Alkali activated materials, especially when activated with waterglass, are subjected to substantial drying shrinkage that hinders their broader industrial application. The effect of shrinkage reducing admixtures (SRA), based on poly(propylene glycol), on drying shrinkage of alkali activated blast furnace slag (BFS) mortars was studied. The aim of this thesis is to determine the efficiency of SRA as well as the influence of different type of alkali activator with varying silicate modulus on drying shrinkage characteristics. It was observed that the high amount of alkalis positively influenced the effect of SRA. The higher the amount of alkalis, the lower the drying shrinkage was. It also caused more water to be incorporated in the alkali activated structure and prevent it from evaporation. Thus, the weight change of such mortars was the lowest. Reduced effect of SRA on mechanical strength properties was observed in mortars with low amount of alkalis which was connected with delayed hydration resulting in insufficient amount of created C-S-H gel. The presented thesis further discussed and underlines the role of different kinds of alkali ions as well as their amount on the properties of alkali activated BFS systems.

L'objet des travaux réalisés dans cette thèse concerne la mise en oeuvre d'un éco-liant à base de co-produits industriels : une cendre volante papetière et un laitier moulu, pour la fabrication de mortiers secs. Cet éco-liant a été élaboré pour remplacer partiellement le ciment comme constituant de matériaux traditionnels d'une part, et recycler en grande quantité l'un des deux déchets industriels, la cendre volante papetière tout en intégrant les notions d'économie circulaire et d'éco-conception d'autre part. La littérature fait état de nombreux travaux sur les différents types de cendres et de laitiers mettant en avant les caractéristiques, la minéralogie, la réactivité de ces cendres volantes papetières et des laitiers moulus. Ces deux coproduits avec environ 20% de SiO2 et 50% de CaO (% pondéraux), ont une composition chimique très proche de celle d'un ciment et développent des propriétés pouzzolaniques qui peuvent suppléer celles du ciment. Leur valorisation comme matériau liant est alors envisageable. Une complète connaissance des propriétés physico-chimiques, structurelles et minéralogiques de la cendre volante papetière et du laitier moulu a conduit à une étude exploratoire de formulations. Des mélanges à partir de 72% de cendres volantes papetières et de 28% de laitier moulu ont été étudiés en se référantà la formulation de base d'un mortier pour en optimiser la teneur en eau et le niveau d'énergie de compactage. Un matériel spécifique pour compacter les éprouvettes prismatiques de dimensions 4x4x16cm3 de mortier a été utilisé. L'effet de l'ajout de trois types d'activateurs i.e. chlorure de calciumCaCl2, métasilicate de sodium Na2O3Si et carbonate de sodium Na2CO3, et d'une faible quantité deciment i.e. 5% et 10% a été analysé mettant en relation la résistance mécanique et la microstructure desmélanges. Deux formulations optimales ont fait l'objet d'analyses relatives à la minéralogie, auxrésistances mécaniques à 2, 7 et 28 jours de cure, à la microstructure avec des images MEB,distributions des pores et à la durabilité. Compte-tenu des résultats satisfaisants obtenus, une approcheà l'échelle semi-industrielle de fabrication de blocs 15x15x15 cm3 à partir des deux formulationsretenues a été menée et discutée. Les premiers résultats montrent un grand intérêt pour la fabricationde pavés et de produits dérivés pour l'aménagement de zones piétonnes ou à circulation réduite. / The aim of this thesis is the development of an eco-binder based on industrial co-products : a wastepapery ash and a ground granulated blast-furnace slag, for the manufacture of dry mortars. On the one hand,this eco-binder was developed to replace partially cement as a constituent of traditional materials, andon the other hand to recycle in large quantities one of these two industrial wastes ; wastepaper fly ashwith considering all the notions of circular economy and eco-design. From literature, there are numerousand relevant research works on the different types of ash and slag, highlighting the characteristics, themineralogy, the reactivity of the wastepaper fly ash and ground granulated blast-furnace slags in details.These two co-products with about 20 wt.% SiO2 and 50 wt.% CaO have a chemical composition veryclose to that of a cement and develop pozzolanic properties that can replace those of cement. Theirvalorization as a binder material is then possible. A complete knowledge of the physicochemical, structuraland mineralogical properties of wastepaper fly ash and ground granulated blast-furnace slag led to anexploratory study of formulations for dry mortars. The mixtures containing 72 wt.% of wastepaper fly ashand 28 wt.% of ground granulated blast-furnace slag were investigated with reference to the formulationof a standard mortar to optimize the water content and compaction energy level. A specific equipment forcompacting prismatic specimens with dimensions 4x4x16 cm3 was used. The effect of adding three types ofactivators i.e. calcium chloride CaCl2, sodium metasilicate Na2O3Si and sodium carbonate Na2CO3, anda small amount of cement i.e. 5 wt.% and 10 wt.% was analyzed. The relation between mechanical strengthand the microstructure of the mixtures has been detailed and discussed. Two optimal formulations wereimplemented and, mineralogy, mechanical strength at 2, 7 and 28 days of curing, microstructure withSEM images, pore distributions and durability have been considered and analyzed. Taking into accountthe satisfactory results obtained, a semi-industrial approach to manufacture 15x15x15 cm3 blocks fromthe two selected formulations was conducted and discussed. The first results show a great interest in themanufacture of blocks of pavement and derived products for the construction of pedestrian or reducedtraffic areas.

