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Geopolymers have received increasing attention as a promising sustainable alternative to ordinary Portland cement (OPC). However, the relationship among the synthesis, geopolymerization process, microstructures, molecular strucutres and mechanical properties of geopolymers remains poorly understood. To fill this knowledge gap, this dissertation focuses on the correlation of chemical composition-reaction kinetics-microstructure-mechanical properties of geopolymers. This study also sheds light on the durability, environmental impact and engineering applications of geopolymers from practical perspectives. The first part of this dissertation presents a comprehensive study on red mud-class F fly ash based geopolymers (RFFG). Firstly, RFFG with a high 28-day mechanical strength were successfully synthesized under the ambient condition of 23°C and 40 to 50% relative humidity. A nominal Na/Al molar ratio of 0.6 ~ 0.8 with a Si/Al ratio of 2 was found to be a good starting chemical composition for RFFG synthesis. Secondly, the reaction kinetics and its relation to the mechanical properties of RFFG were investigated by monitoring the development of geopolymer gels, reaction rate, porosity and mechanical properties of RFFG samples cured at room temperature, 50°C and 80°C for up to 120 days. The asymmetric stretching FTIR band of Si-O-T (T is Si or Al) centered around 960-1000 cm-1, which is the characteristic band of geopolymer gels, was observed to shift to a lower wavenumber at the early stage of the synthesis and shift to a higher wavenumber later on during the synthesis. The shift of Si-O-T band indicates that the geopolymerization took place in three stages: dissolution to Al-rich gels at Stage I, Al-rich gels to Si-rich gels at Stage II and Si-rich gels to tectosilicate networks at Stage III. The mechanical strength of RFFG barely increased, increased slowly by a limited amount and developed significantly at these three stages, respectively. An elevated curing temperature enhanced the early strength of RFFG, whereas an excessively high curing temperature resulted in a higher pore volume that offset the early-developed strength. Lastly, the remaining mechanical properties of the RFFG samples after soaking in a pH = 3.0 sulfuric acid solution for up to 120 days and the concentration of heavy metals leached from RFFG samples after the soaking were measured. The RFFG samples’ resistance against sulfuric acid was found to be comparable to that of OPC, and leaching concentrations of heavy metals were much lower than the respective EPA limits for soil contaminations. The degradation in mechanical properties of the RFFG samples during soaking in the acid was attributed primarily to the depolymerization and dealumination of geopolymer gels. The second part of this dissertation is devoted to the investigation of nano-scale mechanical properties and molecular structures of geopolymer gels with grid-nanoindentation and molecular modeling. Four phases (e.g., porous phase, partially developed geopolymer gels, geopolymer gels and unreacted metakaolin or crystals) and their nano-mechanical properties were identified in metakaolin based geopolymers (MKG) with grid-nanoindentation technique. It was found that the proportion of geopolymer gels largely determines the mechanical strength of the resulting geopolymers while other factors (e.g., pores and cracks) also play some roles in macro-scale mechanical strength of geopolymers. The final setting time of the geopolymers increased with the increase in Si/Al ratio and the decrease in Na/Al ratio, while the proportion of geopolymer gels and macro-mechanical strength of geopolymers increased with the increase in both Si/Al and Na/Al molar ratios, within the range of 1.2~1.7 and 0.6~1.0, respectively. In the molecular modeling, a combined density function theory (DFT)-molecular dynamic (MD) modeling simulation was developed to “synthesize� geopolymers. DFT simulation was used to optimize reactive aluminate and silicate monomers, which were subsequently used in reactive MD simulations to model the polymerization process and computationally synthesize geopolymer gels. The influence of Si/Al ratio and simulation temperatures on geopolymerization and resulting molecules of geopolymer gels was also examined. The computationally polymerized molecular structures of geopolymer gels were obtained. The distribution of Si4(mAl) and radial distribution fuctions of Si-O, Al-O, O-O and Na-Al for the models were compared and qualitatively agreed well with the experimental results from nuclear magnetic resonance (NMR) and neutron/X-ray pair distribution function in previous literature. Three polymerization stages: oligomerization, ring formation and condensation, were identified based on the nature of polymerization process, which were found to be affected by the temperature and Si/Al ratio. A higher temperature enhanced the reaction rate while a lower Si/Al ratio resulted in more compact geopolymer networks. The final part of this dissertation presents an experimental feasibility study of using geopolymer in shallow soil stabilization, in which a lean clay was stabilized with MKG at different concentrations. The study confirmed that MKG can be used as a soil stabilizer for clayey soils and the unconfined compressive strength, Young’s modulus and failure strain are comparable to or even better than OPC when the MKG’s concentration is higher than 11%. The binding effect of geopolymer gels on the soil particles was confirmed as the main mechanism for the improvement in mechanical properties of the stabilized soils with the scanning electron microscopy imaging, energy dispersive X-ray spectroscopy analyses and X-ray diffractometry characterization.

