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Geopolymers (GPs) are inorganic binders created by adding alkaline solution (e.g. KOH) to silicates such as furnace slag, fly ash or clay to dissolve Si and Al that polymerises and precipitates to form an inorganic binder material while hardening. GP properties are similar to ordinary Portland cement regarding their high compressive strength or low shrinkage but they are particularly notable for a high resistance to acid and fire. However, the most significant advantage of GP cements is their low CO2 footprint. The most common clay used as GP raw material is kaolin. The aim of this study is to investigate the suitability of illitic clays as a cheaper alternative to kaolin and determine the necessary preparation steps required to produce effective GP binder materials. Three clays dominated by dioctahedral 2:1 layer silicates, in particular interstratifications of mica and smectite were investigated: (1) Illitic clay from Friedland, Northern Germany, containing an irregularly stacked illite-smectite interstratification (R0 I-S), (2) rectorite from Arkansas, USA, as a regular interstratification of mica and smectite, and (3) clay stated as “sárospatakite” from Füzérradvány clay deposit, Northern Hungary, containing a long range ordered I-S (R3). The three types of I-S interstratification-rich clays were extensively characterised and the Friedland clay, as the most probable raw material for GP production, was studied in more detail including several size fraction analyses. These results are used to investigate and determine the parameters necessary to produce suitable precursors for GP binders. Different approaches of clay activation to yield a highly reactive material by milling and heating were examined. Milling was found to be suitable as a preparation step after heating breaking up sintering aggregates to create pathways for the alkaline solution, but not as a substitute for heating. Important parameters for the precursor design such as temperature, time, and heating rate are determined and discussed. Geopolymerisation is considered to be a multi-parameter system and is influenced strongly by the degree of dehydroxylation, Si:Al ratio, or amount of 5-fold coordinated Al. However, in contrast to kaolin-based systems, none of these parameters explain why the illitic Friedland clay heated to 875 °C was found to be most suitable for GP binders. Based on leaching experiments and specific surface area (AS) measurements of the heated Friedland clay, a conceptual model is presented to explain the observed relationship between the heating temperature and the subsequent compressive strength of the GP cement. An optimum between the counteracting reactions of decreasing AS (fewer particles must be covered with GP phase) and decreasing Si+Al dissolved (less GP phase created) is necessary, which exists at 875 °C for the Friedland clay. In this state enough GP phase is created to bind all remaining sintering aggregates to form a cement with high compressive strength. This relationship can be expressed as (Si+Al) / AS (sum of dissolved Si and Al divided by the surface area of grains that must be covered with GP phase), and can be used as a predictive tool for determining the optimal heating temperature. The results presented in this thesis indicate that illitic clays are suitable raw materials as GP binders if the necessary preparation steps of dehydroxylation, sintering and grinding are made. Proxies used to evaluate the optimal conditions for making GP binders are determined including the (Si+Al) / AS ratio as a key relationship that controls the cementation process and determines its ultimate hardness.
Using geopolymers can reduce significant amounts of CO2-emissions during the production compared to Portland cement. Although illite/smectite clays are very abundant on earths crust and rich in SiO2 and Al2O3, studies of their geopolymerization potential are rare. Thus, the illite/smectite clay of Friedland (NE Germany) was calcined (850 °C) and ground to form a reactive metaclay and then mixed with synthetic gibbsite (to test the effect of Al-concentration) and 6 molar NaOH or KOH, in order to study their geopolymerization at 25, 50 and 75 °C within 28 days. The raw clay, the precursors, and the geopolymers were characterized by XRF, XRD, SEM-EDX, Flame-AAS, nitrogen adsorption and compressive strength test. 25 °C was too low to initiate the geopolymerization of illite/smectite. Increasing the curing temperature increased the reactivity of meta-illite/smecite. Si and Al dissolution was confined to the first 24 h, followed by the hardening of the geopolymers within 28 days. At 50°C, KOH-activation formed amorphous and mesoporous aluminosilicates, which significantly cemented the particles and agglomerates of the metaclay. Consequently, geopolymers with high compression strength (~38 N/mm2) were formed. Adding 10 wt% Gibbsite (precursor Si/Al = 2.1) to the metaclay strengthened the formation of amorphous aluminosilicates and increased the compression strength of the geopolymer by 20 % from 38 - 45 N/mm2. At 75 °C, the reactivity of the metaclay in NaOH was higher than in KOH. NaOHactivation at that temperature formed geopolymers with high compression strength (~30 N/mm2) due to the cementation by microporous phillipsite (K-, Na-zeolite) crystals. Thus, alkali-activation of the calcined and ground meta-illite/smectite from Friedland form high strength geopolymers under hydrothermal conditions.
There is a current need for developing improved synthetic porous materials for better constraining the dynamic and coupled processes relevant to the geotechnical use of underground reservoirs. In this study, a low temperature preparation method for making synthetic rocks is presented that uses a geopolymer binder cured at 80 °C based on alkali-activated metakaolin. For the synthesised sandstone, the key rock properties permeability, porosity, compressive strength, and mineralogical composition, are determined and compared against two natural reservoir rocks. In addition, the homogeneity of the material is analysed structurally by micro-computed tomography and high-resolution scanning electron microscopy, and chemically by energy dispersive X-ray spectroscopy. It is shown that simple, homogenous sandstone analogues can be prepared that show permeability-porosity values in the range of porous reservoir rocks. The advance in using geopolymer binders to prepare synthetic sandstones containing thermally sensitive minerals provides materials that can be easily adapted to specific experimental needs. The use of such material in flow-through experiments is expected to help bridge the gap between experimental observations and numerical simulations, leading to a more systematic understanding of the physio-chemical behaviour of porous reservoir rocks.