Increasing awareness of sustainability in the concrete industry forces structural design and executionto focus on avoiding costly and unpredictable maintenance action, instead paying higher attention todamage prevention by direct actions on early stages of production. One of such approaches, whichdeals with the problem of freezing and thawing deterioration, is intentional air bubble introductionto the concrete mix. However, the mechanism of air entrainment in concrete can be negativelyaffected on different stages of production by many factors including cement type, admixture dosage,casting conditions or mixing procedure. Therefore, reliable tools for the end-product evaluationought to be considered. The experimental study, presented in this work, focuses on understandingthe blast furnace slag (BFS) influence as well as admixtures’ dosage effect on pore structure ofhardened concrete. Three types of cement were evaluated, including ordinary portland cement(OPC) and two types of CEM III cements with different BFS percentage. The optimal amountsof air entraining agent (AEA) and super plasticizer (SP) were chosen and later reduced in orderto evaluate their impact on total air content, spacing factor and specific surface of the air voids.The main method chosen for this evaluation was the use of an office flat-bed scanner to acquireimages and application of BubbleCounter software for the analysis of the air void structure. Thisapproach is based on linear traverse method and requires special surface treatment for contrastenhancement. Specimens for the analysis were cut from hardened concrete cubes and polishedto achieve a flat surface. The samples were later treated with black ink and zinc oxide paste toachieve a clear contrast between white voids and black paste/aggregate area. In order to estimatethe accuracy of this method, more conventional tools such as pressurised gauge method and air voidanalyser were applied for comparison. Resulted mixtures showed significant differences in air voidproperties between OPC and BFS containing concrete, with the latter being less affected by AEAdosage reduction. Changes in spacing factor and specific surface were also registered; however,their deterioration did not follow the same pattern as that of total air content. No significantdeviation between the two cements containing BFS was observed. An interesting effect of the usedpolycarboxylate ether SP on the AEA reactivity was registered, showing deterioration of air voidproperties with the decrease of plasticizer amount. Comparison of the results from different air voidanalysis methods, suggested an overall agreement on the measured air void system changes due tochanging the AEA content. However, the BubbleCounter software tended to slightly overestimatethe material’s resistance to freeze and thaw phenomenon, giving the most optimistic values inspacing factor and specific surface of air voids. / Betongindustrins ökande medvetenhet om hållbarhet leder till att man inom dimensionering ochutförande fokuserar mot att undvika kostnadskrävande och oförutsedda underhållsåtgärder ochistället lägga större vikt på att förebygga skador i produktionens tidiga skeden. En av dessaåtgärder, som hanterar problemet frostnedbrytning, är en medveten inblandning av luftbubblor ibetongen. Mekanismen för att skapa luftporssystemet kan emellertid bli negativt påverkad underolika skeden av produktionen av många faktorer såsom cementtyp, tillsatsmedelsdos, gjutvillkoroch blandningsordning. Därför behöver man reflektera över pålitliga verktyg för utvärderingenav slutprodukten. Den experimentella studien, som presenteras i detta arbete, fokuserar motförståelse hur slagg och tillsatsmedelsdos påverkar den hårdnade betongens luftporssystem. Tretyper av cement utvärderades, dels ett normalt portlandcement, dels två typer av CEM III-cementmed olika andelar av slagg. Optimala mängder av luftporbildare och flyttillsatsmedel valdesmen reducerades senare för att undersöka deras inverkan på totalt luftinnehåll samt luftporernasavståndsfaktor och specifika yta. Den huvudsakliga metoden som valdes för denna utvärderingvar en flatbäddsscanner (kontorsmodell) för att ta bilder och användningen av en programvaravid namn BubbleCounter för att analysera luftporssystemet. Detta tillvägagångssätt baseras påanalys av tvärgående linjer och kräver en speciell behandling av ytan för att åstadkomma kontraster.Provkroppar för analysen sågades ut ur hårdnade betongkuber och polerades för att erhålla en jämnyta. Provkropparna var senare behandlade med svart bläck och zinkoxidpasta för att åstadkomma entydlig kontrast mellan de vita porerna och den svarta ytan av cementpasta och ballast. För att studeranoggrannheten hos denna metod användes som jämförelse även mer konventionella metoder sommätningar med trycksatta givare och luftporsanalys. De framtagna blandningarna visade signifikantaskillnader i luftporernas egenskaper mellan betong med normalt portlandcement och betong medslaggcement, där den senare påverkades i mindre grad av reduktioner i dosen luftporbildare.Förändringar I avståndsfaktor och specifik yta noterades också men försämringen följde inte sammamönster som den för totala luftinnehållet. Ingen signifikant skillnad mellan de två cementeninnehållande slagg kunde observeras. En intressant inverkan av det använda polykarboxylateterbaseradeflyttillsatsmedlet på luftporbildarens reaktivitet noterades. Den visade en försämringav luftporernas egenskaper vid en reduktion av mängden flyttillsatsmedel. En jämförelse avresultaten från de olika metoderna för luftporsanalys indikerade en övergripande överensstämmelsegällande de uppmätta luftporssystemens förändring p.g.a. förändringar i mängden luftporbildare.Programvaran BubbleCounter tenderade emellertid att något överskatta materialets motstånd motfrostnedbrytning med de mest optimistiska värdena för luftporernas avståndsfaktor och specifikayta.