Coal powered power plants account for more than 40 percent of the electricity production of the United States. The combustion of coal results in a large number of solid waste materials, or coal combustion byproducts (CCBs). These waste materials are stored in landfill or ponds. The construction industry is heavily reliant on concrete which is used to make the building blocks for any type of structures, bricks. Concrete is a composite material made of a binder and coarse and fine aggregate. The most widely used binder in concrete production is Ordinary Portland Cement (OPC). Since cement manufacture is costly and environmentally damaging, research has increased in recent years to find a more readily available binder. This study aims at investigating the properties of Illinois fly ash as a binder in the production of geopolymer concrete. Geopolymer concrete is an innovative material made by using Alumina and Silica rich materials of geological origins as a binder as well as an alkali activated solution. Sodium Silicate and Sodium Hydroxide were used to make the activator solution of two different ratios. Geopolymer Concrete with a ratio of 1:1 of Sodium Silicate to Sodium Hydroxide reached a compressive strength above 6000 psi while samples made with a ratio of 1:2 reached a compressive strength above 4000 psi. This environmentally-friendly, green concrete was also found to have a cost comparable to conventional concrete.

This research studies the green geopolymer incorporated with phase change material (PCM) for energy saving in buildings. First class F fly ash (FA) based-geopolymer binder was studied. In order to improve the mechanical properties, low calcium slag (SG) was added to the FA to produce geopolymer. The effect of different factors including SG content (at different relative amounts FA/SG = 0/100, 25/75, 50/50, 75/25 and 100/0), NaOH solution at different concentrations (7.5, 10 and 15 M), various curing times (1, 2, 4, 7, 14 and 28 days) and curing temperatures (25 (ambient), 45, 60, 75 and 90°C) was investigated. The unit weight and uniaxial compressive strength (UCS) of the geopolymer specimens were measured. Scanning electron microscopy/energy-dispersive X-ray spectroscopy (SEM/EDX) and X-ray diffraction (XRD) were also performed to characterize the microstructure and phase composition of the geopolymer specimens. The results show that the incorporation of SG not only improves the strength of the geopolymer specimens but also decreases the initial water content and thus the NaOH consumption at the same NaOH concentration required for geopolymer production. In addition, the inclusion of SG increases the unit weight of the geopolymer specimens, simply because SG has a much greater specific gravity than FA. The results also show that the strength of the FA/SG-based geopolymer develops rapidly within only 2 days and no obvious gain of the strength after 7 days. The optimum curing temperature (the curing temperature at which the maximum UCS is obtained) at a FA/SG ratio of 50/50 is around 75°C. Second, FA-based geopolymer concrete was synthesized and the effect of different factors including sodium silicate to sodium hydroxide (SS/SH) ratio, aggregate shape, water to fly ash (W/FA) ratio, curing time, water exposure and PCM inclusion on the compressive strength of the geopolymer concrete specimens cured at different ambient temperatures was studied. The results show that the UCS of the specimens increases with higher SS/SH and W/FA ratios up to a certain level and then starts to decrease at higher ratios. The results also indicate that a major portion of the strength of the specimens cured at ambient temperatures develops within the first four weeks. In addition the strength of the FA-based geopolymer concrete is slightly decreased with water exposure and PCM incorporation. Third, the mechanical and thermal properties of geopolymer mortar synthesized with FA and different amount of PCM were studied and the effect of incorporated PCM on the unit weight and UCS of geopolymer mortar was evaluated. SEM imaging was performed to identify the change of micro structure of the geopolymer mortar after incorporation of PCM. The thermal properties of the geopolymer mortar containing different amount of PCM were also characterized using differential scanning calorimetry (DSC) analysis. In addition model tests were performed using small cubicles built with geopolymer mortar slabs containing different amount of PCM to evaluate the effectiveness of geopolymer mortar wall with incorporated PCM in controlling the heat flow and internal temperature. The results indicate that both the unit weight and UCS of the geopolymer mortar decrease slightly after PCM is incorporated, mainly due to the small unit weight and low strength and stiffness of the PCM, respectively. However, the compressive strength of geopolymer mortar containing up to 20% PCM is still sufficiently high for applications in buildings. The results also show that the incorporation of PCM leads to substantial increase of heat capacity and decrease of thermal conductivity of the geopolymer mortar and is very effective in decreasing the temperature inside the cubicles. Finally, a numerical study on the thermal performance of geopolymer with incorporated PCM was carried out. In order to simulate the heat transfer through geopolymer containing PCM, a simplified method was first presented. The influence of phase transition was linked to the energy balance equation through variable specific heat capacity of the PCM-geopolymer. The thermal properties of the geopolymer containing PCM for the numerical analysis were determined using DSC and guarded heat flow (GHF) tests. The simplified method was validated based on the good agreement between the numerical and experimental results. With the validated model, the effect of various factors including the specific heat capacity, thermal conductivity and wall thickness on the thermal performance of PCM-geopolymer walls was studied. Then a modified numerical method was proposed for simulating the whole thermal transfer processes and the simulation results were used to conduct the economic evaluation of PCM-geopolymer walls for energy savings in buildings.

Alkali-activated binders (AABs) are the third-generation class of binders after lime and Portland cement. These binders have the potential to be made from a variety of industrial waste sources, many of which have remained largely unexplored. Significant drawbacks of AABs are the requirement of highly alkaline solutions for its production and the lack of available data regarding its implementation in the field. To bridge this gap, this study aimed to research the recycling and valorization of tungsten mining waste (TMW) to produce AABs, using waste glass (WG) as a supplementary material for reducing the alkali activator demand. Finally, a connection was made between the fundamental research on AABs and a practical engineering application. A detailed approach was undertaken to determine the most appropriate TMW-WG AAB preparation methods and curing conditions, an understudied area, with a strong emphasis on the microstructural development during hardening. The alkali activator appeared to be sensitive to prolonged stirring, which appeared to induce a stripping effect of the water molecules from the alkali metal ions, leading to a less intense attack on the silicon-oxygen bonds in precursor material. The effects of WG (dissolution and chemical reaction) were investigated to understand its contribution to the AAB system. WG was observed to provide an additional source reactive silica, contributing to the formation of a calcium-containing N-A-S-H gel, and significantly improve the mechanical strength. PCM macro-encapsulated aggregates (ME-LWAs) were also researched and incorporated into the TMW-WG AAB for the development of an energy-saving building material. The ME-LWAs stood out to be leak proof, with excellent thermal stability and thermal conductivity, latent heat capacity and abrasion resistance. It was also found out it is feasible to produce foamed lightweight alkali-activated materials using tungsten mining waste (TMW-WG FAAB) and other precursor materials. FAAB can be used in several applications where low density and fire resistance is required. The TMW-WG FAAB was also designed to suit a wide range of densities and compressive strengths using chemical foaming, achieving very low thermal conductivity. Finally, the TMW-WG AAB proved itself to be convenient to prepare on-site, demonstrating in service its ease of preparation, rapid hardening and durability as a novel road repair mortar.

