Carbonation curing of concrete products has shown potentials for CO2 capture and storage with environmental, technical and economical benefits in global greenhouse gas mitigation exercise. The primary objective of this study is to investigate the effect of early age carbonation on mechanical performance and pH of concrete in an attempt to understand the process and promote large scale applications. / It was found that significant early strength was developed in cement and concrete through early age carbonation curing. The early strength could be maintained and improved due to subsequent hydration. Twenty-eight-day strength of carbonated cement and concrete was comparable to that of hydrated reference if subsequently cured in the air in a sealed bag, but was lower if subsequently cured in water. Treatment with either internal curing using lightweight aggregates or chemical admixture can effectively enhance late strength development in carbonated concrete. / For three typical cement-based products including cement paste compacts, concrete compacts and precast concrete, two-hour carbonation reduced pH value from 12.8 to 11.8 as the lowest and subsequent 28-day hydration could slightly increase pH by 2% as maximum. At any time pH of early age carbonated concrete was always higher than 11.5, a threshold value under which the corrosion of reinforcing steel is likely to occur in concrete. The high pH in early-age carbonated concrete was likely attributed to the fact that early age carbonation was an accelerated hydration process, which was totally different from weathering carbonation in which pH of concrete could be neutralized due to the decomposition of calcium hydroxide and calcium silicate hydrates gel. Therefore, early age carbonation technology is applicable not only to concrete products such as masonry units and paving stones, but possibly to precast concrete with steel reinforcement as well.

Since the energy crisis in 1970’s, research on low energy cements with low CO2-emissions has been increasing. Numerous solutions have been investigated, and the goal of this original research is to create a viable hybrid cement with the components of both Ordinary Portland cement (OPC) and calcium sulfoaluminate cement (CSAC), by forming a material that contains both alite and calcium sulfoaluminate clinker phases. Furthermore, this research focuses on keeping the cost of this material reasonable by reducing aluminum requirements through its substitution with iron. The aim of this work would produce a cement that can use large amounts of red mud, which is a plentiful waste material, in place of bauxite known as an expensive raw material. Modified Bogue equations were established and tested to formulate this novel cement with different amounts of ferrite, from 5% to 45% by weight. This was followed by the production of cement from reagent chemicals, and from industrial by-products as feedstocks (fly ash, red mud and slag). Hydration processes, as well as the mechanical properties, of these clinker compositions were studied, along with the addition of gypsum and the impact of a ferric iron complexing additive triisopropanolamine (TIPA). To summarize this research, the influence of the addition of 5-45% by weight of ferrite phase, was examined with the goal of introducing as much red mud as possible in the process without negatively attenuate the cement properties. Based on this PhD dissertation, the production of high-iron alite-calcium sulfoaluminate-ferrite cements was proven possible from the two sources of raw materials. The hydration processes and the mechanical properties seemed negatively affected by the addition of ferrite, as this phase was not hydrated entirely, even after 6 months of curing. The usage of TIPA counteracted this decline in strength by improving the ferrite hydration and increasing the optimum amount of gypsum required in each composition. The mechanical data were equivalent to OPC strengths for some compositions with 25% ferrite. This preliminary work constitutes the first research phase of this novel cement and requires additional research for its improvement. Topics for additional research are identified in this dissertation.

The NIST miniature paste prism test was developed to assess sulphate resistance of cements faster than the commonly used ASTM C 1012 test. The goal of this research is to address the current limitations regarding the NIST procedure to determine the optimum testing parameters and to establish appropriate expansion limits. A range of variables including details of specimen design, curing regime, water-to-cementitious materials ratio, and prism length were tested on the materials with a wide range of sulphate performance. The findings of the study demonstrate that even though it can yield results in only three months, the NIST test can provide an erroneous differentiation between certain cementitious materials. Reliability and repeatability of the test results can be improved by using longer specimens and longer curing times. The NIST test can be used as a preliminary screening test, but users need to be aware of its limitations.

The cement line is the first mineralized matrix deposited on an implant surface during contact osteogenesis forming the bone/implant interface. The hypothesis underlying the present project was that non-collagenous cement line proteins must be deposited into the submicron undercuts on substrate surfaces prior mineralization. In vitro osteogenic cultures were used to grow bone nodules on Thermanox® coverslips modified with calcium phosphate nanocrystals, creating an undercutted surface. Electron microscopy was used to observe cement line formation. BSP immunogold labelling was used to determine if the cement line organic matrix is deposited within undercuts prior mineralization. The results showed the deposited bone nodules, and on test coverslips the deposited cement line was thicker and evenly distributed than control. Furthermore, positive BSP labelling was found within the undercuts prior to cement line mineralization. Thus, it can be concluded that cement line proteins are deposited into submicron undercuts on substrate surfaces prior to mineralization.