Le ciment est la principale source des impacts sur l’environnement de l’utilisation du matériau béton. Afin d’optimiser ce dernier d’un point de vue environnemental, il est nécessaire de réduire son dosage en ciment. Cela peut être entrepris en remplaçant une partie du ciment par des additions minérales lors de sa fabrication.Ces travaux de thèse visent à étudier les phénomènes physico-chimiques ayant lieu lors du processus de carbonatation de bétons à forts taux de remplacement du ciment par des additions minérales ainsi que leur résistance à ce type d’attaque.Une campagne expérimentale a été menée sur des bétons de référence préparés à base de ciments courants et sur des Écobétons préparés en substituant une partie du ciment par des cendres volantes ou du laitier de haut-fourneau. Les différentes études menées portent sur la durabilité des Écobétons vis-à-vis de la carbonatation, sur l’équivalence de performances des Écobétons avec celles des bétons de référence, et sur les paramètres de composition et de microstructure contrôlant la cinétique de carbonatation. La carbonatation a été étudiée en conditions accélérées et naturelles. Les résultats montrent que les Écobétons à forts taux de substitution du ciment par des cendres (50 %) ou du laitier (75 %) pourraient remplacer, dans certains cas, les bétons conformes à la norme en vigueur.En complément à l’étude expérimentale, des simulations numériques du couplage hydratation/séchage ont été menées en vue de déterminer l’effet du séchage sur les propriétés contrôlant la cinétique de carbonatation accélérée des bétons étudiés (la porosité, la quantité de Portlandite et le degré de saturation en eau liquide). Les résultats montrent que la cinétique de séchage augmente avec le taux de substitution du ciment par des additions. Ils remettent aussi en cause la pertinence du préconditionnement des échantillons lors de l’essai de carbonatation accélérée mené selon la norme française XP P 18-458 actuellement en vigueur. / Cement is the main source of environmental impacts of concrete use. It is thus recognized that the most pragmatic solution for minimizing environmental impacts of concrete is the reduction of the cement content. This could be achieved by replacing a part of cement by mineral additions such as fly ash or blast-furnace slag during concrete mixing.The present work aims at studying the physico-chemical phenomena occurring during the process of carbonation of concrete mixtures with high substitution rates of cement by mineral additions and their resistance against this type of attack.An experimental campaign was conducted on reference concrete mixtures prepared with common cements and on other concrete mixtures, called “Écobétons” (Green concretes), prepared by replacing a part of cement by fly ash or blast-furnace slag. The study focused on the Écobétons durability, especially their resistance against carbonation, on the equivalence of Écobétons performances with the reference mixtures performances and on the composition and microstructure parameters controlling the kinetics of carbonation. Carbonation has been studied in natural and accelerated conditions. The results show that Écobétons mixtures with high substitution rates of cement by fly ash (50 %) and blast-furnace slag (75 %) could replace, in some cases, concretes that are in accordance with the current standard.In addition to the experimental study, numerical simulations of the coupling between hydration and drying were conducted in order to determine the effect of drying on the properties controlling the accelerated carbonation kinetics of the studied concrete mixtures (porosity, Portlandite content and water saturation degree). The results show that the kinetics of drying increases with the degree of substitution of cement by mineral additions. They also question the relevance of the preconditioning of the samples during accelerated carbonation test conducted according to the French standard XP P 18-458.