Geopolymers, a class of largely X-ray amorphous aluminosilicate binder materials, have been studied extensively over the past several decades, but largely from an empirical standpoint. The primary aim of this investigation has been to apply a more science-based approach to the study of geopolymers, including introducing a variety of mathematical modelling techniques to the field. The nanostructure of geopolymers is analysed via an extensive literature review, and conclusions regarding the presence and role of crystallinity within the geopolymer structure are drawn. Si/Al ordering within the tetrahedral aluminosilicate gel framework is described by a statistical thermodynamic model, which provides an accurate representation of the distribution of Si and Al sites within the framework as well as physically reasonable values for the energy penalty associated with ordering violation. Framework and extraframework structure within the geopolymer binder are also described by the pair distribution function (PDF) technique, whereby synchrotron X-ray scattering data are converted via a Fourier transform-based method into real-space structural data on an Ångstrom length scale. Real-space Rietveld analysis of geopolymers crystallised at high temperature is used to back-calculate and analyse the original geopolymer structure, and the primary change in very short-range structure from the as-synthesised geopolymer to the high-temperature crystalline product is observed to be a shift in the location of the extraframework charge-balancing cation.

The discovery of geopolymers is a breakthrough which provides a cleaner and environmentally-friendlier alternative to Ordinary Portland Cement (OPC). Since the pioneering days, the understanding of the chemistry, synthesis, and practical application of geopolymers has improved to the extent that commercialisation of geopolymers on a large scale is possible in the near future. However, the fundamental breakthroughs and understanding to date are based on investigations of ‘pure’ raw materials, like metakaolinite. The utilisation of metakaolinite has been useful in a research setting, but will be impractical for widespread application. Therefore, the thesis attempts to do a more detailed study on geopolymers synthesised from waste materials, such as fly ash. The motivation for using fly ash as the main raw material is driven by various factors: (1) it is cheap and available in bulk quantities, (2) it is currently under-utilised, except for its use as an additive in OPC, (3) it has high workability, and (4) it requires less water (or solution) for activation.

Geopolymer cements offer an alternative to, and potential replacement for, ordinary Portland cement (OPC). Geopolymer technology also has the potential to reduce global greenhouse emissions caused by OPC production. There is already a considerable amount of work and research conducted on geopolymers in the past decades, and it is now possible to implement this technology commercially. However, to ensure that geopolymer becomes commercially available and able to be used in the world, further understanding of its ability to provide durable and long lasting materials is required. One main property which is still relatively unexplored compared to other properties is its shrinkage properties. The objective of this thesis is therefore to examine the shrinkage of geopolymers and factors which might influence it. / The factors which influence geopolymer strength were investigated as being the factors which may influence shrinkage. The selection of the activating solution is an important factor in forming the final product of a geopolymer. Activating solution SiO2/Na2O ratio is determined to be an important influence on the shrinkage of geopolymer. SEM images of the samples enable observation of the sample topology and microstructure. An important observation was the existence of a ‘knee point’ which also occurs in OPC shrinkage. The ‘knee point’ is the point where the shrinkage goes from rapid shrinkage to slow shrinkage. From SEMs it is noted that the samples past the knee point are shown to have a smoother topology which means it is more reacted. / Autogenous shrinkage is an important issue for OPC containing a high amount of silica, and is also a key factor in geopolymer shrinkage. Autogenous shrinkage is tested by keeping samples in a sealed environment where water lost to drying is kept to a minimum. It is noted that sealing and bagging the samples reduces the shrinkage considerably. The water to cement ratio, which is an important factor in OPC shrinkage, is also explored for the case of geopolymers. Water content plays an important role in determining early stage shrinkage, and has little to no effect on the later stage shrinkage. The water loss from the samples during drying on exposure to environment is noted and compared. The addition of more water did not necessary means that more water was lost. / Addition of slag is known to be beneficial to geopolymers by giving early structural strength and faster setting time. Commercial geopolymer concrete will also include the use of slag. However, the addition of slag up to a certain extent gives a deleterious affect on shrinkage. / A different type of Class F fly ash source with different composition data was used to see its effect on shrinkage, with only a slight influence observed between the two ashes tested. Fly ash was also ground for different lengths of time before use in geopolymerization, with grinding for less than 12 hours giving higher shrinkage than an unground sample, but shrinkage the decreasing with grinding for 18 or 24 hours. This initial higher shrinkage has been attributed to the mechanism of grinding which resulted in unevenly shaped fly ash particles taking up a larger initial volume resulting in higher shrinkage. The sample grinded for 24 hours showed higher shrinkage due to the particle size to be so fine that agglomerates may have form during mixing which would result in a lower reaction rate which increases the shrinkage. Elevated curing temperatures also reduce geopolymer shrinkage. / Thus, it is clear that the shrinkage of geopolymers is influenced by a wide range of variables, and more notably by a few important variables: activating solution ratio, addition of water, grinding and bagging. The shrinkage of geopolymers can be correlated to the strength to a certain extent. However, the understanding of the shrinkage of geopolymers is still at a very initial phase, and further research is required.

