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No / Hydration of five Roman and American natural cements was analyzed using X-ray diffraction, mercury intrusion porosimetry, and scanning electron microscopy of cement pastes. Two cements were prepared in the laboratory by burning marls from geological sources in Poland (Folwark) and Austria (Lilienfeld). The selection of raw materials and burning conditions were optimized so that the hydraulic nature and appearance of the final burnt materials matched as closely as possible historic Roman cements widely used in the 19th and the beginning of the 20th centuries in Europe to decorate buildings. Three other cements are produced commercially: quick setting Prompt cement from Vicat, France, and Rosendale cements from Edison Coatings Inc., USA. The hydration of the cements studied was shown to comprise two distinct stages. The immediate setting and early strength is due to the formation of calcium aluminum oxide carbonate (or sulfate) hydroxide hydrates. The development of long-term strength is brought about by the formation of calcium silicate hydrates. Similarities and differences between the individual cements are discussed.

No / The presence of free water in mortars destined for silo or bagged storage can lead to the degradation of the binder phase. Such water may be present as a result of using wet, as-delivered sand or as a consequence of prior processes such as de-activation of Roman cement. Thus, water must be removed from the system prior to storage. Part 1 of this paper describes the control of a technique by which quicklime is added to the wet system which principally dries it by both slaking the quicklime and evaporation as a consequence of the exothermic slaking reaction. Two examples of mortars are presented in which excess water is removed from the system by the inclusion of quicklime. In the first, the water is present in the as-delivered sand and the binder is a combination of the slaked lime and ggbs. In the second, the water remains after pre-hydration of a Roman cement which is a process to retard its rapid setting characteristics. It is shown that optimally dried mortars are not subject to degradation following storage of both mortar types. (C) 2015 Elsevier Ltd. All rights reserved.

This dissertation describes new methods for measuring surface forces using evanescent waves, and applications to non-DLVO forces. An evanescent wave, generated at a solid-liquid interface, is scattered by AFM tips or particles attached to AFM cantilevers. The scattering of this wave is used to determine absolute separation between surfaces and/or the refractive index as a function of separation in AFM measurements. This technique is known as evanescent wave atomic force microscopy (EW-AFM). The scattering of an evanescent wave by Si3N4 AFM tips is large and decays exponentially with separation from a refractive index boundary. Thus, scattering is a useful method for measuring the separation between a Si3N4 tip and sample. This method has been used to measure the absolute separation between a tip and sample in the presence of an irreversibly adsorbed polymer film. Measurement of the film thickness and time response of the polymer to applied loads has also been studied. These measurements are not possible using current AFM techniques. In addition to measurements in polymer systems, the simple scattering profile from Si3N4 tips was used to re-examine short range hydration forces between hydrophilic surfaces. Results presented in this thesis suggest this force does not depend on the hydrated radius of the ion between glass and silicon nitride. The scattering generated by a Si3N4 tip has also been used to measure the refractive index of bulk fluids and thin films between hydrophobic surfaces. Based on these results, I have shown that a long-range attraction between hydrophobic surfaces is accompanied by an increase in the refractive index between the tip and surface. From this I have concluded that the attractive force, measured in this study, is the result of an increase in the concentration of organic material between surfaces. Finally, I have shown that the scattering profile depends on the material and size of the scattering object. Scattering from silicon nitride tips is exponential with separation. In contrast, the scattering profile from silicon tips, which are similar in size and geometry, is not a simple exponential. The scattering profile of larger spherical particles attached to cantilevers is also not exponential. It is approximately the sum of two exponentials. The functional form of the scattering profile with separation is consistent with the transmission of evanescent light through flat planar films. This result would suggest that a re-examination of the separation-dependence of scattering in TIRM measurements is necessary. / Ph. D.

