The carbonation of the building materials based on the ordinary Portland cement is relatively well-known and extensively studied phenomenon. Conversely mechanism, reaction products and factors affecting the carbonation of the alkali activated materials are still not sufficiently clarified. In this work, the progression of the carbonation of the alkali activated materials under different conditions was investigated. The reaction products and the microstructural changes were determined by XRD respectively SEM-EDX analysis. The corrosive conditions due to the decreasing of the pH of the binders by the carbonation were observed by XPS analysis of the steel fibers. The carbonation of the alkali activated samples was compared with the reference samples based on the Portland composite cement. Besides these analyzes, the mechanical properties of the binders were monitored.

This thesis is focused on the principles of behavior of shrinkage reducing agents (SRA) in alkali-activated materials based on blast furnace slag. The main focus of this work is selecting the most suitable admixture based on experiments, by which will be achieved through minimal shrinkage and will have negative effect on the properties of alkali-activated blast furnace slag at the same time. In experimental section of this work, the surface tension as individual additives as their mixtures with pore solution were measured primarily. Then the testing samples composed of blast furnace slag, water glass and addition of SRA were prepared. Of these samples was measured shrinkage and weight loss. Moreover, their mechanical properties such as flexural and compressive strength were monitored. Next, the beginning and the end of solidification was studied using the Vicat device and last but not least workability. The hydration process of alkali-activated materials with SRA was measured calorimetrically. Finally the microstructure in prepared samples was observed using scanning electron microscopy (SEM-EDS) and the total porosity was determined by mercury porosimeter.

abstract: This dissertation aims at developing novel materials and processing routes using alkali activated aluminosilicate binders for porous (lightweight) geopolymer matrices and 3D-printing concrete applications. The major research objectives are executed in different stages. Stage 1 includes developing synthesis routes, microstructural characterization, and performance characterization of a family of economical, multifunctional porous ceramics developed through geopolymerization of an abundant volcanic tuff (aluminosilicate mineral) as the primary source material. Metakaolin, silica fume, alumina powder, and pure silicon powder are also used as additional ingredients when necessary and activated by potassium-based alkaline agents. In Stage 2, a processing route was developed to synthesize lightweight geopolymer matrices from fly ash through carbonate-based activation. Sodium carbonate (Na2CO3) was used in this study to produce controlled pores through the release of CO2 during the low-temperature decomposition of Na2CO3. Stage 3 focuses on 3D printing of binders using geopolymeric binders along with several OPC-based 3D printable binders. In Stage 4, synthesis and characterization of 3D-printable foamed fly ash-based geopolymer matrices for thermal insulation is the focus. A surfactant-based foaming process, multi-step mixing that ensures foam jamming transition and thus a dry foam, and microstructural packing to ensure adequate skeletal density are implemented to develop foamed suspensions amenable to 3D-printing. The last stage of this research develops 3D-printable alkali-activated ground granulated blast furnace slag mixture. Slag is used as the source of aluminosilicate and shows excellent mechanical properties when activated by highly alkaline activator (NaOH + sodium silicate solution). However, alkali activated slag sets and hardens rapidly which is undesirable for 3D printing. Thus, a novel mixing procedure is developed to significantly extend the setting time of slag activated with an alkaline activator to suit 3D printing applications without the use of any retarding admixtures. This dissertation, thus advances the field of sustainable and 3D-printable matrices and opens up a new avenue for faster and economical construction using specialized materials. / Dissertation/Thesis / Doctoral Dissertation Civil, Environmental and Sustainable Engineering 2019

This thesis examines the possibility of creating composite mainly from waste materials. The matrix of this composite was prepared from fly ash type F, which was activated by sodium water glass. Wood chips were used as a filler. This thesis includes theoretical and experimental parts. The theoretical part deals with the most important issues of wood composites with an inorganic matrix as well as basic components of investigated composite, ie alkaline activated fly ash and wood. In the experimental part, the fly ash pastes were prepared, from which the most suitable mixture was chosen for the composite preparation. Properties of wood composite with alkali activated fly ash matrix were investigated depending on the dose of wood chips.

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

Ground granulated blast furnace slag is a by-product of the steel industry and is often used in combination with ordinary Portland cement as a binder in concrete. When concrete is exposed to high temperatures, physical and chemical transformations lead to significant loss of mechanical properties. This study aims to investigate the effect of high temperatures and rehydration on the mechanical properties, microstructure and phase composition of alkali activated slag. The results of the research could make an important contribution to decisions made concerning the reconstruction of structures affected by fire. In suitable cases it would be possible to regenerate parts of a structure instead of totally rebuilding it.

