It is quite well known that fracture behavior of concrete is complex and is influenced by several factors. Apart from material properties, geometric parameters influence fracture behavior and one notable phenomenon is size effect. The existence of the size effect in concrete is well known and various attempts to model the behavior is well documented in literature. However the approach by Bazant to describe the size effect behavior in concrete has received considerable attention. The major advantage of developing the size effect law for concrete is the ability to describe the fracture behavior (namely failure strength) of large size structures inaccessible to laboratory testing. The prediction of size effect is done on the basis of laboratory testing of small size geometrically similar structures. In all the models developed earlier heterogeneity of concrete has not been quantitatively simulated. Hence, the complete description considering heterogeneity in concrete is attempted using the lattice model to understand size effect behavior in concrete. In the present study, a detailed description of the heterogeneity in concrete is at- tempted by 3D lattice structure. Analytical treatment to gain insights to fracture behavior is difficult and hence a numerical approach capable of handling the het- erogeneous nature of the material is adopted. A parametric study is performed to understand the influence of various model parameters like mesh size, failure criterion, softening model. The conventional size effect studies for 2D geometrically similar structures are performed and a comparison is done with experimentally observed behavior. The variation of fracture process zone with respect to structure size is observed as the reason for size effect. The influence of variation in properties of ag- gregate, matrix and interface are studied to explain the deviation in pre-peak and post-peak response. A statistical study is performed to establish the size dependence of linear regression parameters (Bf ‘t and D0) which are used in Bazant size effect law. An analytical framework is also proposed to substantiate the above results. Size effect in concrete is generally attributed to the effect of depth viz. the dimension in the plane of loads. However although the effect of thickness viz. a dimension in a plane perpendicular to that of the loads is not considered in concrete. The same is quite well known in fracture of metals. Therefore the variation in grading of aggregates along with the influence of thickness on fracture behavior is analysed. To understand the thickness effect a comparison of 2D and 3D geometrically similar structures is performed to understand the effect of thickness on fracture parameters. Heterogeneity is a matter of scale. A material may be homogeneous at a coarser scale while at a finer scale it is heterogeneous. Hence only way to capture the effect of the behavior at micro level on the behavior at meso level particularly in a heterogeneous material like concrete is by a multi-scale modelling. The best numerical tool for multiscale model of a heterogeneous material is lattice model. The heterogeneous nature of concrete is not just due to the presence of aggregates but is evident right from the granular characteristics of cement. The hydration of cement grain leads to the development of products with varying mechanical and chemical properties. As the micro-crack initiation and development of thermal cracking is observed at the micron level, understanding of hydration behavior in concrete can be thought of as a pre-requisite for complete understanding of fracture behavior. The properties of matrix and interface observed during hydration modelling can also be used as an input for fracture predictions at upper scale models (eg. mesoscale). This can also be used to study the coupling of scales to understand the multi-scale fracture behavior in concrete. A numerical model is hence developed to study the hydration of concrete. Due to the existence of complex mechanisms governing the hydration behavior in con- crete and the large number of parameters affecting its rate, the hydration of a grain is assumed to proceed in isolation. A single particle hydration model is developed to study the hydration of isolated grain. A shrinking core model usually used to describe the burning of coal is adopted as a base model for analytically describing the hydra- tion behavior. The shrinkage core model in literature is modified to be applicable to hydration of cement matrix. The effect of particle diameter as well as changing water concentration is incorporated into the model whereas the influence of reduction in pore sizes as well as the effect due to embedding of particles and the constraint due to hydration of neighbouring particles is accounted using correction factor. The effect of temperature on rate of hydration is considered to be independent of the physical and chemical aspects of grain. Hence a temperature function developed using Arrhe- nius equation and activation energy is incorporated separately. The porous nature of reaction products affects the diffusivity leading to the development of tortuous path for flow of water through the hydrated portion. Knowing the tortuosity it is possible to obtain the diffusivity which in turn can be used as an input to the lattice model. An algorithm is developed to determine the tortuosity in diffusion of water through the reaction products. The tortuosity depends on the distribution of pores in the hydrated system. This requires the use of simulation technique to generate the initial position of voids. A simulation technique is also required to generate the initial con- figuration of hydrating cement system. In order to generate the initial configurations of such systems a numerical technique to generate a large scale assembly of particles is proposed. In the present work, parameters of Bazant's size effect law Bf’t and D0 are shown to depend on structure size and heterogeneity. The span to thickness ratio of the structure increases fracture energy and also substantially influences the response of structure. The variation in failure load occurring due to the heterogeneous nature of the material is shown to follow a normal distribution. The fracture behavior of a material is seen to be influenced strongly by the variation in the strength of matrix and interface. The model proposed to describe the hydration process of cement can be used to determine the properties of matrix and interface. The degree of hydration as well as the embedded centre plane area can be adopted as a measure of strength of matrix and interface. The understanding of the hydration process and the wall effect around the aggregate surface can possibly improve our ability to predict the strength of interface. The material strength of the interface is certainly a necessary input to the lattice model. Infact experimental determination of interface strength is a lot more complicated than the present numerical approach. The only weakness of the present numerical approach is the assumption regarding certain empirical constants which of course may be improved further. Understanding of material behavior can be further improved if a molecular dynamics approach is adopted to describe the hydration behavior of cement. The approach via molecular dynamics is suggested as a problem for future research.

