμές pH και οι πολύπλοκες στερεοχημικές δομές των ένυδρων αλάτων του πυριτικού ασβεστίου (C-S-H gel) στο τσιμέντο, μπορούν να εγκλωβίσουν πολλά χημικά είδη βαρέων μετάλλων στο πλέγμα τους, καθιστώντας τα έτσι ανενεργά. Ο βαθμός σχηματισμού των ένυδρων πυριτικών αλάτων είναι επίσης, ρυθμιστικός παράγων του πορώδους, της σκληρότητας και της αντοχής του σκυροδέματος. Οι κυριότεροι τύποι του C-S-H gel που εντοπίζονται στα συστατικά του τσιμέντου είναι το πυριτικό διασβέστιο Ca2SiO4 και το πυριτικό τριασβέστιο Ca3SiO5. Εύλογα λοιπόν, η μελέτη της θερμοδυναμικής και της κινητικής σχηματισμού των αλάτων αυτών είναι πολύ σημαντική. Στην παρούσα εργασία, πραγματοποιήθηκε μελέτη της κινητικής της καταβύθισης του C-S-H gel σε υπέρκορα υδατικά διαλύματα παρασκευαζόμενα από στόκ διαλύματα Ca(NO3)2 και Na2Si3O7 σε σταθερή θερμοκρασία 25°C. Η επίδραση παραμέτρων, όπως το pH των υπέρκορων διαλυμάτων και του γραμμομοριακού λόγου των συγκεντρώσεων Ca/Si στα διαλύματα, μελετήθηκαν σε συνθήκες σταθερού pH με την προσθήκη διαλύματος NaOH από αυτόματο τιτλοδοτητή. Η κινητική ανάλυση έδειξε ότι ο μηχανισμός της ανάπτυξης των κρυσταλλικών στερεών γίνεται κυρίως με επιφανειακή διάχυση και εξαρτάται από το pH των διαλυμάτων στην περιοχή pH 10-12. Η ταυτοποίηση των ιζημάτων με τεχνικές περίθλασης ακτίνων Χ (ΧRD), υπερύθρου (FTIR) και με θερμοσταθμική ανάλυση, έδειξε τον σχηματισμό C-S-H gel με πιθανή συγκαταβύθιση άμορφης σίλικας. Το γεγονός ότι το καθορίζον την ταχύτητα στάδιο είναι η επιφανειακή διάχυση των δομικών μονάδων οδηγεί στο συμπέρασμα ότι η τροποποίηση της επιφάνειας των κρυστάλλων παρέχει την δυνατότητα ελέγχου του ρυθμού σχηματισμού του C-S-H gel και κατ’ επέκταση των ιδιοτήτων του τσιμέντου κατά την ενυδάτωσή του. Η τροποποίηση της επιφάνειας μπορεί να πραγματοποιηθεί με την βοήθεια υδατοδιαλυτών και μη χημικών ουσιών οι οποίες μπορούν να αλληλεπιδράσουν με την επιφάνεια, αλλοιώνοντας τον αριθμό και την ενεργότητα των κρυσταλλικών κέντρων ανάπτυξης. Βάσει των αποτελεσμάτων της επίδρασης της παρουσίας προσθέτων στην κινητική της καταβύθισης, πραγματοποιήθηκαν δοκιμές σε δοκίμια τσιμέντου στα οποία έγινε και εφαρμογή πολυμερών (υδατοδιαλυτών και μη) και μετρήθηκαν η υδροπερατότητα και η αντοχή τους, ιδιότητες που εξαρτώνται από τον βαθμό σχηματισμού του πυριτικού ασβεστίου. / The widespread use of cement as a building material in modern construction, including use for embedding radioactive wastes makes it a material of paramount importance. The formation of calcium silicate hydrates is of key importance for the determination of the cement characteristic properties including porosity, strength and hardness. The main types of C-S-H gel identified between cement components include di-calcium silicate Ca2SiO4 and tri-calcium silicate Ca3SiO5. Since these silicate salts during the cement hydration interact with water yielding C-S-H gel, the investigation of homogeneous precipitation of this phase is very interesting. In the present work the kinetics of spontaneous C-S-H gel precipitation in aqueous solutions was investigated at constant solution pH from supersaturated solutions at 25°C. The pH range investigated covered the range between 10-12. The effect of the solution pH and of the molar calcium:silicate ratio in the supersaturated solutions was investigated. Plots of the rates of precipitation as a function of the solution supersaturation, showed a high order dependence suggesting that the rate determining step for the precipitation of C-S-H gel was surface diffusion. The rates were found to be pH dependent in the range investigated. The precipitate was identified by powder X-ray diffraction, infrared spectrometry (FTIR) and thermogravimetric analysis as a mixture of calcium silicate hydrate gel and amorphous silica. The fact that the rate determining step was surface diffusion control, suggested that it is possible to control the rate of precipitation through surface modification, possibly treating the surface with compounds which may interact, resulting in poisoning of the active crystal growth sites. It is anticipated that control of kinetics may result in the control of the rate and of the extent of C-S-H gel formation and subsequently of the cement properties during its hydration. On the basis of the results obtained for the precipitation of C-S-H gel in the presence of additives, a series of experiments was done on cement specimens using both water soluble and compounds soluble in organic solvents. In general, the presence of the tested additives resulted in a significant reduction of water uptake suggesting, indirectly, that the formation of C-S-H gel was suppressed. Moreover the resistance to friction was reduced, possibly due to the fact that the compounds tested formed soft but impermeable to water, surface films.