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This master thesis presents the effects of fly ash on the properties of alkali activated slag concrete, commonly referred as Geopolymer concrete (GPC). Cement manufacturer are major producers of CO2 which negatively affects the environment. Due to the increased construction activities and environmental concern, it is necessary to introduce alternative and eco-friendly binders for concrete. Slag and fly ash based concrete, which is by-product from industrial waste, is probably the best replacement for OPC concrete due to less or nil environmental issue. Most of the researchers have already concluded that slag and fly ash can be used as binders in concrete by activating them with alkali activator solution (e.g. by sodium silicate or sodium carbonate). In the present work concretes were produced by varying the proportion of slag to fly ash (40:60, 50:50, 60:40 & 80:20); amount of alkali activators (5, 10 & 14) and chemical modulus of sodium silicate (Ms) (0.25, 0.5 & 1).  Setting times and compressive strength values were evaluated. Results showed that decrease in fly ash content irrespective of % of alkali activators and alkali modulus (Ms), the compressive strength was increasing and setting time was getting shorter. The produced concretes showed increasing compressive strength with increase in % of alkali activator for Ms 0.5 and 1, while for Ms=0.25 the strength was decreasing with increase in % of alkali activators. From this it can be concluded that, Ms=0.5 was the optimum point below which the reaction got slower. Based on the initial investigations, mix S8:F2-SS10(1) and S8:F2-SS10(0.5) showed most promising results in terms of fresh and hardened concrete properties and were easy to handle. Consequently, the above mentioned mixture was chosen to be studied in more detail. The experimental program for these mixes included determination of slump flow, compressive strength (7, 14, 28 days) and shrinkage (drying and autogenous). The results shows that, strength increased with time and comparatively mix with Ms=0.5 showed higher compressive strength than mix with Ms=1, due to higher alkalinity of the pore solution. Mix with Ms=1 showed higher drying shrinkage compared to mix with Ms=0.5, which was explained by higher alkalinity of the solutions (Ms=0.5) leading to rapid formation of aluminosilicate gel. Autogenous shrinkage appeared to be higher for mix with Ms=0.5. This was associated with lower modulus which leads to densification of concrete microstructure at early ages. Pore diameter decrease and the water trapped in the pores exerted increasing tensile stress resulting for higher autogenous shrinkage.

Neste trabalho foram realizadas análises estruturais de dois conjuntos de vidros metafosfatos ternários relevantes em potenciais aplicações: aluminofosfatos e álcalis mistos. Para os aluminofosfatos a análise estrutural tem por objetivo verificar a existência de comportamentos preferenciais da conectividade entre os grupos fosfatos e os átomos de Al, e verificar a possível extensão a estes sistemas ternários de princípios de ligação química e ordem local inferidos em fosfatos binários, sendo os sistemas estudados K(1-x)Alx(PO3)(2x+1) e Na(1-x)Alx(PO3)(2x+1) . Para os vidros de álcalis mistos, a análise estrutural tem por objetivo identificar se existe segregação ou mistura aleatória das duas espécies de cátions, e determinar quais modificações na ordem local de cada álcali são induzidas pela troca de espécies, sendo os sistemas estudados LixNa(1-x)(PO3), KxNa(1-x)(PO3, RbxNa(1-x)(PO3), RbxLi(1-x)(PO3) e CsxLi(1-x)(PO3). As informações estruturais nestes vidros foram obtidas através de técnicas de Ressonância Magnética Nuclear (RMN) de estado sólido de 7Li, 23Na, 27Al, 31P, 87Rb e 133Cs. A conectividade entre a rede de fosfatos e os átomos de Al foi estudada utilizando informações a respeito da distribuição de espécies tetraédricas de fosfatos Q2m , sendo m = 0,1, 2 o número de pontes P-O-Al por tetraedro, obtidas através de RMN de 31P, e do número de coordenação médio do Al obtido através de RMN de 27Al. Da análise quantitativa da evolução das diferentes populações Q2m com a concentração de Al, juntamente com o número de coordenação médio do Al, foi possível verificar a existência de comportamentos preferenciais na organização estrutural: tetraedros fosfatos compartilham um vértice único (oxigênio não-ponte) com os poliedros de coordenação do Al. Esta organização de médio alcance é mantida até uma determinada concentração de Al, onde todo tetraedro forma uma ponte P-O-Al . A distribuição das espécies Q2m resultante é do tipo