Thesis (Ph.D.)--University of Delaware, 2005. / Principal faculty advisor: Darrin J. Pochan, Dept. of Materials Science. Includes bibliographical references.

Chemical strengthening via ion exchange is commonly used in the industry to produce ultra-thin and resistant glasses used for high-tech applications. This process results in the formation of an ion-exchanged region near the glass surface that is under significant compressive stress, which tremendously improves the mechanical strength and the scratch resistance of the glass. The aim of this thesis is to deepen our fundamental understanding of the ion-exchange mechanisms. Since the mechanical strength against brittle fracture of ion-exchanged glasses depends on the compressive stress at the surface and the depth of interdiffusion, special attention was paid to the two main parameters affecting those properties: the parent glass composition and stress relaxation processes.First, the effect of the parent glass composition on interdiffusion properties was analyzed. We focused our study on the effect of the alkali oxide:alumina ratio and the ionic potential (charge:radius) of divalent cations on the interdiffusional properties. An increase of the Al2O3 content in Na+/K+ ion-exchanged silicate glasses leads to a reduction of the depth of interdiffusion layer and an enhancement of the surface compressive stress. These trends are shown to be consistent with the compositional variation of the glass connectivity and hence, the stress relaxation occurring during the ion-exchange. It is also found that the depth of interdiffusion is higher for glasses containing divalent cations with a higher ionic potential such as Mg and Zn. This is attributed to the larger free volume available and the weaker Na-O bonds in those glasses. Second, the structural origin of stress relaxation is investigated. In the Na+/K+ ion exchanged glasses, the K+-foreign cations are introduced in the cages of the Na+-host cations. Due to stress relaxation, the size of the K-O coordination shell in ion-exchanged glasses increases. This increase is achieved by two structural adaptation mechanisms: a contraction of the Na-O, Ca-O and Mg-O coordination shell and both a shortening of the Si-NBO distances and an opening of the Q4 Si-O-Si angles. The greater knowledge developed in this thesis on the effect of parent glass composition on interdiffusion mechanisms and stress relaxation processes provides further insight into practical ways to optimize the mechanical strength of ion-exchanged glasses. / Doctorat en Sciences de l'ingénieur et technologie / info:eu-repo/semantics/nonPublished

The system kaolinite - carbon black consisting of cheap precursors has been investigated, in terms of its potential to form A1₂ O₃ - SiC composites. The carbothermal reduction process of mullite and silica was studied, in detail, in the range 1275° to 1810° C and over different periods, both under sintering as well as hot-pressing conditions. It was established that the reduction of mullite and silica starts around 1450° C, where the rate of reaction is very slow. Until about 1800° C during the reduction of mullite, SiO₂ gets preferentially reduced, thus forming a composite ceramic consisting of SiC and A1₂ O₃ phases. The kinetics of the formation of SiC + A1₂ O₃ were followed in the range 1590° - 1660° C and it was noted that under hot-pressing conditions they follow a contracting cylinder model. The rate of reaction increased with the increase in temperature and followed a parabolic path with time because of the geometry of the hot-pressed specimens at each temperature. This indicated that the gas diffusion in and out of the system along the edges of the cylindrical specimens is the rate controlling step. The activation energy of the reduction process was calculated to be 922 KJ/mole. The application of pressure prior to the carbothermal reduction process seemed to be not favourable for the formation of SiC and A1₂ O₃, however, when applied after the beginning of soaking period, this greatly improved the densities and formation of SiC and A1₂ O₃. The microstructure of the samples was analysed using SEM and TEM. It was found that the grain size of the composite ceramic was of the order of 0.2μm. SiC was present mainly in the form of fine platelets. Finally, the isothermal compaction behaviour of the system was studied under a constant pressure in the temperature range 1200° C - 1800° C, during which the formation and carbothermal reduction of mullite and silica took place. A mathematical model based on the least squares fitting was used to fit the compaction curves. Due to the complex nature of the compaction data an empirical approach was used to interpret the data and a viscoelastic model was developed. It was found that the interactive-double-Kelvin unit having two elastic and two viscous components explained the type of compaction behaviour observed in the kaolinite + C system. One of the viscous components (η₁) and one of the elastic components (M₁) were found to be temperature sensitive. It is concluded that starting from the cheap precursors (kaolinite and carbon black) a particulate composite of A1₂ O₃,-SiC can be produced by hot-pressing technique. SiC-whisker formation is not encountered in this system. The very fine grain size of the paniculate composite, resulting in a small flaw size, should provide the composite ceramic with good mechanical properties. / Applied Science, Faculty of / Materials Engineering, Department of / Graduate