The aim of this study was to assess the strength, durability properties and corrosion resistance of concrete samples using supplementary cementitious blended materials. In this investigation, three supplementary concrete materials (SCMs) were used together with ordinary Portland Cement (OPC) to form cementitious blends at different proportions. The supplementary materials are silica fume (SF), ground granulated blast furnace slag (GGBS) and fly ash (FA). Sixteen (16) different proportions of the cementitious blends were produced. Tests carried out on concrete samples include slump test, compressive strength, oxygen permeability, sorptivity, porosity, chloride conductivity test, resistance to chloride and sulphate attack. The electrode potentials of tested samples were also observed using electrochemical measurements. Concrete specimens prepared with 10%, 20%, 30%, 40%, up to 60% of blended cements replacement levels were evaluated for their compressive strength at, 7, 14, 28, 90 and 120 days while the specimens were evaluated for durability tests at 28, and 90 days respectively. The results were compared with ordinary Portland cement concrete without blended cement. Voltage, and temperature measurements were also carried out to understand the quality of concrete. The corrosion performance of steel in reinforced concrete was studied and evaluated by electrochemical half-cell potential technique in both sodium chloride, and magnesium sulphate solutions respectively. The reinforced concrete specimens with centrally embedded 12mm steel bar were exposed to chloride and sulphate solutions with the 0.5 M NaCl and MgSO4 concentrations respectively. An impressed voltage technique was carried out to evaluate the corrosion resistance of the combination of quaternary cementitious blended cement, so as to get the combination with optimum performance. Improvement of strength, durability, and corrosion resistance properties of blended concrete samples are observed at different optimum percentages for binary, ternary and quaternary samples. The effect of cementitious blends is recognized in limiting the corrosion potential of the tested SCM concrete samples. Generally, the cementitious blends with limited quantity of SF to 10% have the potential to produce satisfactory concrete. These should however be used for low cost construction, where high quality concrete is not required. / Civil and Chemical Engineering / M. Tech. (Chemical Engineering)

Made available in DSpace on 2014-07-29T15:18:24Z (GMT). No. of bitstreams: 1 pretextual.pdf: 140883 bytes, checksum: 5d9ee4b9b3884a0032825e604304580f (MD5) Previous issue date: 2009-09-28 / Increasing the durability of concrete structural elements is primordial, especially those related to power generation in eolic areas that are subjected to the phenomenon of reinforcement corrosion. In this context, this study aims to evaluate the overall protection ability of concrete to the phenomenon of reinforcement corrosion induced by chlorides. To this end, it was adopted a statistical program based on a fractional factorial design in which the variables studied were as follows: the water-binder ratio (0.35, 0.45 and 0.55), the type of mineral admixture (silica fume and blast furnace slag at specific levels), the type of corrosion inhibitor (calcium nitrite, sodium nitrite and amine) and the level of corrosion inhibitor (minimum and maximum recommended by each manufacturer). In the concrete investigations, the tests performed were corrosion potential, polarization resistance and electrochemical impedance. Throughout the experiments, it was possible to testify the beneficial effect of reducing the water-binder ratio. It was also possible to prove the very positive effect of the incorporation of mineral admixtures, especially of silica fume. The satisfactory performance of various inhibitors evaluated was also verified, specially when concrete contains mineral admixtures. A parallel study was conducted to make a comparative analysis of inhibitors at the same range of concentrations (at solid levels of 0.76%, 2.21% and 3.66% of the compound on the cement mass), nevertheless this study have demonstrated that fixing contents for all inhibitor is not appropriated, and the recommended dosages by the manufacturer is the best condition. As the levels recommended by manufacturers, it was found that the higher percentages have not worked well for sodium nitrite otherwise, for amine and nitrite calcium, the higher levels implied better results. Regarding the tannin inhibitor also assessed in the parallel study mentioned above (related to specific inhibitors), its good performance related to corrosion inhibition happened just for the content of 0.76% (the lowest levels). For the other contents, it was verified anomalous results. These results demonstrated that each type of corrosion inhibitor has its optimal concentration for use in concrete. Based on a cost-benefit analysis and evaluating the increase in the concrete value for cubic meter (in R$) in the presence of inhibitors at the same contents, it was verified a relative parity prices among the tested nitrites and an extremely high cost of amine. However, when performing the same analysis but using the levels recommended by the manufacturers for each inhibitor independent, it was found that the large disparity in prices between nitrite and amine was reduced considerably. An assessment of technical and economic feasibility was also performed based on the efficiency of corrosion inhibition and cost per cubic meter of concrete mixtures that did not show a typical depassivation of their stell bar up to the attack age evaluated / O aumento da durabilidade é um aspecto primordial para os elementos estruturais de concreto, em especial aqueles constituintes das estruturas de geração de energia em parques eólicos, sujeitos ao fenômeno de corrosão das armaduras. Nesse contexto, este trabalho tem como objetivo geral avaliar a capacidade de proteção de diferentes concretoS frente ao fenômeno da corrosão da armadura induzida por cloretos. Para tanto, foi adotado um planejamento estatístico baseado em um modelo fatorial fracionado em que as variáveis estudadas foram: a relação água/aglomerante (0,35; 0,45 e 0,55), o tipo de adição mineral (sílica ativa e escória de alto-forno, em teores específicos), o tipo de inibidor de corrosão (nitrito de cálcio, nitrito de sódio e amina) e o teor de inibidor de