binária em função da concentração de Al: { Q20, Q21 } até concentrações intermediárias e { Q21, Q22 } para concentrações altas. Para os metafosfatos de álcalis mistos, o comportamento do desvio químico de 23 Na e 133Cs revela um efeito sistemático de aumento/decréscimo no tamanho do ambiente de coordenação ao redor dos álcalis em função da substituição. O ambiente de O dos álcalis de menor raio iônico resulta comprimido quando ocorre a substituição deste por uma espécie de raio iônico maior, e vice-versa. Com relação à distribuição dos álcalis na rede vítrea, as evoluções dos desvios químicos em função da substituição excluem a possibilidade de segregação dos álcalis ou separação de fase. A análise do acoplamento dipolar homonuclear de 23 Na, através da medida do segundo momento, revelou que a mistura de Na com o segundo álcali não é aleatória, existindo uma maior probabilidade de um Na ter outro Na como próximo vizinho. A correlação entre o grau de não-aleatoriedade na dispersão do Na e o incremento na magnitude do efeito de álcalis mistos na condutividade DC dos metafosfatos de Rb-Na, K-Na e Li-Na sugere que os fenômenos estão fundamentalmente relacionados. Esta seria a primeira evidência de vínculo entre uma propriedade estrutural da distribuição dos álcalis e o efeito de álcalis mistos de uma propriedade dinâmica. / In this work, the structure of two ternary metaphosphate glass systems was analyzed: aluminum-phosphates and mixed-alkali. The aim of the study in aluminum-phosphates is to determine the existence of preferential structural connectivities between phosphate groups and Al, and to verify the possible extension to these ternary glasses of principles of structural organization valid in binary phosphates. The aluminum metaphosphates studied here were K(1-x)Alx(PO3)(2x+1) and Na(1-x)Alx(PO3)(2x+1) . In mixed-alkali metaphosphates the goal of the structural analysis is the identification of the way in which alkali cations are distributed in the glass network (segregation versus random mixture), and to determine what kind of modification in the local order around the alkalis are induced by the substitution of species. The mixed-alkali metaphosphate studied here were LixNa(1-x)(PO3), KxNa(1-x)(PO3, RbxNa(1-x)(PO3), RbxLi(1-x)(PO3) and CsxLi(1-x)(PO3). The structural information was obtained using solid-state Nuclear Magnetic Resonance (NMR) techniques of 7Li, 23Na, 27Al, 31P, 87Rb and 133Cs. The connectivity between the phosphate groups and Al was analyzed studying the populations of phosphate species Q2m, with m=0,1,2 being the number of P-O-Al bridges per tetrahedron, obtained using 31P-NMR, and considering the average coordination number of Al obtained by 27Al-NMR. Through the quantitative analysis of the evolution of the Q2m population with the Al concentration, it was possible to identify the existence of a preferential structural behavior: phosphate tetrahedra share only one common corner (non-bridging oxygen) with the coordination polyhedra around Al. This medium-range organization can be sustained up to a certain concentration of Al, to the point where every phosphate establishes a P-O-Al bridge. The resulting distribution of Q2m species can be identified as binary, as a function of the Al content: { Q20, Q21} up to intermediate concentrations and { Q21, Q22} for higher concentrations. In the mixed-alkali metaphosphates, the behavior of the 23Na and 133Cs chemical shift reveals a systematic increase/decrease in the average size of the coordination environment around the alkalis as a function of the substitution. The O environment around cations with the smaller ionic radius is compressed as this species is substituted by another alkali with bigger ionic radius, and vice-versa. With respect to the alkali distribution in the glass network, the observed evolution of the chemical shift as a function of the cation substitution excludes the possibility of segregation of alkalis or phase separation. The analysis of the 23Na homonuclear magnetic dipolar coupling, through the measurement of the second moment, revealed that the mixture at atomic scale of Na with the second alkali is not random, having a higher probability of a Na being close to other Na than to other alkali. The correlation between the degree of non-random dispersion of Na and the increment in the magnitude of the mixed alkali effect in the dc conductivity of Rb-Na, K-Na and Li-Na metaphosphates indicates a fundamental connection between both phenomena. This may be the first evidence of a relation between a structural property of the alkali distribution and the mixed alkali effect of a dynamical property.