Abstract About 4 Mt of ladle slag is generated in steelmaking processes in Europe per year, a large proportion of which (80%) is placed in landfills or stored. This pattern is expected to continue without further research for their valorisation due to increasing demand for quality steel products worldwide. Ladle slag (LS) produced in Finland possesses large amounts of calcium and aluminium and mineralogical phases which can exhibit cementitious capabilities and can be utilized in applications where expensive commercial cements are currently being used. The aim of this thesis is to investigate the properties of ladle slag in different activation pathways, including alkali activation and use as a hydraulic binder with gypsum. The results showed that ladle slag can be used alone as a precursor in alkali activation or as the sole binder or a co-binder with gypsum in hydraulic binding. Depending on the activation pathway, compressive strength between 35–92 MPa can be achieved after 28 days. The reaction properties of alkali activated ladle slag are characterized, and it is confirmed through X-ray diffraction (XRD) that the reaction product after alkali activation is mainly an x-ray amorphous (calcium aluminate silicate hydrate-like) phase. Characterization techniques (SEM, XRD, TGA and NMR) used to analyze the LS paste binder with just water showed the hydration products of ladle slag to be dicalcium aluminate octahydrate (C₂AH₈), tricalcium aluminate hexahydrate (C₃AH₆), gibbsite (AH₃) and stratlingite (C₂ASH₈) was also identified after a prolonged period of hydration. Furthermore, it was found that to minimize the conversion, the ideal water-to-binder ratio is 0.35. The conversion mechanism is reduced at this ratio and the strength is slightly affected. Another pathway that can be used to annul the conversion of calcium aluminate hydrates formed in LS paste is through the addition of gypsum to the LS paste system to produce an ettringite-rich binder (C₆A\(\bar{S}\)₃H₃₂). When ettringite is formed in place of calcium aluminate hydrates the strength increases, frost resistance is improved, and drying shrinkage is enhanced. Lastly, a potential application of ladle slag as a refractory material was also investigated. / Tiivistelmä Euroopassa syntyy vuosittain noin 4 Mt terästeollisuden sivutuotetta, JV-kuonaa, josta 80 % läjitetään tai kaatopaikoitetaan. Maailmanlaajuisesti syntyvän kuonan määrä tulee todennäköisesti kasvamaan laadukkaiden terästuotteiden ennustetun kysynnän kanssa. Tämän vuoksi kuonalle tulisi löytää hyötökäyttökohde, jota vältyttäisiin läjitykseltä. JV-kuona sisältääkin suuria määriä kalsiumia ja alumiinia sekä mineralogisia faaseja, joilla on sementtimäisiä ominaisuuksia. Näin kuonaa voitaisiin käyttää sovelluksissa, joissa tällä hetkellä käytetään kalliita kaupallisia sementtejä. Tämän väitöskirjan tarkoituksena oli tutkia JV-kuonan ominaisuuksia sementtimäisenä sideaineena alkali-aktivoinnissa sekä hydraulisena sideaineena yksinään että kipsin kanssa sekoitettuna. Väitöskirjan tulokset osoittivat, että JV-kuonaa voidaan käyttää prekursorina alkali-aktivoinnissa tai hydraulisena sideaineena pelkästään veden kanssa tai yhdessä kipsin ja veden kanssa. Saavutetut puristuslujuuset vaihtelivat 35 ja 92 MPa:n välillä, jotka vastaavat normaalin ja erityislujan betonin lujuuksia. JV-kuonan reaktiotuotteet alkali-aktivonnin jälkeen analysoitiin XRD- ja FTIR-analyyseillä. Tuloksista nähtiin, että alkali-aktivoinnin jälkeen reaktiotuote on sementin kaltainen kalsium-aluminatti-silikaati-hydraati (C-A-S-H) -tyyppinen faasi. XRD-, SEM-, TGA- ja NMR-analyysit osoittivat JV-kuonan hydrataatiotuotteiden olevan erilaisia kalsium-aluminaattihydraatteja (C₂AH₈, C₃AH₆, AH₃ ja C₂ASH₈). Tämän vuoksi työssä tutkittiin eri vesi–kuona-suhteita, ja havaittiin, että kun käytetään alhaista kuona-vesi –suhdetta (0,35), reaktiotuoteiden muutos vähenee ja lujuus paranee. Toinen tapa, jolla voidaan estää reaktiotuotteiden muuttuminen, on kipsin lisäys: lisäämällä kipsiä tuotetaan runsaasti ettringiittiä (C₆A\(\bar{S}\)₃H₃₂). Kun ettringiittiä muodostuu kalsium-aluminaattihydraattien sijaan, lujuus kasvaa, pakkaskestävyys paranee ja kuivumiskutistuma paranee. Väitöskirjan viimeisessä osiossa tutkittiin JV-kuonan mahdollista käyttöä tulenkestävänä materiaalina ja huomattiin, että sen tulenkestävyysominaisuudet vaihtelevat käytetyn aktivointityypin mukaan.

