La presente tesis doctoral (i.e., “New developments in calcium phosphate bone cements: approaching spinal applications”) aporta nuevos conocimientos en el campo de los cementos óseos de fosfato de calcio (CPBCs) en relación a su aplicación clínica en el campo de la cirugía vertebral mínimamente invasiva. La hipótesis central de esta investigación fue formulada en los siguientes términos: “Los cementos apatíticos pueden ser (si se optimizan) una alternativa mejor (debido a sus propiedades de fraguado, endurecimiento y bioactividad) a los actuales cementos poliméricos utilizados en vertebroplastia y cifoplastia”. En este sentido, la presente tesis doctoral ha investigado nuevas soluciones para obtener cementos apatíticos con: (a) mejores propiedades mecánicas (Cap. 2); (b) capacidad para desarrollar macroporosidad abierta e interconectada (Cap. 3); (c) mejor estabilidad y reactividad química (Cap. 4 & 5); (d) óptimas propiedades de biocompatibilidad y osteogénicas (Cap. 6, 7 & 8); y (e) mejores propiedades de inyectabilidad (Cap. 7). Además, en esta tesis se ha investigado la aplicación de los ultrasonidos a la monitorización del fraguado inicial de cementos de base cerámica con el objetivo de relacionar la evolución de las propiedades acústicas con las características de inyectabilidad de estos cementos (Cap. 9 &10). El Capítulo 2 muestra que las propiedades mecánicas, de trabajabilidad y de fluidez de los cementos apatiticos pueden mejorarse con la adición de superplastificantes en la fase líquida de los cementos. Los resultados muestran que estos aditivos pueden mejorar la inyectabilidad inicial de los cementos sin afectar a su resistencia mecánica final. El Capítulo 3 muestra que la adición de cristales de sulfato de calcio dihidratado (CSD) a la fase en polvo de un cemento de base alfa-fosfato tricálcico (α-TCP) puede modular la formación de macroporosidad durante su fraguado. Las propiedades resultantes del fraguado de estos nuevos cementos bifásicos son debidas a la disolución del α-TCP y a la precipitación de una matriz de cristales entrecruzados de hidroxiapatita deficiente en calcio (CDHA) que contiene porosidad homogéneamente distribuida gracias a la disolución pasiva de la fase de CSD. Estos cementos bifásicos mostraron resistencias mecánicas adecuadas para la aplicación en hueso trabecular. El Capítulo 4 trata sobre la problemática del proceso de fabricación de la fase reactiva principal de los cementos apatíticos, i.e. del α-TCP (α- Ca3(PO4)2). Los resultados muestran que si la relación calcio-fosforo (Ca/P) de la mezcla reactiva inicial se desvía de la relación estequiométrica Ca/P=1.50 entonces los cementos resultantes poseen malas propiedades de fraguado y de endurecimiento. Estas desviaciones ocurren fácilmente durante el proceso de sinterización del α-TCP cuando los reactivos de mezcla utilizados varían su pureza de un lote a otro. En estos casos el α- TCP obtenido produce cementos no-reactivos, i.e. que no fraguan ni endurecen. El Capítulo 5 plantea nuevas soluciones para controlar y mejorar la reactividad química del α-TCP. En este sentido, se han estudiado nuevas soluciones sólidas sinterizadas del tipo (3.CaO-1.P2O5)1-x(FeO)x con el objetivo de reemplazar al reactivo α-TCP en las actuales formulaciones de CPBCs. Los resultados muestran que la modificación del α-TCP con hierro permite recuperar la reactividad química de cementos no-reactivos de base α-TCP con una mejora adicional de las propiedades de fraguado y reológicas de los cementos resultantes. El Capítulo 6 centra su atención sobre la citocompatibilidad de las nuevas formulaciones de cementos (investigadas en los Caps. 3-5). Los resultados mostraron que los nuevos cementos de fosfato de calcio modificados con hierro (IM-CPCs) poseen características apropiadas de citocompatibilidad ya que la adhesión y la viabilidad celular no fueron afectadas con el tiempo de cultivo por la concentración de hierro. El Capítulo 7 hace referencia a nuevas aproximaciones para mejorar la inyectabilidad de los cementos óseos de base α-TCP. Los resultados demostraron que la adición de nanopartículas de óxido de hierro en la fase en polvo de un cemento de base α-TCP mejora la inyectabilidad inicial y también la resistencia máxima