The NIST miniature paste prism test was developed to assess sulphate resistance of cements faster than the commonly used ASTM C 1012 test. The goal of this research is to address the current limitations regarding the NIST procedure to determine the optimum testing parameters and to establish appropriate expansion limits. A range of variables including details of specimen design, curing regime, water-to-cementitious materials ratio, and prism length were tested on the materials with a wide range of sulphate performance. The findings of the study demonstrate that even though it can yield results in only three months, the NIST test can provide an erroneous differentiation between certain cementitious materials. Reliability and repeatability of the test results can be improved by using longer specimens and longer curing times. The NIST test can be used as a preliminary screening test, but users need to be aware of its limitations.

The cement line is the first mineralized matrix deposited on an implant surface during contact osteogenesis forming the bone/implant interface. The hypothesis underlying the present project was that non-collagenous cement line proteins must be deposited into the submicron undercuts on substrate surfaces prior mineralization. In vitro osteogenic cultures were used to grow bone nodules on Thermanox® coverslips modified with calcium phosphate nanocrystals, creating an undercutted surface. Electron microscopy was used to observe cement line formation. BSP immunogold labelling was used to determine if the cement line organic matrix is deposited within undercuts prior mineralization. The results showed the deposited bone nodules, and on test coverslips the deposited cement line was thicker and evenly distributed than control. Furthermore, positive BSP labelling was found within the undercuts prior to cement line mineralization. Thus, it can be concluded that cement line proteins are deposited into submicron undercuts on substrate surfaces prior to mineralization.

The goal of the thesis is to evaluate if developed phase chemical process models for cement clinker and lime production processes are reliable to use as predictive tools in understanding the changes when introducing sustainability measures. The thesis describes the development of process simulation models in the application of sustainability measures as well as the evaluation of these models. The motivation for developing these types of models arises from the need to predict the chemical and the process changes in the production process, the impact on the product quality and the emissions from the flue gas. The main chemical reactions involving the major elements (calcium, silicon, aluminium and iron) are relatively well known. As for the minor elements, such as sodium and potassium metals, sulphur, chlorine, phosphorus and other trace elements, their influence on the main reactions and the formation of clinker minerals is not entirely known. When the concentrations of minor and trace elements increase due to the use of alternative materials and fuels, a model that can accurately predict their chemistry is invaluable. For example, the shift towards using less carbon intensive fuels and more biomass fuels often leads to an increased phosphorus concentration in the products. One way to commit to sustainable development methods in cement clinker and lime production is to use new combustion technologies, which increase the ability to capture carbon dioxide. Introducing oxy-fuel combustion achieves this, but at the same time, the overall process changes in many other ways. Some of these changes are evaluated by the models in this work. In this thesis, a combination of the software programs Aspen Plus™ and ChemApp™ constitutes the simulation model. Thermodynamic data from FACT are evaluated and adjusted to suit the chemistry of cement clinker and lime. The resulting model has been verified for one lime and two cement industrial processes. Simulated scenarios of co-combustion involving different fuels and different oxy-fuel combustion cases in both cement clinker and lime rotary kiln production are described as well as the influence of greater amounts of phosphorus on the cement clinker quality.

This project researched the fungal and bacterial communities (i.e. biofilms) found on concrete infrastructure in Georgia. Various microbial communities were sampled from four geographically separated sites. The species present in these biofilms were identified through DNA analysis and cultured for testing. A new, rapid test method was developed to accurately simulate field growth conditions in a laboratory environment. Using the newly developed test method, these communities were grown on small mortar tiles, which varied in w/cm, surface roughness, cement type (including photocatalytic cement), and supplementary cementing materials. This research determined that photocatalytic cement was the most effective in decreasing biofilm growth under artificial daylight, but did not increase or decrease growth when not exposed to light. The next most effective ways to decrease growth were lowering w/cm and decreasing surface roughness. The supplementary cementing materials examined did not increase or decrease biofilm growth.

The study of mechanical energy and electrical energy dissipation in cementitious materials can lead to development of high damping concrete for structural applications, and new non-destructive testing techniques for use on existing concrete structures. This research aims to improve mechanical damping properties of cementitious materials and determine durability parameters from complex permittivity measurements. Damping was improved by utilizing poromechanical effects, and by adding viscoelastic and nanometric inclusions. Poromechanics was utilized to model and predict damping on specimens designed to maximize poromechanical effects, and composite theory was used to predict composite bounds for the loss tangent, i.e. modeling the effects on damping due to the addition of viscoelastic inclusions. Experimental results indicated that substantial damping improvement can be realized by both poromechanical effects and adding novel inclusions into cement pastes. The models were able to predict experimentally measured damping as a function of loading frequency. The electrical energy dissipation in cementitious materials was studied by dielectric spectroscopy as a function of moisture state and pore structure/permeability. The results were compared to predictions from multiphase composite modeling, where the properties of the confined water was inversely determined and used to predict moisture content. It was found that moisture state of cementitious materials has a linear relation to the complex permittivity over a wide variety of frequency ranges. Composite model prediction indicated that permeability of saturated cementitious materials studied in this research is likely dependent on the amount of free water in the pores. Permeability can be inferred from the pore structure of the cement paste via complex permittivity measurements by conditioning cement paste at different levels of relative humidity.

Thesis (MEng) -- University of South Australia, 1997