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Thesis (M.S.)--Worcester Polytechnic Institute. / Keywords: Molecular dynamics; hydrophobic zeolite; water; confined media. Includes bibliographical references (p. 71).

"Water behavior in pure silicalite and Dealuminated Zeolite Y (DAY), two highly hydrophobic zeolites, was investigated at different temperatures in the range 100-600 K by molecular dynamics simulations. The Compass forcefield was used to carry out the study. A full flexibility of water molecules and of the zeolite framework was considered. The results show that water behavior is more complex in silicalite than in zeolite DAY. Three different activation energies for water diffusion were obtained in silicalite in the range 250-600 K compared to two for DAY. The values of these activation energies are discussed in detail and are related to the hydrogen bond‘s strength and the zeolite structure. Moreover, from the radial distribution functions (rdfs), it is shown that water mostly exists in the gas phase at room temperature in silicalite whereas liquid water is observed in DAY in agreement with previous experimental observations. The self-diffusion coefficients of water and the rdfs are obtained as a function of temperature in order to explain the behavior differences of water in the two all-silica zeolites. The loading influence on the self-diffusion coefficients is also investigated for both crystals. The results are compared with previous experimental and theoretical studies."

Solid surfaces featuring a spatial variation of surface wettability along particular directions on their surface, referred to as wettability gradient surfaces, are becoming increasingly important in practical applications such as enhancement of boiling and condensation heat transfer and separation of immiscible liquids in smart micro-fluidic devices. With the aid of an external energy input, such as mechanical vibration or impact kinetic energy, a liquid drop on such surfaces gets propelled towards more wettable region on the surface. A fundamental study of impact dynamics of liquid drops on such solid surfaces is relevant in understanding their effectiveness. The present thesis reports a combined experimental and theoretical study on the impact dynamics of liquid drops on solid surfaces comprising a smooth portion and a groove-textured portion separated by a junction line (dual-textured surfaces). Three different dual-textured surfaces – two made of intrinsically hydrophilic stainless steel and one of intrinsically hydrophobic poly-di-methyl-siloxane (PDMS) – are considered. Liquid drops, with Weber number (We) in the range 1–100, are impacted on the junction of the dual-textured surfaces and the entire impact dynamics across the junction is captured using a high speed video camera. Experiments of drop impact on the homogeneous surface portions of dual-textured surfaces (far away from the junction) are also conducted. The temporal variation of drop contact radius measured from the junction line on smooth and groove-textured portions of the dual-textured surfaces exhibits four distinct stages – primary spreading, primary receding, secondary spreading on more wettable surface portion, and final equilibrium – with the final outcome being the bulk movement and deposition of liquid drop away from the junction towards the more hydrophilic surface portion. Secondary parameters characterizing each of these different stages are extracted from these measurements and a one-to-one comparison between dual-textured and homogenous surfaces is presented. A significant effect of dual-texture nature is seen on the receding process of impacting drops. On the dual-textured surfaces, the receding velocity of impacting drop on the groove-textured portion is always greater than that on the smooth portion. The asymmetry in drop receding results in a drop drift velocity towards the more wettable surface portion leading to an enhanced secondary drop spreading on the more wettable smooth portion. The drop drift velocity shows a decrease with We at low We and remains almost constant at higher We after a particular value of We. Correspondingly, the ratio of the maximum drop spread factor achieved during the secondary spreading (βm2) to that during the primary spreading (βm) is seen to decrease with We at low We and remains constant at higher We. Owing to the differences in the static equilibrium wetting difference, βm2/βm is more on the stainless steel dual-textured surfaces than on the PDMS dual-textured surface. The presence of dual-texture results in a higher final spread on more wettable smooth portion and smaller final spread on less wettable textured portion of the dual-textured surfaces and this difference decreases with We. The difference in final spread factors between the smooth and textured portions is more on the stainless steel dual-textured surfaces than the PDMS dual-textured surface. The bulk drop movement (ξ), characterized in terms of distance measured from the junction to the final drop center, decreases with We at low We and remains constant at higher We on the stainless steel dual-textured surfaces whereas it remains constant at low We and decreases at higher We on the PDMS dual-textured surface. ξ on the PDMS dual-textured surface is always less than that on the stainless dual-textured surface due to the lower wetting difference across the junction of the former. Comparison of the trends of secondary parameters with the predictions from theoretical models reported in literature showed a lack of agreement. This is due to various physical processes encountered by impacting drop on the groove-textured surface, identified through experiments of drop impact on homogeneous groove-textured surfaces, such as (i) convex shape of liquid-vapor interface near contact line at maximum spreading, (ii) impregnation of drop liquid into the grooves during impact, and (iii) contact line pinning of spreading drop at the asperity edges of surface texture, as well as the wetting difference in dual-textured surfaces. The inclusion of these physical processes under conventional energy conservation approach is seen to predict the experimentally observed trends of maximum drop spread factor on the groove-textured portions. A force balance model, applied to the liquid drop configuration at the beginning of drop receding on the dual-textured surfaces, predicts the qualitative trend of ξ with We on all surfaces. Drop liquid impregnation into the grooves of textured portion at We > Wecr (critical We corresponding to transition from Cassie to impaled state) is proposed as a possible physical mechanism to account for the explanation of the specific trends of ξ with We. A theoretical model formulated using force balance at the three phase contact line beneath impacting drop on groove-textured surface is presented for the prediction of Wecr.