Thesis (M.Sc. (Chemistry)) -- University of Limpopo, 2015 / This dissertation investigated the properties of ferrierite synthesised using different SiO2 sources under identical conditions. The SiO2 sources used were TEOS, water-glass, Aerosil 200 and Ludox LS-30. The synthesis procedure comprised preparation of a gel with molar composition: 20 Na2O : Al2O3 : 37 pyrrolidine : 66:5 SiO2 : 6:3 H2SO4 : 1460 H2O. This was followed by hydrothermal treatment at 160 oC in a stainless steel autoclave for 72 h. The solid products were characterised by XRD, SEM, NH3-TPD and BET techniques. The ferrierite prepared using sodium silicate was more crystalline than ferrierite zeolites synthesised using Ludox LS-30, Aerosil 200 and tetraethyl orthosilicate as SiO2 sources. An amorphous phase was produced when ferrierite was synthesised using unhydrolysed TEOS as a sole SiO2 source. The physicochemical properties of the materials were not only affected by the nature of the SiO2 source, but also some synthesis manipulations such as acid-hydrolysis and water-glass addition when TEOS was used as a primary silica source. There were improvements in the materials produced when the TEOS was pre-hydrolysed with HCl and also mixed with water-glass in equal proportions. The SEM images of ferrierite materials synthesised using water-glass and Ludox LS-30 were uniform. The water-glass-based materials were thin sheets, flake-like images and Ludox LS-30-based produced thin-plate-like morphologies. The micrograph of ferrierite synthesised using TEOS as the SiO2 source showed hexagonal-type morphology and aggregates of smaller particles. There were two types of shapes in the ferrierite synthesised using Aerosil 200 as the silica source, namely, octagonal prismatic and hexagonal type morphologies. An equimolar mixture of TEOS and water-glass showed octagonal prismatic shape with triangular faces along certain edges of the material. The NH3-TPD acid site distribution profiles showed two peaks of weak acid strength at low temperatures (≤ 350 oC) for the representative H-ferrierite investigated. The ferrierite materials synthesised using unhydrolysed TEOS and Ludox LS-30 as SiO2 sources, showed NH3 desorption peaks at higher temperatures (≥ 350 oC). These peaks correspond to ammonia eluted from strong acid sites. The BET surface area of ferrierite synthesised using water-glass was high, while the material synthesised using unhydrolysed TEOS had the lowest surface area. Novel crystal shapes, comprising octagonal prisms with additional triangular phases, were observed in ferrierite samples prepared by the use of TEOS/water-glass mixture as silica source. The zeolitic materials prepared in this study were tested for the efficiency in the removal of Cu2+ from simulated wastewater, using a batch method. The effects of initial pH, initial concentration, contact time and adsorbent dose on Cu2+ adsorption were studied. All the materials showed maximum metal uptake efficiency at pH 5, and this pH was fixed in further studies involving other variables. It was observed that the metal uptake from aqueous solution increased with contact time and adsorbent dose. The Na-form of ferrierite synthesised using water-glass was the poorest Cu2+ adsorbent with respect to the four variables investigated (pH, contact time, adsorbent dose and initial metal ion concentration). KEY CONCEPTS Acidity, Adsorption, Ferrierite, Morphology, Silica source.

The degradability of wollastonite, montmorillonite and talc in an aqueous solution of acetic acid at different temperatures is main object of this study. Mineral carbonation, i.e. the reaction of calcium and magnesium presented in these three silicates, is a novel and promising approach to carbon dioxide capture and long-term storage. The kinetic of wollastonite, montmorillonite and talc dissolution is studied due to assessment of their efficiency for CCS technologies. The dissolution kinetic is discovered with using measured time dependence of Ca2+ and Mg2+ leached ions concentration.

<p> A number of silicate compounds BaTSiO4 (T = Co, Mg, Zn), Na0.5K0.5GaSiO4 and Sr1-xCaxBeSiO4 (x = 0.0 ~ 0.4) have been characterized by a combination of diffraction techniques. These compounds crystallize with the same (√3XA, C) superstructure of the hexagonal kalsilite (KAlSiO4) structure and belong to the large structural family of stuffed tridymite-derivatives. Their crystal structures have been refined by using powder neutron data (BaTSiO4, T = Mg, Zn), powder X-ray data (Na0.5K0.5 GaSiO4) and single crystal X-ray data (BaCoSiO4 and Sr1-xCaxBeSiO4, x = 0.0 and 0.27). This study shows that these kalsilite-like structures can accommodate cavity and tetrahedral atoms of variable sizes by relatively minor framework distortions and atomic displacements. The formation of the (√3XA, C) superstructure can be correlated with the relative sizes of the tetrahedral and cavity atoms.</p> / Thesis / Master of Science (MSc)

Adsorption of cations by clays has been a subject of investigation for many years. Many proposals have been advanced to explain this process of adsorption. Two proposals have been prominent in recent years. The Marshall "charged lattice" theory attributes adsorption of cations by clays to an electrostatic attration of the clay particles for cations. This charge on the clay particles is attributed to various isomorphic substitutions in the lattice of the clay which result in an unbalanced charge on the particle. This isomorphic substitution can take place either in the silicon-oxygen tetrahedra of the silicate structure or with the aluminum layer of the particle. The Cook "ion-pair" theory make the assumption that the charge on the clay particle is caused by the neutral clay chemisorbing hydroxyl molecules in the compact double layer thus giving the particle its negative charge. Cations are then attracted electrostatically to the diffuse outer layer. Experimental adsorption data is used to evaluate the validity of these two theories. Equations are set up representing mathematically the two mechanisms of adsorption and are tested graphically with the experimental data. These various graphs, in every case, show that the Marshall "charged lattice" mechanism is inconsistent with the experimental data. The Cook theory adequately represents a consistent agreement with this rather complete set of experimental data.