Abstract Millions of tons of mine tailings are generated worldwide annually. Since many valuable metals such as Ag, Cu, Pb, Zn, Au and Ni are usually incorporated into sulphidic minerals, a large proportion of the tailings generated contain high amounts of sulphates and heavy metals. Some of these tailings are used as paste backfill material at mining sites, but large amounts are still being deposited into the tailings dams under water coverage. Sulphidic minerals are stable underground but after mining of the ore and several processing steps these minerals can be oxidized when they come into contact with water and air. This oxidation generates acid and thus reduces the pH of the surrounding environment. Furthermore, the heavy metals present in the mine tailings can be leached into the environment. This phenomenon, called Acid Mine Drainage (AMD), is one of the most critical environmental issues related to the management of sulphidic-rich tailings. Since AMD generation can still occur hundreds of years after closure of the mine, the mine tailings need stable, sustainable and economically viable management methods in order to prevent AMD production in the long term. The aim of this PhD thesis was to study various solidification/stabilization (S/S) methods for the immobilization of sulphidic mine tailings. The main focus was to develop a suitable chemical environment for achieving effective heavy metal (mainly arsenic) and sulphate immobilization while simultaneously ensuring good mechanical properties. Three treatment methods were tested: alkali activation, stabilization using hydrated lime (Ca(OH)2) and blast furnace slag (GBFS), and calcium sulphoaluminate-belite (CSAB) cement stabilization. The mine tailings used in this study contained large amounts of sulphates and heavy metals such as Cr, Cu, Ni, Mn, Zn, V and As. The leaching of arsenic and sulphates from powdered tailings exceeded the legal limits for regular and inert waste. All treatment methods were found to generate a hardened matrix that was suitable for use as a backfilling or construction material, but the calcium-based binding system was the most suitable for effective immobilization of all the heavy metals (including arsenic) and the sulphates. Precipitation in the form of calcium sulphates/calcium arsenate and the formation of ettringite are the main stabilization methods employed in calcium-based stabilization/solidification (S/S) systems. Some evidence of physical encapsulation occurring simultaneously with chemical stabilization was noted. These results can be exploited further to develop more sustainable mine tailing management systems for use in the future. The tailings could be stored in a dry landfill area instead of in tailing dams, and in this way a long-term decrease in AMD generation could be achieved, together with a high potential for recycling. / Tiivistelmä Monet arvometallit kuten kulta, kupari ja nikkeli ovat sitoutuneena sulfidipitoisiin mineraaleihin. Louhittaessa ja rikastettaessa näitä sulfidimineraaleja syntyy miljoonia tonneja sulfidipitoisia rikastushiekkoja vuosittain. Rikastushiekat voivat sisältää myös runsaasti erilaisia raskasmetalleja. Osa rikastushiekoista hyödynnetään kaivostäytössä, mutta suurin osa rikastushiekoista läjitetään edelleen ympäristöön rikastushiekka-altaisiin veden alle. Kun sulfidipitoinen malmi kaivetaan ja käsitellään, sulfidiset mineraalit hapettuvat ollessaan kosketuksissa veden ja hapen kanssa. Hapettuessaan ne muodostavat rikkihappoa, laskien ympäristön pH:ta jolloin useimmat raskasmetallit liukenevat ympäristöön. Muodostuvia happamia kaivosvesiä voi syntyä vielä pitkään kaivoksen sulkemisen jälkeen ja ovat näin ollen yksi suurimmista kaivosteollisuuteen liittyvistä ympäristöongelmista. Lisäksi suuret rikastushiekka-altaat voivat aiheuttaa vaaraa myös ihmisille, mikäli altaan rakenteet pettävät. Rikastushiekkojen kestäviä ja ympäristöystävällisiä varastointimenetelmiä täytyy kehittää, jotta näitä ongelmia voidaan tulevaisuudessa ehkäistä. Tässä työssä tutkittiin menetelmiä, joilla kultakaivoksella syntyvät sulfidipitoiset vaaralliseksi jätteeksi luokitellut rikastushiekat saataisiin stabiloitua tehokkaasti. Työssä keskityttiin kolmeen erilaiseen menetelmään: alkali-aktivointiin, stabilointiin kalsiumhydroksidin ja masuunikuonan avulla ja stabilointiin CSAB sementin avulla. Valmistettujen materiaalien mekaanisia ja