a compresión del cemento sin afectar a sus reacciones físico-químicas de fraguado ni a su citocompatibilidad. El Capítulo 8 se centra sobre el carácter de citocompatibilidad, biocompatibilidad y osteogénico de los nuevos cementos bifásicos porosos/modificados con hierro (estudiados en los Caps. 3-7). Los resultados demostraron que los cementos bifásicos formulados a base de CSD y α-TCP modificado con hierro poseen la habilidad de favorecer la colonización celular in vitro y proporcionan aposición ósea firme in vivo. Se concluye que estas nuevas formulaciones tienen características de cito- y biocompatibilidad de interés como biomaterial para la sustitución/reconstrucción del tejido óseo esponjoso en aplicaciones de cirugía vertebral tales como la vertebroplastia o la cifoplastia. En el Capítulo 9 y en el Capítulo 10 se aproximan los ultrasonidos como una técnica fiable para caracterizar las propiedades iniciales de fraguado de materiales de tipo cemento. Esta técnica no-destructiva permite monitorizar el fraguado del cemento en su totalidad. Los resultados obtenidos relacionan las propiedades acústicas y de material con factores experimentales del proceso de fabricación y con características reológicas. Se concluye que la monitorización ultrasónica del fraguado de cementos óseos puede contribuir a establecer protocolos prácticos adecuados para su inyección mediante técnicas de cirugía mínimamente invasivas en cirugía vertebral. Finalmente, el Capítulo 11 presenta un resumen de los resultados más relevantes de esta investigación. / This thesis is aimed at contributing to close the gap between the research conducted on the field of calcium phosphate bone cements (CPBCs) and their specific spinal clinical use. The main working hypothesis was formulated as follows: “Apatitic cements could be (after further optimization) an alternative or better option (due to its natural setting, hardening and bioactive properties) to the present use of polymeric cements in vertebroplasty and kyphoplasty”. In this regard, this thesis has approached new solutions to obtain apatitic bone cements (ABCs) with: (a) improved mechanical properties (Chapter 2); (b) the ability to develop open-interconnected macroporosity (Chapter 3); (c) improved chemical reactivity and stability (Chapter 4 & 5); (d) suitable biocompatible and osteogenic properties (Chapter 6, 7 & 8); and (e) improved injectability properties (Chapter 7). Moreover, this thesis has also approached ultrasound in order to monitor the early setting stages of ceramic based bone cements to link acoustic and material properties with some intrinsic cement-injectability features (Chapter 9 & 10). Chapter 2 showed that workability, flowing and mechanical properties of ABCs can be improved by adding superplasticizers to the liquid cement phase. The results indicated that superplasticizers can be used to improve the injectability and the strength of apatitic bone cements. Chapter 3 showed that calcium sulfate dihydrate (CSD) crystals can be added into the cement powder phase to modulate the macroporosity of the cement during its setting. This was proved with an alpha-tricalcium phosphate (α-TCP) bone cement. The setting properties of the new biphasic cements resulted from the progressive dissolution-precipitation of α-TCP into calcium-deficient hydroxyapatite (CDHA) crystals and the passive dissolution of the CSD phase, which render porosity homogeneously distributed into an entangled matrix of CDHA crystals. The biphasic cements showed suitable strength for trabecular bone applications. Chapter 4 focused the manufacturing process of α-TCP (α-Ca3(PO4)2), the main cement reactant of most commercial ABCs. It has been shown that if calcium-to-phosphorous (Ca/P) ratio deviated from Ca/P=1.50, the resulting cements had worse setting and hardening properties. These deviations can result from sintering if reactives are not pure from batch to batch; in this case the α-TCP shows no-cement reactivity at all. Chapter 5 approached new solutions to control and improve the chemical reactivity of the α-TCP phase. In this sense, new solid solutions like (3.CaO-1.P2O5)1-x(FeO)x were investigated to replace the α-TCP of the present CPBCs. The results showed that iron modification