Plasticizing and superplasticizing admixtures are the key components of nearly every concrete. These admixtures improve workability of mortar and fresh concrete which lead to facilitation of depositing and compaction. Adding of plasticizers or superplasticizers enables to change properties of fresh and hardened concrete, especially to reduce water-cement ratio, thereby increasing strength and durability of concrete or to improve other properties. The main aim of this thesis is to monitor the effect of plasticizing admixtures and their dosage on the rheology and hydration of concrete with emphasis on the development of hydration temperature. The other goal is to examine their strength qualities. Behaviour of plasticizing admixtures is analysed at first on cement pastes, as simple systems, and then verified on concrete.

This diploma thesis deals with the study of the binder mortar based on calcium sulphate. The theoretical part deals with the general theory of sulfate binders and anhydrite mortars. Further attention is paid to the standard requirements for these binders and mortars and the evaluation of the existing research at the THD Institute. The experimental part is devoted to research of anhydrite mortar for the production of self-leveling mixtures. The subject of the research was the design of a suitable activating agent, performing technological tests on designed anhydrite pastes and mortars and monitoring hydration.

Master of Science / Department of Civil Engineering / Kyle Riding / Concrete is the most widely used construction material. Concrete strength and durability develop from a series of exothermic reactions involving water called hydration. Long-term durability and performance of concrete is very much dependent on the early hydration behavior of cementitious materials. This study examined the effects of curing temperature and access to moisture on the early age reaction rate of cementitious materials, and methods for quantifying these effects. Apparent activation energy (Ea) relates the effects of temperature on the cement hydration reaction. There are various methods and calculation techniques for estimating Ea that result in greatly varying values. Cement paste and mortar are often used to calculate Ea and used later for concrete. Ea values were calculated using cement mortar and paste by isothermal calorimetry and showed excellent correlation. This validates the use of Ea based on cement paste in modeling concrete behavior. Ea values were also calculated by chemical shrinkage and it showed potential for use in calculating Ea. Cementitious materials need free water to be available for hydration to continue. Curing with either waxy curing compounds or ponded water are common practices. The thickness of distilled water, lime-saturated water, and cement pore water used as a curing method affects the rate of hydration. Water-cementitious material ratio (w/cm) and sample depth affect the performance of water curing, with low w/cm being the most significant. Partial replacement of sand by fine lightweight aggregate also improves the hydration of cementitious material much more than conventional water ponding. Curing compounds showed improvements in cement hydration compared to uncured samples.