Geopolymer is a novel cementitious material which can be a potential alternative to ordinary Portland cement (OPC) for all practical applications. However, until now research on this revolutionary material is limited mainly to experimental studies, which have the limitations in considering the details of the atomic- and meso-scale structure and atomic scale mechanisms that govern the properties at the macro-scale. Most experimental studies on geopolymer have been conducted focusing only on the macroscopic properties and considering it as a single-phase material. However, research has shown that geopolymer is a composite material consisting of geopolymer binder (GB), unreacted source material, and, in the presence of Ca in the source material, calcium silicate hydrate (CSH). Therefore, in this research, a multiscale/multiphysics modeling approach has been taken to understand geopolymer structure and mechanical properties under varying conditions and at different length scales. First, GB was prepared at the atomic scale using molecular dynamics (MD) simulations with varying Si/Al ratios and water contents within the nano voids. The MD simulated geopolymer structure was validated based on comparison with experiments using X-ray pair distribution function (PDF), infra-red (IR) spectra, coordination of atoms, and density. The results indicate that the highest strength occurs at a Si/Al ratio of 2-3 and the presence of molecular water negatively affects the mechanical properties of GB. The loss of strength for GB with increased water content is linked to the diffusion of Na atoms and subsequent weakening of Al tetrahedra. The GB was also subjected to nanoindentation using MD and the effect of indenter size and loading rate was investigated at an atomic scale. A clear correlation between the indenter size and observed hardness of GB was observed which proves indentation size effects (ISE). Realizing the composite nature of geopolymer, the presence of unreacted and secondary phases such as quartz and CSH in geopolymer was also investigated. To do that, the mechanical properties of GB, the secondary phases and their interfaces was first determined from MD simulations. Using the MD generated properties, a meso-scale model of geopolymer composite was prepared in Peridynamics (PD) framework which considered large particles of GB and secondary phases of nanometers in size which cannot be easily modeled in MD. The meso-scale model provides a larger platform to study geopolymer in the presence of large nano-voids and multiple phases. Results from the PD simulations were directly comparable to experimentally observed mechanical properties. Findings of this study can be directly used in future to construct more advanced and sophisticated models of geopolymer and will be instrumental in designing the synthesis condition for geopolymer with superior mechanical properties.

Alkali silica reaction (ASR) is detrimental to concrete. It is a time-dependent phenomenon, which can lead to strength loss, cracking, volume expansion, and premature failure of concrete structures. In essence, it is a particular chemical reaction involving alkali hydroxides and reactive form of silica present within the concrete mix. Geopolymer is a type of alkaline activated binder synthesized through polycondensation reaction of geopolymeric precursor and alkali polysilicates. In this thesis, three types of reactive aggregates with different chemical compositions were used. Systematic laboratory experiments and microstructural analysis were carried out for the geopolymer concrete and the OPC concrete made with the same aggregates. The result suggests that the extent of ASR reaction due to the presence of three reactive aggregates in geopolymer concrete is substantially lower than that in OPC based concrete, which is explained by the pore solution change and verified through their microstructural variations and FTIR images.