corrosão (mínimo e máximo recomendado por cada fabricante). Na avaliação dos concretos, foram realizados ensaios de potencial de corrosão, resistência de polarização e impedância eletroquímica. Ao longo de todo experimento foi possível constatar o efeito benéfico da redução da relação a/agl. Também foi possível verificar o efeito extremamente positivo da incorporação das adições minerais, em especial da sílica ativa. Constatou-se também o efeito positivo dos diversos inibidores avaliados, em seus teores mínimo e máximo, beneficio que se mostrou mais pronunciado quando da utilização conjunta com as adições minerais. Um estudo paralelo foi realizado para se fazer uma análise comparativa dos inibidores dentro da mesma faixa de teores empregados (teores de 0,76%; 2,21% e 3,66% de sólidos do aditivo em relação à massa de cimento), no qual se verificou que a utilização desses teores fixos para os diferentes tipos de inibidores não se mostrou tão eficiente quanto em relação à utilização dos aditivos na dosagem de recomendação do fabricante. Quanto a estes teores (recomendados pelos fabricantes), verificou-se que os percentuais mais altos não funcionaram bem para o nitrito de sódio, ao passo que para a amina e para o nitrito de cálcio os teores mais elevados resultaram em melhores resultados. Em relação ao tanino, inibidor que também foi avaliado no estudo paralelo referido anteriormente (específico sobre os inibidores), só houve algum resultado de inibição de corrosão para o teor de 0,76% (mais baixo dos teores), tendo-se obtido resultados anômalos para os outros 2 teores mais altos. Tais resultados permitiram constatar que cada tipo de inibidor de corrosão possui sua concentração ótima de utilização no concreto. Fazendo-se uma análise de custo e avaliando-se o acréscimo em Reais no valor do m3 do concreto proporcionado pelos diversos aditivos inibidores e nos teores de mesma faixa de emprego, verificou-se uma relativa paridade de preços entre os nitritos e um elevadíssimo custo da amina. No entanto, ao se realizar a mesma análise, mas utilizando os teores recomendados pelos fabricantes de cada inibidor, verificou-se que a grande disparidade de preços entre os nitritos e a amina foi reduzida de forma considerável. Uma avaliação da viabilidade técnico-econômica dos concretos também foi realizada, a partir dos dados de eficiência de inibição à corrosão e custo/m3 das misturas que não apresentaram comportamento típico de despassivação de suas armaduras até a idade de ataque considerada

Abstract Pollutant (such as metals and sulphate) contamination exists in the wastewaters of many industries, including mining operations, metal plating facilities, and tanneries. Adsorption is one of the most commonly used processes for the removal of pollutants from waters and wastewaters due to its high efficiency and simple operation. Activated carbon is the most frequently used adsorbent material, although its high cost inhibits its widespread use in wastewater treatment. Therefore, there is a need to develop other adsorbents from alternative inexpensive raw materials such as locally available industrial and mineral waste and by-products. The aim of this thesis was to study the possibility of using industrial waste materials such as carbon residue, metakaolin, blast-furnace slag and analcime as an inexpensive sorbent for iron, copper, nickel, arsenic, antimony and sulphate removal from aqueous solutions. To enhance their adsorption capacity, different chemical treatments (i.e. activation, modification, geopolymerisation) were performed. As a result, the level of removal of iron, copper and nickel by carbon residue and zinc chloride activated carbon residue was higher than that by the commercial activated carbon. Iron chloride modified carbon residue was the most effective sorbent material for sulphate removal when compared to the other studied chemically modified/activated carbon residues. Blast-furnace slag and metakaolin geopolymers as well as their raw materials, were examined for the simultaneous removal of nickel, arsenic and antimony from the spiked mine effluent. In the case of blast-furnace slag, geopolymerisation clearly increased the efficiency of nickel, arsenic and antimony removal to a beneficial level. The barium chloride modified blast-furnace-slag geopolymer was a very efficient sorbent material for sulphate removal and it could thus be a technically feasible sulphate sorbent for wastewater treatment (e.g. in the mining industry in applications in which very low sulphate levels are desired). Barium chloride modified acid washed analcime could also be a potential sorbent for sulphate removal. / Tiivistelmä Teollisuuden jätevedet kuten kaivosvedet ja metalliteollisuuden prosessien jätevedet voivat sisältää monenlaisia haitallisia ja jopa myrkyllisiä aineita kuten metalleja ja sulfaattia. Adsorptiota käytetään yleisesti esimerkiksi metallien ja orgaanisten yhdisteiden poistossa vesiliuoksista, koska se on tehokas ja yksinkertainen menetelmä. Aktiivihiili on yleisimmin käytetty adsorbenttimateriaali vedenpuhdituksessa, mutta sen hinta joissain tapauksissa rajoittaa sen käyttöä. Tämän vuoksi on tarvetta kehittää vaihtoehtoisia adsorbenttimateriaaleja edullisista raaka-aineista. Viime vuosien aikana on raportoitu mm. teollisuus- ja mineraalijätteistä, joita voidaan hyödyntää vesien ja jätevesien puhdistuksessa. Tämän työn tavoitteena oli hyödyntää teollisuudesta muodostuvia jätemateriaaleja (hiilijäännös, metakaoliini, masuunikuona ja analsiimi) raudan, kuparin, nikkelin, arseenin, antimonin tai sulfaatin poistossa malli- ja jätevesistä. Materiaaleja käsiteltiin erilaisilla kemikaaleilla (aktivointi, modifiointi tai geopolymerointi), jotta niiden adsorptiotehokkuudet paranisivivat poistettavia aineita kohtaan. Tulokset osoittivat, että raudan, kuparin ja nikkelin poisto oli sekä käsittelemättömällä että sinkkikloridilla aktivoidulla hiilijäännöksellä korkeampi kuin kaupallisella aktiivihiilellä. Arseenin, nikkelin ja antimonin poistoa kaivosvedestä tutkittiin masuunikuona- ja metakaoliinigeopolymeereillä, joista masuunikuonageopolymeeri osoittautui tehokkaimmaksi metallien poistajaksi. Bariumkloridilla modifioitu masuunikuonageopolymeeri puolestaan poisti erittäin tehokkaasti sulfaattia kaivoksen jätevedestä. Rautakloridilla modifioitu hiilijäännös ja happopesty bariumkloridilla modifioitu analsiimi osoittatuivat myös lupaavaksi materiaaliksi sulfaatin poistossa.