Understanding the physiological and behavioural reasons that result in voluntary water intake and the volume subsequently consumed in both the work place and during and following an exercise setting can provide further information on water balance and the necessity and requirements of water intake. The first study (Chapter 3) aimed to assess hydration status in the adult population at the start and end of a working day and the amount of water from beverages that was consumed. Urine osmolality and urine specific gravity (USG) suggested a large proportion of subjects arrived (osmolality: 54%; USG: 53%) and left (osmolality: 35%; USG: 33%) work in a hypohydrated state, with variation between subjects in the same and different places of work. Reported water intake varied between groups with males consuming more than females. To further examine hydration status it was proposed to assess the use of capillary blood sampling as an alternative to more restrictive venous blood sampling (Chapter 4), however, despite tracking changes in blood parameters in a similar capacity, the inconsistencies of results suggested capillary blood sampling could not be used reliably. The remaining chapters in the thesis examined voluntary water intake. In Chapter 5 this was during and following exercise in the cold. Less water was consumed compared to exercise in a warm environment and there was an indication of a blunted thirst response in the cold. Following high intensity intermittent exercise, more water was voluntarily consumed during a one hour recovery period compared to when continuous exercise of the same average power output was performed (Chapter 6). Following exercise there was increased serum osmolality, serum sodium concentration, plasma vasopressin concentration and blood lactate concentration compared to baseline values. The relative contribution that decreasing blood lactate concentrations and water intake during the recovery period had on serum osmolality could not be determined, so the study in Chapter 7 was carried out. The time period during which voluntary water intake was allowed was manipulated during a recovery period following a period of high intensity intermittent exercise. Allowing water intake for the full hour, the final 30 minutes or not at all, resulted in similar decreases in serum osmolality throughout the duration of the recovery period. A combination of finishing the period of exercise allowing plasma volume restoration, reduction in blood lactate concentration, reduction in serum sodium concentration, a restoration of blood lactate concentration and water intake appeared to contribute to decreased serum osmolality. Sensations of thirst were the main stimulants of voluntary water intake (Chapters 3, 5, 6 and 7), however, following exercise, sensations of thirst resulted in water consumption despite the majority of subjects not losing enough water (>2% body mass loss) to require additional rehydration. In this thesis, it can be concluded that voluntary water intake differs between individuals, between work environments, during and following exercise in different environments and following different exercise intensities. Water intake is generally initiated by sensations of thirst arising from physiological and behavioural mechanisms even in the absence of significant hypohydration and will reduce once satiated.

Statybos pramonėje, mišiniuose vis plačiau naudojamas įvairus tiek natūralių tiek sintetinių ceolitų spektras. Atliktuose tyrimuose buvo naudojamas sintetinis ceolitas – hidrosodalitas (Na6+x(SiAlO4)6(OH)x•nH2O), modifikuotas hidrosodalitas ir fero silicio gamybos atlieka - SiO2 mikrodulkės. Su pastaraisiais pucolaniniais priedais tiriama sąveika su cementu, nustatyta kaip keičiasi cemento stiprio, tankio ir įgėrio savybės. Tyrimai atlikti ruošiant bandinius su 2%, 5%, 10% ir 15% pucolaninių priedų masės santykiais. Atlikus tyrimus nustatyta, kokia daroma įtaka cementinės masės hidratacijos temperatūrai. Nustatytas bandinių stiprumas, tankis po 3, 7 ir 28 parų. Nustatytas bandinių įgėris po 28 parų. Cementinio akmens gniuždomasis stipris nenaudojant priedo ir ilginant hidratacijos trukmę nuo 3 iki 28 parų didėja nuo 59 iki 80 MPa. Panaši priklausomybė stebima ir cementiniuose bandiniuose su pucolaniniais priedais. Ilgėjant hidratacijos trukmei stipriai gniuždant didėja. Tirtose sąlygose didžiausią stiprį gniuždant turėjo bandiniai su 10 % modifikuoto hidrosodalito priedo po 28 parų, gniuždomasis stipris padidėja iki 101 MPa. Galima daryti prielaidą, kad hidrosodalito, modifikuoto hidrosodalito ir SiO2 mikrodulkių pucolaninės savybės pasireiškia ne iš karto, bet išryškėja po ilgesnes hidratacijos trukmės, t. y. po 28 parų. Vykstant hidratacijai nuo 16 iki 28 parų, įgėris sumažėja nuo 13,41% iki 9,04% (esant 2% hidrosodalito kiekiui). Naudojant 5% SiO2 mikrodulkių kiekį... [toliau žr. visą tekstą] / Construction industry is increasingly being used in combination and variety of natural and synthetic zeolites spectrum. A study carried out using synthetic zeolite - hydrasodalite (Na6 + x (SiAlO4) 6 (OH) x • nH2O) modified hydrasodalite silicon production and Fair play - fume SiO2. With the recent pozzolanic additives investigated the interaction with cement, concrete changes in the strength, density and retention properties. Studies carried out in the preparation of the samples with 2%, 5%, 10% and 15% by weight of pozzolanic additives relations. It was determined, which affect the weight of cement hydration temperature. Fixed specimens the strength and the density of 3, 7 and 28 days. Set of samples absorption after 28 days. Compressive strength of cement stone without the use of additive and longer duration of hydration from three to 28 days increased from 59 to 80 MPa. A similar dependence is observed in samples with cement and pozzolanic additives. Hydration with increasing duration of the compressive strength increases. To examine the conditions had the highest compressive strength of samples with 10% modified hydrasodalite additives after 28 days, compressive strength increases to 101 MPa. It can be assumed that hydrasodalite, and SiO2 modified hydrasodalite fume pozzolanic properties are not immediate, but come on after a longer duration of hydration, etc. Y. after 28 days. During the hydration from 16 to 28 days, absorption decreases from 13.41% to 9.04% (at 2%... [to full text]