of α-TCP recovered the chemical reactivity of unreactive α-TCP cements with even better setting and rheological end-cement properties. Chapter 6 focused the attention into the cytocompatibility of the new cement formulations (investigated previously; chapters 3-5). It is showed that the new iron-modified calcium phosphate cements (IM-CPCs) have cytocompatible features (i.e. cells’ adhesion and viability were not affected with culturing time by the iron concentration dose). Chapter 7 concerned a new approach to improve the injectability of α-TCP based bone cements. It has been shown that the addition of iron oxide nanoparticles into the powder phase of α-TCP based cement improved both, the initial injectability and maximum compressive strength of the cement without affecting their physico-chemical setting reactions and their cytocompatibility. Chapter 8 pointed to the cytocompatibility, the biocompatibility and the osteogenic character of new biphasic porous/iron-modified cements (investigated previously; chapters 3-7). The results showed that biphasic cements made of CSD and iron-modified α-TCP had the ability to support cellular colonization in vitro and lead firm bone binding in vivo. It is concluded that these new formulations has cyto- and biocompatible features of interest as further cancellous bone replacement biomaterial for spinal surgery applications such as vertebroplasty or kyphoplasty. Chapter 9 & 10 approached ultrasound as more reliable characterisation technique of the early setting properties of bone cement-like materials than the Gillmore needles standard. This non-destructive technique allowed monitoring the whole setting period of experimental calcium sulphate and calcium phosphate bone cements. The results linked acoustic and material properties with the experimental factors studied and with cement flowing features. It is expected that, after further optimization, ultrasound monitoring should help, in combination with recent approaches that measure certain injectability characteristic for calcium-based bone cements (CBC’s), to set up good practice protocols for CBC’s injection during minimally invasive surgery. Finally, Chapter 11 presents a summary of the major findings of this thesis.

Los cementos de fosfato de calcio son biomateriales utilizados para la regeneración ósea. En esta tesis doctoral se estudia la influencia de la microestructura y la macroporosidad en el comportamiento biológico de un cemento de fosfato de calcio. En la primera parte, se caracterizaron las propiedades físico-químicas y superficiales de dos sustratos de apatita deficiente en calcio con diferente microestructura obtenidos a partir de un cemento de fosfato de calcio (CPC) cuyo principalmente componente es el fosfato tricálcico en fase $\alpha$. % con dos distribuciones de tamaño de partícula distintos. Se estudió la influencia de la microestructura en el comportamiento celular y la adsorción de proteínas como la albúmina, la fibronectina y la lisozima. El uso de dos agentes desorción (EDTA y SDS) permitió evidenciar la influencia de la morfología y tamaño de los cristales de apatita en la fuerza de adhesión de las proteínas estudiadas. Los cultivos celulares con la línea MG-63 mostraron el efecto de la microestructura y el intercambio iónico sobre la proliferación celular. Se observó asimismo una estimulación en la diferenciación celular en uno de los sustratos que fue atribuido a un efecto de la topografía. En la segunda parte, se desarrolló un cemento macroporoso inyectable para aplicaciones médicas, utilizando como agente espumante una solución proteica de albumen. Se optimizó la obtención de la macroporosidad a partir de variables como: la distribución del tamaño de partícula, la relación entre la fase sólida y la fase líquida, la cantidad de agente espumante y la adición de un agente de cohesión como el alginato de sodio para posibilitar su inyección directa en el lugar de implantación. Por último, se demostró mediante estudios \emph{in vivo} en fémur de conejos un mayor potencial de regeneración ósea por parte del cemento macroporoso en comparación con su homólogo microporoso, al obtenerse una mayor cantidad de tejido óseo y una mayor reabsorción en el cemento macroporoso.