kemiallisia ominaisuuksia arvioitiin. Tavoitteena oli ymmärtää, miten eri menetelmät soveltuvat raskasmetallien (erityisesti arseenin) ja sulfaattien sitoutumiseen ja mikä on eri komponenttien rooli reaktioissa. Alkali-aktivoimalla rikastushiekkaa sopivan sidosaineen kanssa saavutettiin hyvät mekaaniset ominaisuudet ja useimmat haitta-aineet sitoutuivat materiaaliin. Ongelmia aiheuttivat edelleen sulfaatit ja arseeni. Kalsiumpohjaiset menetelmät sitoivat raskasmetallit (myös arseenin) ja sulfaatit tehokkaimmin. Sulfaatit ja arseeni saostuivat muodostaen niukkaliukoisia komponentteja kalsiumin kanssa. Samanaikaisesti rakenteeseen muodostui ettringiittiä, jolla on tutkitusti hyvä kyky sitoa erilaisia raskasmetalleja rakenteeseensa. Raskasmetallit myös kapseloituivat rakenteen sisään. Työn tuloksia voidaan hyödyntää, kehitettäessä rikastushiekkojen turvallista varastointia. Kun materiaalille saavutetaan riittävän hyvä lujuus ja kemiallinen stabiilius, rikastushiekat voitaisiin läjittää tulevaisuudessa kuivalle maalle altaan sijaan. Näin vältyttäisiin rikastushiekka-altaiden rakentamiselta ja voitaisiin vähentää happamien kaivosvesien muodostumista pitkällä ajanjaksolla. Saavutettujen tulosten perusteella rikastushiekkoja voidaan mahdollisesti tulevaisuudessa hyödyntää myös erilaisissa betonin tapaisissa rakennusmateriaaleissa.

The biological sludge formed in the pulp and paper wastewater treatment constitutes a costlyproblem to dispose off due to poor dewaterability. It is often incinerated or used as soilconditioner improvement. By using anaerobic digestion of the biological sludge, thedewaterability can be increased. Thanks to the formation of biogas, the sludge volume isdecreased and energy can be recovered as methane. By pre-treating the sludge, the biogasproduction can be increased, making the anaerobic digestion more economically feasible. Eleven samples of biological sludges from six Swedish pulp and paper mills, chosen torepresent different types and sizes of mills available in Sweden, were pre-treated with alkali(NaOH, pH12), heat (80˚C, 1 hr) and electroporation (2000 pulses, 10 kV/cm). Initialmethane production rate and methane potential of all sludges and pre-treatments weredetermined using batch experiment. A combination of two sludges (from the same mill) pretreatedwith alkali and heat was further investigated in a semi-continuous digester experiment. The batch experiments showed that alkali pre-treatment had the greatest positive effect onmethane production. Heat treatment performed second best, whereas electroporation had no orlittle effect. Overall, pre-treatments increased the initial methane production rate, but withinsignificant effects on the methane potential. Heat pre-treatment showed no difference inbiogas production compared to the control in the semi-continuous digester experiment. Alkalitreatment was shown to inhibit biogas production and cause high accumulation of acetate. Itcould not be concluded whether it was an effect from hydroxide or sodium ion addition.Further analysis of the NaOH impact on floc structure, toxicity and bioavailability issuggested to determine the suitability of alkali-treated sludge for anaerobic digestion. / Bioslam, som bildas vid vattenreningen på pappers- och massabruk, utgör en kostnad attomhänderta på grund av avvattningssvårigheter. Kvittblivning sker oftast genom förbränningeller användning som jordförbättringsmedel. Genom rötning kan slammet bli merlättavvattnat och tack vare att det bildas biogas minskar slamvolymen samtidigt som energikan utvinnas från metanet. Produktionen av biogas kan ökas genom att förbehandla slammetinnan rötning, vilket skulle innebära ekonomiska fördelar. Denna studie har undersökt effekten av förbehandling för elva bioslam från sex svenskapappers- och massabruk, valda att representera olika typer och storlekar på svenska bruk.Behandlingen gjordes med alkali (NaOH, pH12), värme (80˚C, 1 h) och elektroporering(2000 pulser, 10 kV/cm). Effekten av förbehandling på initial metanproduktionshastighet ochmetanpotential undersöktes med hjälp av satsvis utrötning (batch) av alla slam. Enkombination av två slam från samma burk utvärderades i ett semi-kontinuerligt rötningsförsökefter förbehandling med värme och alkali. Resultatet från utrötningsförsöket visade att den alkaliska förbehandlingen hade störst positivinverkan på metanproduktionen. Värmebehandlingen