Chemistry at silicone-inorganic oxide interfaces

This dissertation describes research performed using siloxane polymers. This includes the reactions of siloxane polymers with inorganic oxide surfaces to form covalently attached monolayers, and the electrical properties of crosslinked silicone composite films fabricated by compounding with nickel particles. In addition to these topics, the use of contact line pinning as a practical and controllable method for the deposition of materials on superhydrophobic and chemically patterned surfaces is also described. The first chapter provides a general review of siloxane polymer chemistry, focusing in particular on the relationship between molecular structure and physical properties. The use and fabrication of silicone composite materials is also discussed, including typical methods for crosslinking siloxane polymers and the effects of filler materials. Finally, contact angle hysteresis and contact line pinning phenomena are presented. Following this introduction, four separate but interrelated projects are presented. First, the surface modification of titania via hydridomethylsiloxanes is discussed. This work represents an extension of the reaction of hydridosilanes and provides an environmentally clean method for the hydrophobization of titania. Linear and cyclic hydridomethylsiloxanes, as well as hydridomethylsiloxane-co-dimethylsiloxane polymers, are used as reagents and the resulting surfaces are discussed. Unpredicted results from this method lead to the consideration of poly(dimethylsiloxane) as a previously unconsidered reagent presented in the next project. The second project discusses the covalent attachment of siloxane polymers, particularly poly(dimethylsiloxane), to a range of inorganic oxide surfaces, including titania, nickel oxide, alumina, and silica. This reaction is presented as a thermally activated equilibrium process, and offers insight into certain aging processes found in silicone materials. Particular focus is made on the development of a highly reproducible method for the fabrication of low contact angle hysteresis surfaces. Furthermore, this reaction is shown to be general for the siloxane bond through the reaction of functional and cyclic siloxanes. The third project describes the preparation of electrically conductive silicone coatings, containing nickel and titania particles. The effect of nickel concentration and geometry on the electrical properties of these coatings is examined and the effects on the percolation threshold are presented. In addition to this, the addition of titania nanoparticles to diminish electrical conductance is also investigated. The fourth project discusses the contact line pinning of liquids on hydrophobic surfaces. In this chapter, the use of ionic liquids exhibiting no vapor pressure is used to experimentally determine the de-wetting process of liquids from pillared, superhydrophobic surfaces through micro-capillary bridge rupture. Furthermore, this technique is used as a preparative technique for the fabrication of individual salt crystals supported on pillared surfaces

Contact angle hysteresis: a different view and a trivial recipe for low hysteresis hydrophobic surfaces

Contact angle hysteresis is addressed from two perspectives. The first is an analysis of the events that occur during motion of droplets on superhydrophobic surfaces. Hysteresis is discussed in terms of receding contact line pinning and the tensile failure of capillary bridges. The sign of the curvature of the solid surface is implicated as playing a key role. The second is the report of a new method to prepare smooth low hysteresis surfaces. The thermal treatment of oxygen plasma-cleaned silicon wafers with trimethylsilyl-terminated linear poly(dimethylsiloxane) (PDMS - commercial silicone oils) in disposable glass vessels is described. This treatment renders silicon/silica surfaces that contain covalently attached PDMS chains. The grafted layers of nanometre scale thickness are liquid-like (rotationally dynamic at room temperature), decrease activation barriers for contact line motion and minimize water contact angle hysteresis. This simple method requires neither sophisticated techniques nor substantial laboratory skills to perform

Dip-Coating Crystallization on a Superhydrophobic Surface: A Million Mounted Crystals in a 1 cm(2) Array