Carbon dioxide is considered to be the major source of GHG responsible for global warming; man-made CO₂ contributes approximately 63. 5% to all greenhouse gases. The cement industry is responsible for approximately 5% of global anthropogenic carbon dioxide emissions emitting nearly 900 kg of CO₂ for every 1000 kg of cement produced! Amine absorption processes in particular the monoethanolamine (MEA) based process, is considered to be a viable technology for capturing CO₂ from low-pressure flue gas streams because of its fast reaction rate with CO₂ and low cost of raw materials compared to other amines. However, MEA absorption process is associated with high capital and operating costs because a significant amount of energy is required for solvent regeneration and severe operating problems such as corrosion, solvent loss and solvent degradation. This research was motivated by the need to design size and cost analysis of CO₂ capture process from cement industry. MEA based absorption process was used as a potential technique to model CO₂ capture from cement plants. In this research four cases were considered all to reach a CO₂ purity of 98% i) the plant operates at the highest capacity ii) the plant operates at average load iii) the plant operates at minimum operating capacity and iv) switching to a lower carbon content fuel at average plant load. A comparison among four cases were performed to determine the best operating conditions for capturing CO₂ from cement plants. A sensitivity analysis of the economics to the lean loading and percent recovery were carried out as well as the different absorber and striper tray combinations.

Deterioration of reinforced concrete structures due to reinforcement corrosion is a serious problem that faces concrete infrastructure worldwide. Effect of the rebar corrosion in the shear span on the structural behaviour is not fully addressed in the published literature. This study examined the effects of corrosion of the longitudinal reinforcement in the shear span on the structural behaviour of RC beams and the effectiveness of three rehabilitation schemes on the structural performance of such beams. The experimental program consisted of testing fifteen medium-scale reinforced concrete beams (150mm wide x 350mm deep x 2400mm long) under static load. Test variables included: span to depth ratio, the degree of corrosion and the anchorage end condition and repair schemes. Two span to depth (a/d) ratios were considered: a/d=3.4 with one-point loading and a/d=2.4 with two-point loading. Two anchorage end-conditions were used: bonded or un-bonded reinforcement in the an-chorage zone. Four degrees of corrosion were chosen to simulate minor (2.5% to 5% mass loss), medium (7.5% mass loss), and severe (15% mass loss) degrees of corrosion. Corrosion was induced in the longitudinal reinforcement in the shear-span using accelerated corrosion techniques based on Faradays’ law. Three different repair scenarios were applied. The first scenario included removing the deteriorated concrete, cleaning the corroded steel and patching with a new self-compacting concrete. The second scenario included U-wrapping the beams cross-section using Glass fiber reinforced cement-based composite (GFRCM), and Carbon fiber reinforced cement-based composite (CFRCM) without removing the deteriorated concrete. The third scenario included patch repair and confinement by wrapping with GFRCM or CFRCM. Following corrosion and repair, all specimens were loaded statically to failure. Test results showed no major effect of shear-span corrosion on the flexural behaviour for the beams with end anchorage whereas a noticeable effect on the flexural behaviour was observed for beams with no end anchorage regions. The corrosion degree and the shear span to depth ratio affected the mode of failure for the specimens with no end anchorages. The type of repair significantly affected the overall behaviour of the corroded specimens. An analytical model was proposed and used to predict the load-deflection response of the tested specimens. The program calculated the mid-span deflection for a given load as an integration of the deflection of a series of elements, with the deflection being based on the elongation of the steel reinforcement in each element. A modified bond stress-slip model was incorporated into the calculations to account for the change in bond strength caused by the corrosion and/or confinement that are provided by repairs. The predicted results were in reasonable agreement with the experimental results.