One of the essential requirements of biomolecular modeling is an accurate description of water as a solvent. The challenge is to make this description computationally facile -- reasonably fast, simple, robust and easy to incorporate into existing software packages, yet accurate. The most rigorous procedure to model the effect of aqueous solvent is to explicitly model every water molecule in the system. For many practical applications, this approach is computationally too intense, as the number of required water atoms is on an average at least one order of magnitude larger than the number of atoms of the molecule of interest. Implicit solvent models, in which solvent molecules are replaced by a continuous dielectric, have become a popular alternative to explicit solvent methods. However, implicit solvation models often lack various microscopic details which are crucial for accuracy. One such missing effect that is currently missing from popular implicit models is the so called effect of charge hydration asymmetry (CHA). The missing effect of charge hydration asymmetry -- the asymmetric response of water upon the sign of solute charge -- manifests a characteristic, strong dependence of solvation free energies on the sign of solute charge. Here, we incorporate this missing effect into the continuum solvation framework via the conceptually simplest Born equation and also in the generalized Born model. We identify the key electric multipole moments of model water molecules critical for the various degrees of CHA effect observed in studies based on molecular dynamics simulations using different rigid water models. We then use this gained insight to incorporate CHA first into the Born model, and then into the generalized Born model. The proposed framework significantly improves accuracy of the hydration free energy estimates tested on a comprehensive set of varied molecular solutes -- monovalent and divalent ions, small drug-like molecules, charged and uncharged amino acid dipeptides, and small proteins. We finally develop a methodology to resolve the issue with unacceptably large uncertainty that stems from a variety of fundamental and technical difficulties in experimental quantification of CHA from charged solutes. Using the proposed corrections in the continuum framework, we untangle the charge-asymmetric response of water from its symmetric response, and further circumvent the difficulties by extracting accurate estimate propensity of water to cause CHA from accurate experimental hydration free energies of neutral polar molecules. We show that the asymmetry in water's response is strong, about 50% of the symmetric response. / Ph. D.

Polyelektrolyte (PEs) bilden eine große Klasse von Materialien, die in der wissenschaftlichen Forschung immer mehr Beachtung findet. Aufgrund der Lange-Bereich Elektrostatic ist das theoretische Verständnis von PE-Lösungen im Vergleich zu ihren neutralen Gegenstücken noch relativ schlecht gewesen, dadurch die Rationalisierung der Gegenionskondensation auf hochgeladenen PEs herausfordern. Die Komplexität des Problems wird noch zusätzlich durch die gleichzeitige Anwesenheit monovalenter und divalenter Gegenionen in der Lösung, was vielen biologische Umgebungen entspricht, erhöht. Dies beeinflusst die PE-Protein Komplexierungen, damit ihren Funktionen und Anwendungen in der Biomedizin und Biotechnologie. In dieser Arbeit führen wir eine umfassende Analyse der Ladungs- und Hydratationsstruktur von dendritischen PEs in einem monovalenten Salz unter Verwendung von atomistischen Molekulardynamik (MD) Computersimulationen mit explizitem Wasser durch. Darüber hinaus untersuchen der kompetitiven Adsorption der monovalenten und divalenten Gegenionen am globulären PE mit Hilfe theoretischer Mean-Field-Modelle, vergröberter und atomistischer (expliziter) Wasser-Simulationen und Kalorimetrie-Experimenten. Wir befassen uns mit der Herausforderung, eine genau definierte effektive Ladung und ein Oberflächenpotential der PEs für praktische Anwendungen zu finden, und präsentieren ein neuartiges kompetitives Ionenbindungsmodell, das einen aussagekräftigen Vergleich zwischen Theorie, Simulationen und Experimenten gewährleistet. Diese Arbeit stellt eine systematische elektrostatischen Beschreibung von PE vor, untersucht die thermodynamische PE-Wasser Signatur und analysiert die kompetitiven Bindung von monovalenten und divalenten Gegenionen an PEs. Es wird ein tieferer Einblick in die physikochemischen Aspekte von PE-Gegenionen- und PE-Wasser-Wechselwirkungen erhalten, was für das rationale Design von PEs auf einer gezielten Anwendungsbasis von entscheidender Bedeutung ist. / Polyelectrolytes (PEs) represent a broad class of materials that are getting an increasing attention in the scientific community. However, due to the long-range electrostatics, the theoretical understanding of PE solutions has been relatively poor compared to their neutral counterparts, thereby challenging the rationalization of the counterion condensation on highly charged PEs. Moreover, the counter-intuitive footprint of PE-water thermodynamics, and the simultaneous presence of the divalent and the monovalent counterions in the solution, as is reminiscent of many biological environments, escalates the complexity and richness of the problem. This affects the PE-proteins complexations, and thus their functions, applications in biomedicine and biotechnology. In this thesis, we conduct a comprehensive analysis of the charge and hydration structure of dendritic PEs in a monovalent salt using all-atom explicit-water molecular dynamics computer simulations, and investigate a competitive sorption of mono- versus divalent ions on globular PEs using mean-field theoretical models, all-atom and coarse-grained simulations and calorimetry experiments. We address the challenges of obtaining a well-defined effective charge and surface potential of the PE for practical applications and present a novel competitive ion binding model, ensuring a meaningful comparison between theory, simulations and experiments. This thesis lays out a systematic PE electrostatic characterization, explores PE-water thermodynamics, and analyses the competitive binding of divalent and monovalent counterions on the PE. A deeper insight into the physicochemical aspects of PE-counterion and PE-water interactions is achieved, which is vital towards the rational design of PEs on a targeted application basis.