Investigating wetting characteristics on microstructured surfaces for superhydrophobicity and metal microcasting

The engineering of liquid behavior on surfaces is important for infrastructure, transportation, manufacturing, and sensing. Surfaces can be rendered superhydrophobic by microstructuring, and superhydrophobic devices could lead to practical corrosion inhibition, self-cleaning, fluid flow control, and surface drag reduction. To more fully understand how liquid interacts with microstructured surfaces, this dissertation introduces a direct method for determining droplet solid-liquid-vapor interfacial geometry on microstructured surfaces. The technique performs metrology on molten metal droplets deposited onto microstructured surfaces and then frozen. Unlike other techniques, this visualization technique can be used on large areas of curved and opaque microstructured surfaces to determine contact line. This dissertation also presents measurements and models for how curvature and flexing of microstructured polymers affects hydrophobicity. Increasing curvature of microstructured surfaces leads to decreased slide angle for liquid droplets suspended on the surface asperities. For a surface with regularly spaced asperities, as curvature becomes more positive, droplets suspended on the tops of asperities are suspended on fewer asperities. Curvature affects superhydrophobicity because microscopic curvature changes solid-liquid interaction, pitch is altered, and curvature changes the shape of the three phase contact line. This dissertation presents a model of droplet interactions with curved microstructured surfaces that can be used to design microstructure geometries that maintain the suspension of a droplet when curved surfaces are covered with microstructured polymers. Controlling droplet dynamics could improve microfluidic devices and the shedding of liquids from expensive equipment, preventing corrosion and detrimental performance. This dissertation demonstrates redirection of dynamic droplet spray with anisotropic microstructures. Superhydrophobic microstructured surfaces can be economically fabricated using metal embossing masters, so this dissertation describes casting-based microfabrication of metal microstructures and nanostructures. Low melting temperature metal was cast into flexible silicone molds which were themselves cast from microfabricated silicon templates. The flexibility of the silicone mold permits casting of curved surfaces, which this dissertation demonstrates by fabricating a cylindrical metal roller with microstructures. The metal microstructures can be in turn used as a reusable molding tool. This dissertation also describes an industrial investment casting process to produce aluminum molds having integrated microstructures. Unlike conventional micromolding tools, the aluminum mold was large and had complex curved surfaces. The aluminum was cast into curved microstructured ceramic molds which were themselves cast from curved microstructured rubber. Many structures were successfully cast into the aluminum with excellent replication fidelity, including circular, square, and triangular holes. This dissertation demonstrates molding of large, curved surfaces having surface microstructures using the aluminum mold. This work contributes a more full understanding of the phenomenon of superhydrophobicity and techniques for the economic fabrication of superhydrophobic microstructures.

A geometric study of liquid retention in open-cell metal foams

Open-cell metal foams show promise as an emerging novel material for heat exchanger applications. The high surface-area-to-volume ratio suggests increased compactness and decrease in weight of heat exchanger designs. However, the metal foam structure appears conducive to condensate retention, which would degenerate heat transfer performance. This research investigates the condensate retention behavior of aluminum open-cell metal foams through the use of static dip tests and geometrical classification via X-ray Micro-Computed Tomography. Aluminum open-cell metal foam samples of 5, 10, 20, and 40 pores per inch (PPI), all having a void fraction greater than 90%, were included in this investigation. In order to model the condensate retention behavior of metal foams, a clearer understanding of the geometry was required. After exploring the ideal geometries presented in the open literature, X-ray Micro-Computed Tomography was employed to classify the actual geometry of the metal foam samples. The images obtained were analyzed using specialized software from which geometric information including strut length and pore shapes were extracted. The results discerned a high variability in ligament length, as well as features supporting the ideal geometry known as the Weaire-Phelan unit cell. The static dip tests consisted of submerging the metal foam samples in a liquid, then allowing gravity-induced drainage until steady-state was reached and the liquid remaining in the metal foam sample was measured. Three different liquids, water, ethylene glycol, and 91% isopropyl alcohol, were employed. The behaviors of untreated samples were compared to samples subjected to a Beomite surface treatment process, and no significant differences in retention behavior were discovered. The dip test results revealed two distinct regions of condensate retention, each holding approximately half of the total liquid retained by the sample. As expected, condensate retention increased as the pores sizes decreased. A model based on surface tension was developed to predict the condensate retention in the metal foam samples and verified using a regular mesh. Applying the model to both the ideal and actual metal foam geometries showed good agreement with the dip test results in this study.

Synthesis and structural stability of metal-organic frameworks

Metal-organic frameworks (MOFs) have attracted significant attention during the past decade due to their high porosity, tunable structures, and controllable surface functionalities. Therefore many applications have been proposed for MOFs. All of them however are still in their infancy stage and have not yet been brought into the market place. In this thesis, the background of the MOF area is first briefly introduced. The main components and the motifs of designing MOFs are summarized, followed by their synthesis and postsynthetic modification methods. Several promising application areas of MOFs including gas storage and separation, catalysis and sensing are reviewed. The current status of commercialization of MOFs as new chemical products is also summarized. Examples of the design and synthesis of two new MOF structures Eu(4,4′,4′′,4′′′-(porphine-5,10,15,20-tetrayl)tetrakis(benzoic acid))·2H2O∙xDMF and Zn4O(azobenzene-4,4’-dicarboxylic acid)3∙xNMP are described. The first one contains free-base porphyrin centers and the second one has azobenzene components. Although the structures were synthesized as designed, unfortunately they did not possess the expected properties. The research idea to use MOFs as template materials to synthesize porous polymers is introduced. Several methods are discussed to grow PMMA into IRMOF-1 (Zn4O(benzene-1,4-dicarboxylate)3, IR stands for isoreticular) structure. High concentration of the monomers resulted in PMMA shell after MOF digestion while with low concentration of monomers no PMMA was left after digestion due to the small iii molecular weight. During the study of this chapter, Kitagawa and co-workers published several papers on the same topic, so this part of the research was terminated thereafter. Many MOFs are reported to be unstable in air due to the water molecules in air which greatly limited their applications. By incorporating a number of water repelling functional groups such as trifluoromethoxy group and methyl groups in the frameworks, the water stability of MOFs are shown to be significantly enhanced. Several MOFs inculding Banasorb-22 (Zn4O(2-trifluoromethoxybenzene-1,4-dicarboxylate)3), Banasorb-24 (Zn4O(2, 5-dimethylbenzene-1,4-dicarboxylate)3) and Banasorb-30 (Zn4O(2-methylbenzene-1,4-dicarboxylate)3) were synthesized and proved to have isostructures with IRMOF-1. Banasorb-22 was stable in boiling water steam for one week and Banasorb-30’s shelf life was over 10 months under ambient condition. For comparison, IRMOF-1’s structure collapses in air after a few hours to several days. Although MOF is a very popular research area nowadays, only a few studies have been reported on the mechanical properties of MOFs. Many of MOF’s applications involve high pressure conditions, so it is important to understand the behavior of MOFs under elivated pressures. The mechanical properties of IRMOF-1 and a new MOF structure Eu2(C12N2O4H6)3(DEF)0.87(H2O)2.13 were studied using diamond anvil cells at Advanced Photon Source. IRMOF-1 experienced an irriversible phase transtion to a nonporous phase followed by amorphization under high pressure. Eu2(C12N2O4H6)3(DEF)0.87(H2O)2.13 showed reversible compression under pressure up to 9.08GPa.