Carbon dioxide is considered to be the major source of GHG responsible for global warming; man-made CO₂ contributes approximately 63. 5% to all greenhouse gases. The cement industry is responsible for approximately 5% of global anthropogenic carbon dioxide emissions emitting nearly 900 kg of CO₂ for every 1000 kg of cement produced! Amine absorption processes in particular the monoethanolamine (MEA) based process, is considered to be a viable technology for capturing CO₂ from low-pressure flue gas streams because of its fast reaction rate with CO₂ and low cost of raw materials compared to other amines. However, MEA absorption process is associated with high capital and operating costs because a significant amount of energy is required for solvent regeneration and severe operating problems such as corrosion, solvent loss and solvent degradation. This research was motivated by the need to design size and cost analysis of CO₂ capture process from cement industry. MEA based absorption process was used as a potential technique to model CO₂ capture from cement plants. In this research four cases were considered all to reach a CO₂ purity of 98% i) the plant operates at the highest capacity ii) the plant operates at average load iii) the plant operates at minimum operating capacity and iv) switching to a lower carbon content fuel at average plant load. A comparison among four cases were performed to determine the best operating conditions for capturing CO₂ from cement plants. A sensitivity analysis of the economics to the lean loading and percent recovery were carried out as well as the different absorber and striper tray combinations.

Saskatchewan Ministry of Highways and Infrastructure (MHI) is responsible for maintaining approximately 26,100 km of two lane equivalent highways network. Most highways in Saskatchewan are constructed primarily of granular materials. Granular materials serve various purposes in a pavement structure. In particular, granular materials distribute stress within the road structure and reduce the stress applied to the subgrade. Granular materials also mitigate pumping of subgrade fines into surfacing materials, as well as provide drainage for the pavement structure.<p>As a result of the rapid deterioration of roadways and the increasing highway traffic, a significant portion of the Saskatchewan highway system is in need of rehabilitation in the next couple of decades. However, increasing costs associated with road construction as well as budget constraints render many conventional rehabilitation solutions untenable in many applications. In addition, the depletion of quality aggregate also exists in many areas of Saskatchewan. Given that much of Saskatchewan granular pavement system will be in need of strengthening in the next few decades, there is a need to apply new cost-effective and aggregate-preserving pavement rehabilitation technologies such as cold in-place recycling and base strengthening.<p>The goal of this research is to improve the engineering design and performance of recycled and stabilized granular base systems under Saskatchewan field state conditions. The specific objectives of this research are to characterize the conventional laboratory behaviour, moisture sensitivity, and mechanistic behaviour of various granular base strengthening systems in the laboratory, to characterize the structural responses of various granular base strengthening systems in the field, and to evaluate the pavement thickness design and responses of various granular base pavement structures.<p>This research is based on a cold in-place recycling and base stabilization project undertaken by Saskatchewan MHI in fall 2006. Control Section (C.S.) 15-11 between km 5.0 and km 8.0 was selected as a typical thin granular pavement under primary weight loadings that required strengthening. Unstabilized granular base, cement stabilized granular base, and cement with asphalt emulsion stabilized granular base were constructed and evaluated in this research. Materials employed on C.S. 15-11 were sampled and prepared for the various laboratory tests performed in this research. Conventional tests performed included sieve analysis, Atterberg limits, sand equivalent, standard proctor compaction, and California bearing ratio strength and swell test. Advanced mechanistic and moisture sensitivity testing included indirect tensile strength, moisture capillary rise and surface conductivity, unconfined compressive strength, and rapid triaxial frequency sweep testing.<p>The cement and cement with emulsion asphalt stabilization of the granular base were found to improve the conventional, mechanical and moisture susceptibility properties of in situ C.S. 15-11 granular base materials. The cement stabilization applied on C.S. 15-11 provided a high degree of improvement relative to the cement with emulsion stabilization. The cement stabilization was found to be relatively easy to apply in construction, whereas the cement with emulsion stabilization was more difficult, particularly due to the problems associated with cold temperatures during late season construction.