L’objectif de la thèse est de comprendre le comportement géochimique de l’arsenic dans les remblais miniers en pâte cimentés. Cette technique est employée depuis plusieurs années pour remblayer les galeries de mine exploitées à l’aide des rejets de concentrateurs. Pour cette étude, deux types de remblais sont élaborés en laboratoire : des échantillons de remblai minier en pâte synthétiques, fabriqués à partir de silice et enrichis artificiellement en arsenic, et des remblais miniers en pâte élaborés à partir de rejets miniers arséniés. Dans les deux cas, différents liants cimentaires sont testés. Plusieurs types d’investigations sont menés sur les échantillons de remblai en pâte cimentés. Une caractérisation minéralogique est effectuée à l’aide de divers outils. En parallèle, les échantillons de remblais sont soumis à différents tests de lixiviation complémentaires, afin d’évaluer la mobilité/rétention de l’arsenic dans ces matrices. Enfin, une modélisation géochimique est mise en œuvre à partir des résultats issus des deux études précédentes, afin d’affiner les connaissances sur la nature et la stabilité des composés arséniés dans les remblais étudiés. Les résultats obtenus indiquent que l’arsenic est mieux stabilisé dans les matrices à base de ciment Portland et de laitier de haut-fourneau que dans les remblais à base de cendres volantes. Le comportement à la lixiviation variable d’une matrice à l’autre s’explique par des spéciations et des mécanismes de piégeage de l’arsenic variés. L’arsenic peut précipiter sous forme de minéraux arséniés, principalement sous forme d’arséniates de calcium, mais aussi de divers autres composés secondaires variables d’une matrice à l’autre. Un piégeage physique des grains de rejets miniers arséniés par les hydrates cimentaires peut aussi avoir lieu, par formation d’un revêtement limitant l’oxydation des sulfures porteurs d’arsenic. Tous ces mécanismes interviennent dans la stabilisation/solidification de l’arsenic. / The objective of this study is to understand the geochemical behaviour of arsenic in cemented paste backfills. This technique consists in transporting the tailings in the mine openings. Two types of backfills are prepared in the laboratory for this study. First, synthetic cemented paste backfills artificially spiked with arsenic are synthesized, using silica in replacement of the tailings. In parallel, other cemented paste backfill specimens are prepared with arsenic-rich tailings. In the two cases, various types of hydraulic binders are tested. Several types of investigations are conducted on the cemented paste backfill specimens. A mineralogical characterization is carried out with the help of specific tools. At the same time, cemented paste backfill samples are submitted to several complementary leaching tests, to assess the mobility/immobilization potential of arsenic in these matrices. Finally, geochemical modeling is implemented, based on the results of the two previous studies, in order to refine the understanding of the nature and stability of the arsenic compounds. The results show that arsenic is better immobilized in Portland cement and slag-based matrices, rather than in fly ash-based matrices. The variable leaching behaviour from a given matrix to another is due to different arsenic trapping mechanisms. Arsenic can precipitate and form several arsenic minerals, mainly calcium arsenates, but also various other secondary compounds, which are different from a matrix to another. Physical entrapment of the tailings grains by the cementitious minerals can also occur, by formation of a coating around the grains, limiting the oxidation and dissolution of arsenic-bearing sulfides (passivation). These mechanisms are involved in the stabilization/solidification of arsenic by cemented paste backfills.