No description available.

Thesis. 1976. Ph.D.--Massachusetts Institute of Technology. Dept. of Earth and Planetary Sciences. / Microfiche copy available in Archives and Science. / Bibliography: leaves 147-157. / Ph.D.

La réaction alcali-silice (RAS) reste un problème majeur de durabilité du béton. Plusieurs chercheurs ont étudié l'utilisation d'ajouts cimentaires (AC) et de certains résidus industriels comme mesure fiable pour contrôler l'expansion associable à la RAS dans le béton. Les ajouts cimentaires ont également été utilisés comme outil pour réduire l'impact environnemental de la production du ciment. À cette fin, des granulats réactifs ont été sélectionnés et combinés à différentes proportions de résidus d'aluminosilicate (SiAl) produits lors d'un processus industriel visant l'extraction du lithium dans un cadre d'exploitation minière. Des éprouvettes de barres de mortier (AMBT) et de prismes miniatures du béton (MCPT) ont été préparées avec différentes proportions de SiAl (10%, 15%, 20%, 25%, 30% et 40% de remplacement massique du ciment - systèmes binaires), de même qu'en combinant des proportions de SiAl avec des ajouts cimentaires conventionnels comme des cendres volantes (CV), du laitier de haut fourneau (LHF) et de la fumée de silice (FS) dans des mélanges ternaires, et ce afin d'évaluer l'expansion de la RAS conformément aux essais accélérés CSA A23.2-25A/28A et AASHTO T 380-19. Les résultats d'essais réalisés sur éprouvettes de béton (essai MCPT) ont montré une diminution de 82 à 89% de l'expansion aux échéances critiques pour les spécimens incorporant 15 à 25% de SiAl (systèmes binaires incorporant les granulats réactifs Spratt et Sudbury). Dans les mélanges ternaires, la tendance bénéfique était similaire et, par exemple, l'incorporation d'un pourcentage de 10%SiAl+10CV à 10%SiAl+15%CV a réduit l'expansion de 83% et 91%, respectivement, par rapport au mélange de référence composé de ciment Portland seulement (mélanges incorporant le calcaire Spratt). Ces niveaux de réduction de l'expansion par rapport à celle obtenue pour les éprouvettes de référence permettent dans bon nombre de cas de rencontrer les limites d'acceptation pour les formulations (ternaires) efficaces contre la RAS, mais pas toujours. Les éprouvettes incorporant au moins de 20% de l'aluminosilicate (SiAl) à l'étude ont permis d'atténuer l'expansion de la RAS causée par l'utilisation de granulats réactifs (Spratt et Sudbury). Pour corréler les résultats obtenus lors des essais accélérés, ceux-ci ont été comparés à des essais réalisés sur des blocs de béton fabriqués avec la même proportion d'AC et exposés à des conditions naturelles pendant 20 ans. / The alkali-silica reaction (ASR) remains a major concrete durability problem around the world. Several researchers have studied the effectiveness of supplementary cementitious materials (SCMs) and other industrial waste materials as a measure to control ASR expansion in concrete. SCMs have also been used as a tool to reduce the environmental impact of cement production. For this purpose, selected reactive aggregates were combined with an Aluminosilicate residue (SiAl) produced during lithium extraction from a mining operation. Accelerated Mortar bar (AMBT) and Miniature Concrete Prism (MCPT) tests were performed on specimens that were prepared with various SiAl proportions (10%, 15% 20%, 25%, 30% and 40% by cement mass - binary systems), as well as by combining various proportions of SiAl with conventional SCMs such as a fly ash (FA), slag (SL) and silica fume (SF) in ternary mixes. The objective was to evaluate the effectiveness of those SCMS in reducing ASR expansion in accordance with accelerated tests CSA A23.2-25A/28A and AASHTO T 380-19. MCPT test results showed expansion reduction of 82 to 89% at selected critical testing periods for specimens incorporating 15 to 25% of SiAl (binary mixtures with reactive Spratt and Sudbury aggregates). In the case of ternary blends, a similar beneficial trend was observed; for example, increasing the amount of FA from 10 to 15% in a mixture incorporating 10% SiAl resulted in expansion reductions improving from 83 to 91% compared to the control OPC concrete (mixtures with the Spratt reactive aggregate). Such levels of expansion reductions allowed for a large number of the ternary mixtures tested to meet the acceptance limit proposed for the MCPT, but not always. Specimens incorporating at least 20% of the aluminosilicate (SiAl) residues were useful to prevent ASR expansion caused by the use of reactive aggregates (Spratt and Sudbury). To correlate the results obtained from the accelerated tests, those were compared with expansion trends measured on concrete blocks built with the same amount of SCMs and exposed to natural conditions for a period of 20 years.