<p>The rapid triaxial tester (RaTT) was found to be a practical and useful apparatus to characterize the mechanistic constitutive behaviours of granular materials. The C.S. 15- 11 in situ unstabilized base was found to have the poorest mechanistic behaviour among all three granular bases on C.S. 15-11, as expected. Cement stabilization improved the mechanistic behaviour of the in situ material significantly by providing the highest mean dynamic modulus, lowest mean Poissons ratio, lowest mean radial microstrain, and the lowest mean phase angle. The cement with emulsion asphalt stabilization also provided a considerable improvement on mechanistic behaviour of C.S. 15-11 granular base materials. However, the degree of improvement was less than the cement stabilization system.<p>Non-destructive falling weight deflection measurements taken across the field test sections showed that the stabilization systems yielded a significant improvement of primary structural response profiles across the C.S. 15-11 test sections after stabilization. The cement stabilization system was found to yield the most significant structural improvements among all the test sections constructed on the C.S. 15-11. The deflection measurements taken in 2007 after hot mix asphalt paving further identified that the unstabilized system is more sensitive to the freeze-thaw effects relative to cement stabilization and cement with emulsion stabilization systems.<p> This research also showed that the Saskatchewan MHI structural design system is not applicable to the design of stabilized granular base systems. Evaluation of the thickness design for C.S. 15-11 showed the unstabilized and the cement with asphalt emulsion stabilized test section met the criterion of fatigue cracking, but failed to meet the criterion of structural rutting in MHI design system. However, the cement stabilized section met both fatigue cracking and rutting criteria. The structural evaluation revealed that mechanistic pavement response analysis and validation are necessary in the thickness design of stabilized granular systems such as C.S. 15-11, where traditional MHI design system is not applicable. This research employed finite element modeling and linear elastic pavement modeling software to determine the maximum shear stresses within granular base under typical Saskatchewan stress state conditions. The maximum shear stress values were found to locate on top of granular base courses under the applied circular loading edges ranging from 177 kPa to 254 kPa. These maximum shear stresses within the C.S. 15-11 test section granular base courses under field stress states were compared to maximum shear stresses occurring within samples measured by rapid triaxial testing performed in this research. The comparison showed that the ranges of shear stresses applied in the laboratory RaTT testing were close to shear stresses of granular bases in the field computed from modeling. Therefore, this research showed a good correlation of lab RaTT testing and field results for granular pavements.<p>In summary, this research met the objectives of mechanistically evaluating various granular base stabilization systems in Saskatchewan by means of various laboratory testing, non-destructive field testing, as well as mechanistic modeling and analysis. This research provided valuable data and showed considerable potential for improving design, construction, and QA/QC of conventional and stabilized granular base systems in Saskatchewan.

This multi-scale investigation aimed to provide new knowledge and understanding of creep and shrinkage of high performance lightweight concrete (HPLC) by assessing prestress losses in HPLC prestressed members in a large-scale study; by quantifying the effect of the constituent materials and external conditions on creep and shrinkage in a medium-scale study; and by improving the fundamental understanding of creep and shrinkage in a small-scale study. Creep plus shrinkage prestress losses were between two and eight times lower than those estimated for the design standards and approximately 50% of those measured in similar strength normal weight high performance concrete girders. The lower creep and shrinkage exhibited by HPLC was found to be caused by a synergy between the pre-soaked lightweight aggregate and the low water-to-cementitious material ratio matrix. That is, the water contained in the lightweight aggregate contributes to enhance hydration by providing an internal moist curing. The water in the aggregate also contributes to maintain a high internal relative humidity which reduces or eliminates autogenous shrinkage. This higher internal relative humidity also reduces creep by preventing load-induced water migration. Finally, lightweight aggregate exhibits a better elastic compatibility with the paste than normal weight aggregate. This improved elastic matching and the enhanced hydration are believed to reduce peak deformations at the ITZ which further decreases creep and shrinkage.