L’étude menée s’attache à évaluer le potentiel d’activation du laitier de haut fourneau dans un liant ternaire constitué de ciment alumineux, de sulfate de calcium et de laitier. Dans ce système ternaire, le constituant majoritaire est le sulfate de calcium. Le potentiel d’un tel système n’est pas encore connu mais cette étude vise à renseigner sur les principaux avantages et limites d’utilisation. D’un point de vue des propriétés d’usage de ce liant, la prise, le durcissement rapide et la montée des résistances sont assurés par le liant ettringitique. Ensuite, et uniquement si la dessiccation est évitée, le laitier de haut fourneau réagit et dans ce cas, l’apport du laitier dans de tels systèmes est double. Il contribue à l’augmentation des performances mécaniques à moyen et long terme et à limiter l’expansion sous eau. D’un point de vue de la compréhension des mécanismes d’hydratation, une démarche expérimentale originale est mise en place et dévoile le potentiel du laitier. Elle est basée sur la comparaison des performances obtenues avec différentes cures. Le potentiel d’hydratation du laitier est amplifié lorsque le système subit un séchage puis une réhydratation. Cependant, les techniques utilisées (diffraction des rayons X et calorimétrie différentielle à balayage) ne sont pas adaptées au suivi et à la quantification de laitier consommé. Ainsi, la compréhension de l’hydratation s’appuie sur des techniques dites indirectes. Une semi-quantification par diffraction des rayons X est réalisée pour le suivi et l’évaluation de la mayénite, le sulfate de calcium (anhydre ou dihydraté), la syngénite et l’ettringite, l’analyse thermogravimétrique permet de mesurer le degré d’hydratation du système, et la porosimétrie mercure informe sur les changements microstructuraux. La plus grosse difficulté dans ces travaux a porté sur le suivi et la quantification des phases amorphes (anhydres ou hydratées), telles que le laitier, les gels de C-S-H et d’AH3, et c’est pour cette raison qu’une approche par modélisation a été mise en place afin d’identifier le rôle de chaque constituant du système ternaire [Ciment Alumineux – Sulfate de Calcium – Laitier] et particulièrement du laitier lors de l’essai de réhydratation. L’approche par modélisation permet de mieux identifier les phénomènes chimiques et physiques ayant lieu lors de l’hydratation du liant. Elle est utilisée pour expliquer les observations macroscopiques (comme les performances mécaniques) et aide à déterminer les cinétique d’hydratation dans le milieu poreux. Le modèle utilisé n’est pas encore parfaitement au point mais il a permis d’identifier les différentes séquences d’hydratation (à savoir que le liant ettringitique réagit dans les premiers instants et qu’ensuite, l’hydratation de l’anhydrite entraine la formation de gypse et l’hydratation du laitier est effective à long terme) et de confirmer que la réaction du laitier est lente. / The potential of activation of a Ground Granulated Blast Furnace Slag has been evaluated into a ternary system comprising of a Calcium Sulfate as major component and a Calcium Aluminate Cement. This system is not well known and the main goal of this study is to determine its main advantages and limitations. From the usage properties point of view, fast setting and initial strengths are governed by the ettringitic binder. Then, and only if the dehydration is avoided, slag reacts. In this case, slag contributes to the increase of mechanical performances at medium and long terms and to limit the expansion under water. From an understanding point of view, the original experimental approach reveals the potential of the slag. It is based on a comparison of performances with different types of curing methods. The potential of hydration of the slag is amplified when the system is dehydrated during a few days and then rehydrated. However, slag contribution is complex to establish because analytical methods to follow-up slag consumption (such as X-ray Diffraction and Differential Scanning Calorimetry analysis) are not well adapted. So, to understand the hydration mechanisms, indirect approaches are used. Semi-quantitative methods by X-ray Diffraction to follow-up the mayenite, calcium sulfate, syngenite and ettringite, ThermoGravimetric Analysis to measure degree of hydration and Mercury Intrusion Porosimetry to identify microstructural changes have been carried. The most important difficulty concerns the identification and quantification of amorphous phases such as slag, C-S-H and AH3. That is why a modelling approach is necessary to understand the role of each compound in the ternary mixture and in particular the obvious contribution of slag during rehydration test. This modelling approach increases knowledge of the physical and chemical phenomena in this ternary binder. It is useful to explain the observed macroscopic properties such as strength and helps to determine the kinetics of hydration in porous environment. Even if this model is still under development, it has allowed identifying the sequences of hydration (ettringitic binder reacts at very initial time, then anhydrite transforms into gypsum and slag reacts at long term) and confirms therefore that the reaction of slag is slow.

Geopolymers are a relatively new class of materials that have many broad applications, including use as substitute for ordinary Portland cement (OPC), use in soil stabilisation, fire resistant panels, refractory cements, and inorganic adhesives. Geopolymers are an alternative binder to Portland cement in the manufacture of mortars and concrete, as its three-dimensional alumino silicate network develops excellent strength properties. Use of geopolymers in place of ordinary Portland cement is also favoured owing to the possible energy and carbon dioxide savings. Geopolymer is typically synthesized by alkali activation of pozzolanas at moderate temperatures (< 1000C). The focus of the thesis is synthesis and characterization of geopolymers as construction materials. In this context, the role of compositional factors, such as, pozzolana type (fly ash, kaolinite, metakaolinite, ground granulated blast furnace slag, red soil), alkali (sodium hydroxide is used in this study) activator concentration, Si/Al (Si= silicon, Al = aluminium) ratio of the pozzolana and environmental factors, namely, curing