Adequate fluid consumption is central to human survival. Previous literature suggests that there some misconceptions regarding hydration and fluid balance in some populations. Available data also show that the role of thirst sensations in maintaining fluid balance in different settings is also equivocal. Therefore, this thesis aimed to examine the perception of hydration, thirst and fluid intake in freeliving populations, to examine the feasibility of thirst as a marker of hydration status and to investigate the effect of thirst related sensations on fluid balance in resting and exercising individuals under different ambient temperatures. The findings in this thesis (Chapter 3) show that individuals who work within the fitness industry demonstrated substantial knowledge about drinking practices, hydration status and health consequences of water consumption, but lack understanding on the type of beverages that adequately hydrate the body. Further, thirst perception and mood states did not affect (P>0.05) the fluid intake in free living individuals (Chapter 4) and resting individuals under cool and warm exposure (Chapter 6), but some other factors such as subjective feelings of mouth dryness and the extent of hydration status might influence the fluid intake behaviour in these populations. In addition, following ingestion of flavoured carbohydrate drinks, thirst sensations was rated lower over time (P<0.05) during exercise in the cool, but was higher over time in the warm temperature (Chapter 7). Moreover, subjective feelings related to dehydration such as mouth dryness, thirst perception, desire to drink (water pleasantness) and hunger rating could be used as index of hydration status to signify at least a 1% body mass loss due to food and fluid restriction in resting individuals (Chapter 5). In conclusion, the findings in this thesis provide some new insight with respect to hydration, thirst and fluid balance in different populations under different settings. Nevertheless, some inconclusive findings regarding the role of thirst related sensations in fluid balance require further investigations.

Objectives. This study aimed to provide data on water intake from food and beverages of free-living adults in their natural environment, and investigate how this is affected by physiological, psychological, social and environmental factors. A further aim was to monitor the hydration status of free-living adults and relate this data to water intake. Methods The consumption of all food and beverages was recorded in a diary over three consecutive days by 80 healthy adults (40 males, 40 females), aged 18 to 65 years, who were instructed to continue their normal eating and drinking habits and lifestyles throughout the study. The data was analysed to determine total daily water intake and how this was affected by time of day, day of the week, presence of others, location of consumption, age and subjects mood. A further 20 healthy subjects (10 males, 10 females) repeated these procedures but also had blood samples taken for monitoring of blood indices (haemoglobin concentration, haematocrit, sodium concentration, and potassium concentration) and provided urine samples for the measurement of urine indices (volume, colour, specific gravity, osmolality and sodium, potassium, chloride, and creatinine concentrations). Results The total volume of water consumed by the 80 subjects was 2229  882 ml/day (mean  standard deviation). Females tended to consume more water than males (2402  827 ml/day vs 2056  911 ml/day, P = 0.079). Similar volumes were consumed by the additional 20 subjects in the hydration status study. Females appeared euhydrated; males appeared mild dehydrated, having a higher morning and 24-hour urine specific gravity and osmolality than females (P < 0.05, respectively). Conclusions The mean daily total volume of water consumed by females in this study was greater than the adequate intake value set by the European Food Safety Authority; for males it was lower. Females were euhydrated during the study but males tended to be mild dehydrated, reflecting their comparative water intakes.