Grinding of clinker is the last and most energy-consuming stage of the cement manufacturing process, drawing on average 40% of the total energy required to produce one ton of cement. During this stage, the clinker particles are substantially reduced in size to generate a certain level of fineness as it has a direct influence on such performance characteristics of the final product as rate of hydration, water demand, strength development, and other. The grinding objectives tying together the energy and fineness requirements were formulated based on a review of the state of the art of clinker grinding and numerical simulation employing the Markov chain theory. The literature survey revealed that not only the specific surface of the final product, but also the shape of its particle size distribution (PSD) is responsible for the cement performance characteristics. While it is feasible to engineer the desired PSD in the laboratory, the process-specific recommendations on how to generate the desired PSD in the industrial mill are not available. Based on a population balance principle and stochastic representation of the particle movement within the grinding system, the Markov chain model for the circuit consisting of a tube ball mill and a high efficiency separator was introduced through the matrices of grinding and classification. The grinding matrix was calculated using the selection and breakage functions, whereas the classification matrix was defined from the Tromp curve of the separator. The results of field experiments carried out at a pilot cement plant were used to identify the model's parameters. The retrospective process data pertaining to the operation of the pilot grinding circuit was employed to validate the model and define the process constraints. Through numerical simulation, the relationships between the controlled (fresh feed rate; separator cut size) and observed (fineness characteristics of cement; production rate; specific energy consumption) parameters of the circuit were defined. The analysis of the simulation results allowed formulation of the process control procedures with the objectives of decreasing the specific energy consumption of the mill, maintaining the targeted specific surface area of the final product, and governing the shape of its PSD.

Most engineering as well as pavement materials are composites composed of two or more components to obtain a variety of solid properties to support internal and external loading. The composite materials rely on physical or chemical properties and volume fraction of each component. While the properties can be identified easily, the volume fraction is hard to be estimated due to the volumetric variation during the performance in the field. Various test procedures have been developed to measure the volume fractions; however, they depend on subjective determination and judgment. As an alternative, electromagnetic technique using dielectric constant was developed to estimate the volume fraction. Empirical and mechanistic approaches were used to relate the dielectric constant and volume fraction. While the empirical models are not very accurate in all cases, the mechanistic models require assumptions of constituent dielectric constants. For those reasons, the existing approaches might produce less accurate estimate of volume fraction. In this study, a mechanistic-based approach using the self consistent scheme was developed to be applied to multiphase materials. The new approach was based on calibrated dielectric constant of components to improve results without any assumptions. Also, the system identification was used iteratively to solve for dielectric parameters and volume fraction at each step. As the validation performed to verify the viability of the new approach using soil mixture and portland cement concrete, it was found that the approach has produced a significant improvement in the accuracy of the estimated volume fraction.

Fly ashes generated from fluidized bed combustion of low calorific value, high ash content Turkish lignites are characterized by high content of acidic oxides, such as SiO2, Al2O3 and Fe2O3, varying in the range 50-70%. However, there exists no study for the investigation of the possibility of using these ashes as concrete admixture. Therefore, in this study, characterization of fly ashes from fluidized bed combustion of a Turkish lignite and evaluation of these fly ashes as a substitute for Portland cement in production of pastes and mortars were carried out. The samples were subjected to chemical, physical, mineralogical and morphological analyses. Results of chemical and physical analyses of three fly ash samples show that they satisfy the requirements of EN 197-1, EN 450 and ASTM C 618, except for CaO and SO3, owing to high content of acidic oxides of these ashes contrary to majority of FBC fly ashes reported in the literature. In addition to characterization studies, water requirement, compressive strength, setting time and soundness tests were also performed for 10%, 20% and 30% fly ash-cement blends and the reference cement. Results of these tests reveal that the blends meet compressive strength, setting time and soundness requirements of ASTM C 595 without any pre-hydration treatment, and that fly ashes from fluidized bed combustion of Turkish lignites have significant potential for utilization as an admixture in manufacture of blended cements.