period and temperature are examined. Besides synthesizing geopolymers that could be an alternate to concrete as construction material, sand-sized aggregates were synthesized using geopolymer reactions. This was done as river sand is becoming scarcer commodity for use as construction material. Several compositional and environmental factors were varied in geopolymer synthesis in order to identify the optimum synthesis conditions that yield geopolymers with maximum compressive strength. Besides varying external (compositional and environmental) factors, the role of internal microstructure in influencing the compressive strength of the geopolymer was examined. Micro-structure examinations were made using X-ray diffraction (XRD), scanning electron microscopy (SEM) and mercury intrusion porosimetry (MIP) studies. The studies on compositional and environmental factors in geopolymer synthesis brought out several interesting results. The results firstly brought out that amongst the pozzolanas studied, ASTM class F fly ash is most suited for maximum compressive strength mobilization upon geopolymer reactions. Moderate temperature (75-1000C) was adequate to mobilize large compressive strengths. Room temperature curing needed more than 7 days before the pozzolana-NaOH paste began to develop strength. Curing period of 56 days was needed for the geopolymer to develop significant strength (19.6MPa). A similar range of compressive strength could be developed by the pozzolana-NaOH paste upon curing for 3 days at 1000C. Likewise curing the pozzolana-NaOH paste at temperatures > 1000C led to reduction in compressive strength from shrinkage and breakage of bonds. A caustic soda (NaOH) concentration of 10 M was adequate to develop maximum compressive strength of the geopolymer. Caustic soda concentrations in excess of 10 M did not result in further improvement of strength. The Si/Al ratio also contributes to strength mobilization. The Si/Al ratio of the geopolymer was enhanced by mixing commercially obtained silica gel with the pozzolana. Maximum strength mobilization was observed at Si/Al ratio = 2.45 corresponding to 6.5 % silica gel addition to the pozzolana (on dry mass basis). Comparing compressive strengths of geopolymers with varying silica gel contents, geopolymer specimens with least water content and largest dry density did not exhibit maximum compressive strength indicating that the physico-chemical (bond strength, micro-structure) played a pivotal role than physical parameters (dry density, water content) in dictating the strength of the geopolymer. MIP results showed that bulk of the porosity in fly ash geopolymer specimens is contributed by macro pores and air voids. Geopolymerization leads to bulk consumption of cenospheres in fly ash and forms polymerized matrix with network of large pores. After geopolymerization, all the main characteristic peaks of Al–Si minerals observed in fly ash persisted, suggesting that no new major crystalline phases were formed. Presence of small amount of inorganic contaminants in fly ash can drastically reduce the strength of the fly ash geopolymer. For example, 5-20 % presence of red soil reduces the strength of fly ash geopolymer by 16 to 59 %. Presence of unreacted clay coupled with less porous structure is responsible for the reduction in compressive strength of fly ash geopolymer subjected to red soil addition. MIP studies with geopolymers also revealed that there is good bearing between compressive strengths and maximum intruded volume (from MIP test) of geopolymers. For example, fly ash geopolymer specimen exhibits highest total intruded volume (0.3908 cc/g) and largest compressive strength of 29.5 MPa, while red soil geopolymer specimen exhibit least intruded volume (0.0416 cc/g) and lowest compressive strength (5.4 MPa). Further, analysis showed that specimens with larger airvoids+macropores volume had larger compressive strength, suggesting that geopolymers with more porous microstructure develop larger compressive strength. All geopolymer specimens exhibited tri-modal nature of pores i.e. macro-pore mode (entrance pore radius: 25-5000 nm), mesopore mode (entrance pore radius: 1.25 to 25 nm) and air void mode (entrance pore radius >5000 nm). The micro pores (entrance pore radius < 1.25 nm) do not contribute to porosity of the geopolymer specimens. Sand particles prepared from geopolymer reactions (FAPS or fly ash geopolymer sand) predominated in medium sized (2mm to 0.425 mm) sand particles. Their particle size distribution characteristics (uniformity coefficient and coefficient of curvature) classified them as poorly graded sand (SP). Dissolution, followed by polymerization reactions led to dense packing of the Si–O–Al–O– units that imparted specific gravity of 2.59 to FAPS particles which is comparable to that of river sand (2.61). Dissolution in strongly alkaline medium imparted strongly alkaline pH (12.5) to the FAPS particles. The river sand is characterized by much lower pH (7.9). Despite being characterized by rounded grains, the FAPS particles mobilized relatively high friction angle of (35.5o) than river sand (∅ = 28.9o). The river sand-mortar (RS-M) and fly ash geopolymer sand-mortar (FAPS-M) specimens developed similar 28-day compressive strengths, 11.6 to 12.2 MPa. Despite its higher water content, FAPS-mortar specimens developed similar compressive strength and initial tangent modulus (ITM) as river sand-mortar specimens. The FAPS-M specimen is more porous (larger intruded volume) with presence of larger fraction of coarser pores. Total porosity is majorly contributed by macro-pores (67.92%) in FAPS-M specimen in comparison to RS-M specimen (macro-pores = 33.1%). Mortar specimens prepared from FAPS and river sand exhibit similar pH of 12.36 and 12.4 respectively. FAPS-mortar specimens have lower TDS (1545 mg/L) than river sand-mortar specimens (TDS = 1889 mg/L). The RS-M and FAPS-M specimens exhibit leachable sodium levels of 0.001 g Na/g RS-M and 0.007 g Na/g-FAPS-M respectively in the water leach tests. The larger leachable sodium of FAPS-M specimen is attributed to residual sodium hydroxide persisting in the FAPS even after washing. The ultra-accelerated mortar bar test (UAMBT) shows that the percentage expansion of FAPS-M and RS-M specimens are comparable and range between 0.07 to 0.08 %.