Silicon wafers (silicon dioxide surfaces) were patterned by photolithograpy to contain 3 mu m (width) x 6 pm (length) x 40 mu cm (height) staggered rhombus posts in a square array (20 mu m center-to-center spacing). These surfaces were hydrophobized using a vapor phase reaction with tridecafluorooctyldimethylchlorosilane and exhibit "superhydrophobicity" (water contact angles of theta(A)/theta(R) = 169 degrees/156 degrees). When a section of a wafer is submerged in and withdrawn from water, the superhydrophobic surface emerges, apparently completely dry. lithe same procedure is performed using aqueous sodium chloride as the liquid bath, individual crystals of the salt can be observed on the top of each of the posts. "Dip-coating crystallization" using an aqueous sodium chloride solution of 4.3 M produces crystals with similar to 1 mu m dimensions. A less concentrated solution, 1 M NaCl, renders crystals with similar to 500 nm dimensions. These experiments suggest that superhydrophobic surfaces that emerge from water and are "apparently completely dry" are, in fact, decorated with micrometer-size (several femtoliters) sessile water drops that rapidly evaporate. This simple technique is useful for preparation of very small liquid drops or puddles (of controlled composition) and for preparation of arrays of controlled size, crystalline substances (dip-coating crystallization)

Hydrophobization of Inorganic Oxide Surfaces Using Dimethylsilanediol

Dimethylsilanediol is a stable crystalline solid that was described in 1953. As the monomer of an important class of commercial products (poly­(dimethylsiloxanes)–silicones, PDMS) and as a simple molecule in its own right (the silicon analog of acetone hydrate), it has been neglected by several fields of fundamental and applied research including the hydrophobization of inorganic oxide surfaces. We report that dimethylsilanediol is a useful reagent for the surface modification (hydrophobization) of oxidized silicon and other oxidized metal surfaces and compare the wetting properties of modified solids with those of conventionally modified surfaces. That water is the only byproduct of this modification reaction suggests that this and likely other silanediols are useful surface-modification agents, particularly when substrate corrosion or the competitive adsorption of byproducts is an issue. We note that dimethylsilanediol is volatile with a significant vapor pressure at room temperature. Vapor-phase surface modifications are also reported

Poly(Methyl Vinyl Ketone) as a Potential Carbon Fiber Precursor

Given their increasing importance in a variety of applications, the preparation of carbon fibers with well-defined chemical structures and innocuous byproducts has garnered a growing interest over the past decade. We report the preparation of medium molecular weight poly­(methyl vinyl ketone) (PMVK) as a potential carbon fiber precursor material which can easily undergo carbonization via the well-known, acid-catalyzed aldol condensation with water as a sole byproduct. Rheological studies further show that PMVK (MW ∼ 50 kg/mol) exhibits excellent physical and thermal properties for the spinning of single and multifilament fibers and easily produces carbon yields of 25% at temperatures as low as 250 °C. Analysis of the carbonized product also suggests a more defect-free structure than commercially available carbon fibers

Rediscovering Silicones: Unreactive Silicones React with Inorganic Surfaces

Chemical reactions of linear trimethylsilyl-terminated poly(dimethyl siloxane)s with the surfaces of oxidized silicon, titanium; aluminum, and nickel are reported. These reactions lead,to covalently, attached poly(dimethylsioxane) polymer and to hydrophobized inorganic surfaces Linear silicones of this type (silicone oils) are generally not considered to be reactive with inorganic oxide Surfaces and an enormous research effort over the last 50 years to develop other silicone oils gents with reactive functional groups did not consider the simple alternative we report. In retrospect, with the acknowledgment of the facile equilibration of siloxane chains with either acid or base catalysis (that was well-known in the 1940s and 1950s), the synthetic approach to functionalized inorganic surfaces by use of linear silicones is obvious. We also report the reactions of poly[3,3,3-trifluoropropyl)rnediyIsfloxane], poly[(3-aminopropyl)methylsiloxane-rodimethylsiloxane], poly(phenylmethylsiloxane-co-dimethylsiloxane), and p-oly(d.dimethylsiloxane-block-ethylene oxide) with oxidized silicon surfices, which suggest that this reaction is general for silicones