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 diploma thesis is focused on the use of the waste glass with different fineness on alkali - activated composites, mainly based on slag and fly ash. The theoretical part is focused on materials that are most used for alkaline activation - slag, fly ash and their composites with waste glass. The theoretical part also deals with the alkaline activation of composites from these materials and the factors that influences the microstructure and properties of these composites. In the experimental part were prepared composites from slag and fly ash with a waste glass as substitute. These composites then have been examined on mechanical properties and microstructure, also how different fineness of glass influences these properties. Then it will be decided whether it is economically advantageous grinding waste glass to finer fractions

V mnoha oborech jsou stále využívána anorganická filtrační media založená na materiálech, jejichž výroba využívá primární suroviny. Jejich výroba je tedy energeticky náročná a v důsledku nákladná a neohleduplná k životnímu prostředí. Cílem této práce je ověřit možnost využití alkalicky aktivovaných materiálů na bázi sekundárních surovin, především vysokopecních strusek (BFS) a popílků z uhelných elektráren (FA), pro výrobu porézních médií schopných v budoucnosti nahradit keramické a jiné anorganické filtry. Výzkum je rozvinut skrze experimentální design založený na výpočetním schématu samostatně vyvinutém s pomocí programu MATLAB. Toto schéma počítá vhodná složení směsí na základě poměrů obsahu nejdůležitějších oxidů ve vstupních surovinách. Tak je zajištěno zohlednění proměnlivého složení vstupních surovin a práce je tím hodnotnější, že její výsledky jsou skrze početní nástroj zohledňující základní oxidové složení surovin zobecnitelné. Zároveň byly však pro srovnání a lepší názornost závislostí vlastností na složení navrhnuty a připraveny i série vzorků založené vždy pouze na jedné ze surovin. Z výsledků vyplývá, že pevnost vzorků z těchto směsí (vytvrzených 24 hodin při 70 °C) ve čtyřbodové ohybové zkoušce dle ČSN EN 12390 5 může přesáhnout 7,6 MPa. Dosažením co možná nejvyšší porozity však zákonitě negativně ovlivňuje pevnost materiálu a výsledný materiál tedy dosahuje pevnosti těsně nad hranicí 6,3 MPa. Výsledky obecně dokazují, že nejvíce je pevnost materiálů ovlivněna poměrem SiO2/Al2O3 a množstvím alkalického aktivátoru. Z výsledků vyplývá, že alkalicky aktivované materiály (AAM) na bázi strusky dosahují i více než dvojnásobné pevnosti analogických materiálů na bázi elektrárenského popílku. Velikost pórů materiálů připravených z tříděných surovin s velikostí zrna od desítek po lehce přes sto mikronů se ve většině případů pohybuje v rozmezí desetin ž jednotek mikronů, v případě výsledného materiálu je to pak přibližně 0,2 mikronu. Celková porozita lisovaných těles se pohybuje těsně pod 40 %, což je v tomto případě téměř dvojnásobek ve srovnání s totožnými materiály na bázi netříděných surovin. Výsledky rovněž ukazují, že materiály na bázi strusky vykazují nižší porozitu než ty na bázi popílku, což je patrně způsobeno rozdílnou morfologií částic obou materiálů – částice strusky jsou nepravidelně hranaté a částice popílku kulaté. V průběhu experimentální činnosti byla pozorována tvorba výkvětů u materiálů na bázi elektrárenských popílků. Pomocí Energo-disperzní spektroskopické analýzy (EDS) byly výkvěty identifikovány jako hydroxid sodný procházející karbonatací za účasti vzdušného CO2. Test permeability vyžadoval, kvůli velmi jemné povaze porézní struktury, přípravu asymetrických filtračních přepážek. Tyto přepážky dosáhli propustnosti 138 L/h.m2.bar pro vodu a 1320 L/h.m2.bar pro vzduch.