presterade näst bäst, medanelektroporeringen visade sig ha liten eller ingen effekt. Generellt sett ökade den initialametanproduktionshastigheten till följd av förbehandling, medan metanpotentialen förblevoförändrad. Värmebehandling gav ingen effekt på biogasproduktionen i det semikontinuerligarötningsförsöket jämfört med kontroll, medan alkalisk förbehandling inhiberadebiogasproduktionen och orsakade höga koncentrationer av ackumulerat acetat. Det kunde inteavgöras huruvida det var natrium- eller hydroxidjoner, som orsakade inhiberingen. För attkunna utvärdera möjligheten att röta slam, som förbehandlats med NaOH, rekommenderasvidare analys av dess påverkan på flockstruktur, toxicitet och biotillgänglighet.

This paper establishes Low-Tension-Gas (LTG) as a method for sub-miscible tertiary recovery in tight sandstone and carbonate reservoirs. The LTG process involves the use of a low foam quality surfactant-gas solution to mobilize and then displace residual crude after waterflood. It replicates the existing Alkali-Surfactant-Polymer (ASP) process in its creation of an ultra-low oil-water interfacial tension (IFT) environment for oil mobilization, but instead supplements the use of foam over polymer for mobility control. By replacing polymer with foam, chemical Enhanced Oil Recovery (EOR) methods can be expanded into sub-30 mD formations where polymer is impractical due to plugging, shear, or the requirement to use a low molecular weight polymer. Overall results indicate favorable mobilization and displacement of residual crude oil in both tight carbonate and tight sandstone reservoirs. Tertiary recovery of 75-95% ROIP was achieved for cores with 2-15 mD permeability, with similar oil bank and other ASP analogous process attributes observed. Moreover, similar recovery was achieved during testing at high initial oil saturation (56%), indicating high process tolerance to oil saturation and potential application for implementation at secondary recovery. In addition, a number of tools and relations were developed to improve the predictive relationship between observed coreflood properties and actual mobilization or displacement mechanisms which impact reservoir-scale flooding. These relations include qualitative dispersion comparison and calculation of in-situ gas saturation, macroscopic mobility ratio at the displacement fronts, and apparent viscosity of injected fluids. These tools were validated through use of reference gas and surfactant floods and indicate that stable macroscopic displacement can be achieved through LTG flooding in tight formations. Furthermore, to better reflect actual reservoir conditions where localized fractional flow of gas can vary substantially depending on mixing or gravity phenomenon, two additional sets of data were developed to empirically model behavior. Through testing of LTG co-injection at a number of discrete fractional flow values over a wide range, recovery was shown to achieve a relative maximum at 50% gas fractional flow which also corresponded with optimal observed mobility control as measured by the previously established tools. Likewise, through testing of surfactant-alternating-gas (SAG) injection cycling, displacement and overall recovery were shown to be improved versus reference co-injection flooding. Finally, by comparing the observed displacement and mobility data among co-injection and surfactant-alternating-gas floods, a new displacement mechanism is introduced to better relate actual displacement conditions with observed macroscopic mobility data. This mechanism emphasizes the role of liquid rate in actual displacement processes and a mostly static gas saturation (independent of gas rate) in altering liquid relative permeability and diverting injected liquid into lower permeability zones. / text

