Zeolites are microporous crystalline materials, which are widely used in catalysis, adsorption, and ion-exchange processes. However, in most cases, the synthesis of novel zeolites as functional materials still relies on trial-and-error methods, which are time consuming and expensive. Therefore, the motivation for this thesis work is to understand the zeolite synthesis mechanismand further develop knowledge for manipulating zeolite properties and ultimately the rational design of porous materials. This work focused on formation of silicalite-1 (pure-silica ZSM-5) from basic aqueous solutions containing tetraorthosilicate (TEOS) as silica source, and tetrapropylammonium (TPA) cations as the organic structure-directing agent. The presence of silica precursor particles with size of 2-5 nm in these mixtures prior to and during hydrothermal treatments have been observed through dynamic light scattering (DLS), small-angle X-ray (SAXS) and transmission electron microscopy (TEM). However, to quantify composition and the molecular structure transformation of these silica precursor particles during zeolite synthesis is still a technical challenge. Another important yet unresolved question is how organocations interact with these nanoparticles and direct zeolite nuclei. Unlike many studies performed analyzing the inorganic phase (silica) present in synthesis mixtures, this study quantified the organocation-silica particle interaction and its ultimate effect on zeolite growth mainly through probing the behavior of the organocations. Pulsed-field gradient (PFG) NMR was used to capture the mobility change of organocations, and was complemented with scattering measurements (DLS, SAXS) on the silica nanoparticles. On the basis of the measurement results, the thermodynamic and kinetic properties of the organic-inorganic interaction were derived. Upon aging at room temperature, this interaction manifested as binding of TPA onto the silica particles due to electrostatic interactions, and such binding behavior can be well described by the Langmuir adsorption model. Upon hydrothermal treatment, a fraction of TPA adsorbed at room temperature dissociates from the growing silica nanoparticles and the corresponding desorption profiles were fitted well by the pseudo-second order kinetic model. The addition of tetramethylammonium (TMA) as "competitors" promoted TPA desorption kinetics and hindered silica nanoparticle growth due to stronger association of TMA with particles than that of TPA. Finally, the TPA adsorption strength increased via addition of monovalent salts with increasing ionic size whereas that of TMA shows an opposite trend. This suggests one potential route for tuning the organic-silica precursor particle interactions and thus possibly affecting some kinetics steps in the synthesis.

No / There is considerable interest, both fundamental and technological, in understanding how additives and impurities influence crystal nucleation, and in the modulation of nucleation in a predictable way by using designer additives. An appropriate additive can promote, retard, or inhibit crystal nucleation and growth, assist in the selective crystallization of a particular enantiomer or polymorphic form, or enable crystals of a desired habit to be obtained.[1¿3] Applications involving additives include the control of the nucleation of proteins,[4] the inhibition of urinary-stone formation[5] and of ice formation in living tissues during cryoprotection,[6] their use as antifreeze agents in Antarctic fish,[7,8] the prevention of blockages in oil and gas pipelines as a result of wax precipitation[9] and gas-hydrate formation,[10] crystal-twin formation,[11] and as a possible basis for the antimalarial activity of some drugs.[12]We report herein the mode of action and explicit (apparently intuitive) rules for designing additive molecules for the modulation of crystal nucleation. The mode of action and the design features have been derived from molecular-dynamics simulations involving simple models.[13] These findings will help to rationalize how known nucleation inhibitors and modulators exert their effect and aid in the identification or design of new additives for the inhibition or promotion of nucleation in specific systems.

Indiana University-Purdue University Indianapolis (IUPUI) / Background: Elucidating the lithium disilicate system like the popular IPS e.max® CAD (LS2), made specifically for Computer-Aided Design and Computer-Aided Manufacturing (CAD-CAM), as a function of temperature unravels new ways to enhance material properties and performance. Objective: To study the effect of various thermal processing on the crystallization kinetics, crystallite microstructure, and strength of LS2. Methods: The control group of the LS2 samples was heated using the standard manufacturer heating-schedule. Two experimental groups were tested: (1) an extended temperature range (750-840 °C vs. 820-840 °C) at the segment of 30 °C/min heating rate, and (2) a protracted holding time (14 min vs. 7 min) at the isothermal temperature of 840 °C. Five other groups of different heating schedules with lower-targeted temperatures were evaluated to investigate the microstructural changes. For each group, the crystalline phases and morphologies were measured by X-ray diffraction (XRD) and scanning electron microscope (SEM) respectively. Differential scanning calorimeter (DSC) was used to determine the activation energy of LS2 under non-isothermal conditions. A MTS universal testing machine was used to measure 3-point flexural strength and fracture toughness, and elastic modulus and hardness were measured by the MTS Nanoindenter® XP. A one-way ANOVA/Tukey was performed per property (alpha = 0.05). Results: DSC, XRD, and SEM revealed three distinct microstructures during LS2 crystallization. Significant differences were found between the control group, the two aforementioned experimental groups, and the five lower-targeted-temperature groups per property (p<0.05). The activation energy for lithium disilicate growth was 667.45 (± 28.97) KJ/mole. Conclusions: Groups with the extended temperature range (750-840 °C) and protracted holding time (820-840 °C H14) produced significantly higher elastic-modulus and hardness properties than the control group but showed similar significant flexural-strength and fracture-toughness properties with the control group. In general, explosive growth of lithium disilicates occurred only when maximum formation of lithium metasilicates had ended.