Three sets of concrete blocks were cast to investigate the effects of natural exposure conditions, at the macro and microclimate scale, and field curing on the performance and durability of OPC and OPCjGGBS concretes. These are termed the Loughborough winter series, the Loughborough summer series and the Muscat summer series. Three concrete mixes were investigated in the two Loughborough series (30 and 50 MPa OPC concrete mixes and a 30 MPa OPCjGGBS concrete mix) and two in the Muscat weather series (the two 30 MPa concretes). A group of specimens were cast with each mix consisting of 600 x 500 x 150mm concrete blocks plus control cubes and prisms. The samples were cured in-situ and exposed to a range of curing methods and microclimates. Surface zone properties (up to 50mm depth) were evaluated by air permeability, sorptivity, carbonation, thermogravimetry (TG) and mercury intrusion porosimetry (MIP) tests, conducted after 3 and 12 months of site exposure. The results revealed distinct variations due to macroclimate, microclimate, curing, concrete type and age. The air permeability, sorptivity and carbonation of the concrete exposed under moderate and rainy conditions of a Loughborough summer season were lower than identical concrete cast and cured during a very cold and dry Loughborough winter season. Further, the sorptivity of concrete subjected to the hot and dry climatic conditions of Muscat was significantly higher than companion samples subjected to the temperate Loughborough climate. Significant variations in properties were observed within the two sides of the same concrete element, each subjected to a different microclimate. The air permeability, sorptivity, carbonation and porosity were reduced with increased hessian curing duration. However, premature drying of wet hessian during curing had an adverse effect on concrete quality as this produced concrete of higher permeability and carbonation than non-cured concrete. The application of controlled permeability formwork was effective in improving the concrete's sub-surface properties. The curing affected zone (CAZ) extended to approximately 20mm below the surface of the concrete that was exposed to the Loughborough winter and summer climate, and 40-50mm for the concrete exposed to the Muscat climate, with notable variation in properties due to climate and curing. The TG and MlP results provided insights into the mechanisms associated with the variations in the three concrete's properties due to natural field exposure.

This project was undertaken to gain a better understanding of the hydration behaviors of gas phase ions from solutions containing amino acids and peptides. In order to characterize their hydration behavior, the molecules of interest in solutions were first converted into gas phase ions by electrospray ionization (ESI). The completely desolvated ions were then deliberately dispersed into an inert bath gas, usually nitrogen, containing accurately known concentrations of solvent vapor. The resulting mixtures of ions and bath gas were subsequently passed into a vacuum chamber by way of an adiabatic supersonic free jet expansion. The cooling during that expansion caused solvation of the ions, the extent of which was determined by a quadrupole mass analyzer. Mass analysis of the solute ions in the absence of vapor showed peaks with the mass to charge ratios corresponding to the desolvated ions. On the other hand, mass spectrometric analyses of ions in the presence of solvent vapor showed sequences of peaks corresponding to the solvated ions with varying numbers of water molecules. The extent of the ion solvation was controlled by varying the concentration of solvent vapor in the bath gas. Two different scales were proposed for the evaluation of the relative affinities of amino acids for water molecules. One was based primarily on the assumption that the affinities of amino acids for water molecules are directly proportional to their gas phase solvation rate constants (k). An alternative approach produced an affinity scale based on the extent of ion hydration occurred during the free jet expansion. It was found that the addition of a polar solvent vapor to the bath gas at low concentrations substantially enhanced the production of the bare solute ions from the evaporating charged droplets. This remarkable result not only provided a means to increase the ion production and thus detection sensitivity of mass spectrometric analyses, but also yielded important information regarding the ion formation mechanism of ESI. Additional studies revealed that the extent of the increase in ion yield was directly related to the charge state and molecular weight of the solute ions. In sum, this evidence strongly indicated that gas phase ions produced from charged droplets, as in electrospray ionization, must proceed by the sequence of events assumed in the Ion Evaporation Model proposed by Iribarne and Thomson rather than in the Charged Residue Model originally proposed by Malcolm Dole and coworkers. The hydration behaviors of electrospray ions from peptides with similar primary amino acid sequences and capable of forming ions with more than one charge state were also investigated. In a study with dipeptides, the extent of hydration was found to vary widely and to depend not only on the chemical composition of the ions but also on their configurations and charge states. The results obtained with lysine oligomers clearly indicated that the number of charges on an ion played an important role in the solvation process. An exception to this generalization was found in an experiment with multiply protonated pentalysine ions. For example, the quadruply protonated monomers of that species were found to undergo charge reduction via proton exchange with the surrounding water molecules in such a way as to maximize the distance between charges on the molecule, thereby reducing the internal repulsive forces.The hydration study of angiotensin II and III showed that while the former has an additional hydrophilic amino acid on the N-terminus, the latter peptide was more hydrophilic. This result suggests that the hydrophilicities of peptides are not a simple sum of the hydrophilicities of the individual amino acid components. As further evidence of interaction complexity, the Magic Number Clusters containing 21 water molecules were obtained with the doubly protonated angiotensin III, but not with the doubly protonated angiotensin II. Taken together, these observations seem to indicate that the multiply charged ions of angiotensin II and III had different structural conformations.