This thesis is unique in that it investigated two completely different forms of concrete deterioration: physical sulfate attack and the alkali-silica reaction (ASR). Research was undertaken to better understand physical sulfate attack in order to provide much needed guidance on how to prevent durable this form of deterioration. A testing regime was designed to evaluate and analyze different concrete mixtures with varying water to cementitious material ratios (w/cm), cement types (Type I and V), and use of supplementary cementing materials (SCMs) in accelerated laboratory exposure and outdoor exposure testing. The accelerated laboratory testing evaluated the performance of concrete cylinder segments fully submerged in 30% (by mass of solution) sodium sulfate solution exposed to a temperature and humidity cycle that would promote cycles of alternative conversion between anhydrous sodium sulfate (thenardite) and decahydrate sodium sulfate (mirabilite). In the outdoor exposure site, two different sized concrete cylinders per mixture proportion were partially submerged in 5% (33,000 ppm) sodium sulfate solution and exposed to alternative wetting and drying conditions, along with, temperature fluctuations that would promote conversion between thenardite (Na2SO4) and mirabilite (Na2SO4∙10H2O). With regard to ASR test methods, it has been shown with past research that it is not possible to evaluate “job mixtures” or determine alkali thresholds using ASTM C 1293 (Concrete Prism Test) with evaluating aggregates and concrete mixture proportions for the susceptibility of ASR when testing job mixtures. The most commonly cited issue with the concrete prism test is excessive leaching of alkalis during the course of the test, which may not be a major issue when using the standard, high-alkali concrete mixtures as per ASTM C 1293 but is clearly an issue when testing lower-alkali concrete mixtures. For low-alkali mixtures, alkali leaching can reduce the internal alkali content below the threshold that triggers expansion for a given aggregate. A comprehensive study was initiated that evaluated various modifications to ASTM C 1293, with the intention of developing a testing regime better suited to testing “job mixes” and/or low-alkali concrete mixtures. / text

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No description available.

Using recycled concrete aggregate (RCA) as a replacement for natural aggregate in new concrete is a promising way to increase the overall sustainability of new concrete. This has been hindered, however, by a general perception that RCA is a sub-standard material due to the lack of technical guidance, specifically related to long-term durability, on incorporating RCA into new concrete. The goal of this research project was to determine whether current testing methods could be used to assess the potential alkali-silica reactivity of concrete incorporating RCA. The test methods investigated were ASTM C1260 and ASTM C1567 for assessing natural aggregate susceptibility to alkali-silica reactivity (ASR), and the ability of supplementary cementitious materials (SCMs) to mitigate ASR, respectively. Seven different RCA sources were investigated. It was determined that ASTM C1260 was effective in detecting reactivity but expansion varied based on RCA processing. Depending on the aggregate type and the extent of processing, up to a 100% increase in expansion was observed. Replicate testing was performed at four university laboratories to evaluate repeatability and consistency of results. The authors recommend modification to the mixing and aggregate preparation procedures, when testing the reactivity of RCA using ASTM C 1260. This study also investigated the efficacy of replacing portland cement with supplementary cementitious materials (SCMs), known to mitigate alkali-silica reaction (ASR) in concrete with virgin aggregates, to control ASR in concrete incorporating reactive RCA. The SCMs investigated as part of this study included: fly ash (class F), silica fume, and metakaolin. The results of modified alkali-silica reactivity tests, ASTM C1260 and ASTM C1567 (AMBT), are presented for two different recycled concrete aggregates when using 100% portland cement, binary blends of portland cement and fly ash, and ternary blends of portland cement, fly ash and metakaolin or silica fume. The results indicate that SCMs can effectively mitigate ASR in concrete made with RCA. A 40% replacement of portland cement with class F fly ash was able to reduce expansions to below 0.10% in the AMBT for concrete containing 100% of a highly reactive recycled concrete aggregate. A ternary blend, however, of portland cement with a class F fly ash and metakaolin was most effective for both RCAs tested in this study. Higher levels of mitigation may be required for some RCAs, compared to the level required to mitigate ASR in concrete made with their original natural aggregates, depending on the age and composition of the RCA. / Graduation date: 2012