Alan M. Lyons

Superhydrophobic TiO2–Polymer Nanocomposite Surface with UV-Induced Reversible Wettability and Self-Cleaning Properties

Multifunctional superhydrophobic nanocomposite surfaces based on photocatalytic materials, such as fluorosilane modified TiO2, have generated significant research interest. However, there are two challenges to forming such multifunctional surfaces with stable superhydrophobic properties: the photocatalytic oxidation of the hydrophobic functional groups, which leads to the permanent loss of superhydrophobicity, as well as the photoinduced reversible hydrolysis of the catalytic particle surface. Herein, we report a simple and inexpensive template lamination method to fabricate multifunctional TiO2-high-density polyethylene (HDPE) nanocomposite surfaces exhibiting superhydrophobicity, UV-induced reversible wettability, and self-cleaning properties. The laminated surface possesses a hierarchical roughness spanning the micro- to nanoscale range. This was achieved by using a wire mesh template to emboss the HDPE surface creating an array of polymeric posts while partially embedding untreated TiO2 nanoparticles selectively into the top surface of these features. The surface exhibits excellent superhydrophobic properties immediately after lamination without any chemical surface modification to the TiO2 nanoparticles. Exposure to UV light causes the surface to become hydrophilic. This change in wettability can be reversed by heating the surface to restore superhydrophobicity. The effect of TiO2 nanoparticle surface coverage and chemical composition on the mechanism and magnitude of wettability changes was studied by EDX and XPS. In addition, the ability of the surface to shed impacting water droplets as well as the ability of such droplets to clean away particulate contaminants was demonstrated.

Fabricating Superhydrophobic Polymer Surfaces with Excellent Abrasion Resistance by a Simple Lamination Templating Method

Fabricating robust superhydrophobic surfaces for commercial applications is challenging as the fine-scale surface features, necessary to achieve superhydrophobicity, are susceptible to mechanical damage. Herein, we report a simple and inexpensive lamination templating method to create superhydrophobic polymer surfaces with excellent abrasion resistance and water pressure stability. To fabricate the surfaces, polyethylene films were laminated against woven wire mesh templates. After cooling, the mesh was peeled from the polymer creating a 3D array of ordered polymer microposts on the polymer surface. The resulting texture is monolithic with the polymer film and requires no chemical modification to exhibit superhydrophobicity. By controlling lamination parameters and mesh dimensions, polyethylene surfaces were fabricated that exhibit static contact angles of 160° and slip angles of 5°. Chemical and mechanical stability was evaluated using an array of manual tests as well as a standard reciprocating abraser test. Surfaces remained superhydrophobic after more than 5500 abrasion cycles at a pressure of 32.0 kPa. In addition, the surface remains dry after immersing into water for 5 h at 55 kPa. This method is environmental friendly, as it employs no solvents or harsh chemicals and may provide an economically viable path to manufacture large areas of mechanically robust superhydrophobic surfaces from inexpensive polymers and reusable templates.

Polymers from fatty acids: poly(ω-hydroxyl tetradecanoic acid) synthesis and physico-mechanical studies.

This Article describes the synthesis and physicomechanical properties of bioplastics prepared from methyl ω-hydroxytetradecanoic acid (Me-ω-OHC14), a new monomer available by a fermentation process using an engineered Candida tropicalis strain. Melt-condensation experiments were conducted using titanium tetraisopropoxide (Ti[OiPr](4)) as a catalyst in a two-stage polymerization (2 h at 200 °C under N(2), 4 h at 220 °C under 0.1 mmHg). Poly(ω-hydroxytetradecanoate), P(ω-OHC14), M(w), determined by SEC-MALLS, increased from 53K to 110K as the Ti(OiPr)(4) concentration increased from 50 to 300 ppm. By varying the polymerization conditions (catalyst concentration, reaction time, second-stage reaction temperature) a series of P(ω-OHC14) samples were prepared with M(w) values from 53K to 140K. The synthesized polyesters with M(w) ranging from 53K to 140K were subjected to characterization by DSC, TGA, DMTA, and tensile testing. Influences of P(ω-OHC14) molecular weight, melting point, and enthalpies of melting/crystallization on material tensile properties were explored. Cold-drawing tensile tests at room temperature for P(ω-OHC14) with M(w) 53K-78K showed a brittle-to-ductile transition. In contrast, P(ω-OHC14) with M(w) 53K undergoes brittle fracture. Increasing P(ω-OHC14) M(w) above 78K resulted in a strain-hardening phenomena and tough properties with elongation at break ~700% and true tensile strength of ~50 MPa. Comparisons between high density polyethylene and P(ω-OHC14) mechanical and thermal properties as a function of their respective molecular weights are discussed.

A high-precision apparatus for the characterization of thermal interface materials.

An apparatus has been designed and constructed to characterize thermal interface materials with unprecedented precision and sensitivity. The design of the apparatus is based upon a popular implementation of ASTM D5470 where well-characterized meter bars are used to extrapolate surface temperatures and measure heat flux through the sample under test. Measurements of thermal resistance, effective thermal conductivity, and electrical resistance can be made simultaneously as functions of pressure or sample thickness. This apparatus is unique in that it takes advantage of small, well-calibrated thermistors for precise temperature measurements (+/-0.001 K) and incorporates simultaneous measurement of electrical resistance of the sample. By employing precision thermometry, low heater powers and minimal temperature gradients are maintained through the meter bars, thereby reducing uncertainties due to heat leakage and changes in meter-bar thermal conductivity. Careful implementation of instrumentation to measure thickness and force also contributes to a low overall uncertainty. Finally, a robust error analysis provides uncertainties for all measured and calculated quantities. Baseline tests were performed to demonstrate the sensitivity and precision of the apparatus by measuring the contact resistance of the meter bars in contact with each other as representative low specific thermal resistance cases. A minimum specific thermal resistance of 4.68x10(-6) m(2) K/W was measured with an uncertainty of 2.7% using a heat transfer rate of 16.8 W. Additionally, example measurements performed on a commercially available graphite thermal interface material demonstrate the relationship between thermal and electrical contact resistance. These measurements further demonstrate repeatability in measured effective thermal conductivity of approximately 1%.

Thermal analysis of graphite and carbon-phenolic composites by pyrolysis-mass spectrometry

Abstract Dynamic mass spectrometry was used to characterize the pyrolytic degradation of graphite and carbon black-phenolic resin composites. Measurements were obtained on the overall yield, composition and formation rates of the volatile pyrolysis products. Pyrolysis was found to occur by three general processes: 1. (1) low temperature outgassing of free phenol present in the resin material 2. (2) formation of water from post-cure reactions at 150–300°C 3. (3) thermal fragmentation of the polymer structure above 350°C to yield low molecular weight species. Each of these processes was significantly affected by the presence of the carbon black filler material, with substantially lower yields (

Design and Fabrication of a Hybrid Superhydrophobic–Hydrophilic Surface That Exhibits Stable Dropwise Condensation

Condensation of water vapor is an essential process in power generation, water collection, and thermal management. Dropwise condensation, where condensed droplets are removed from the surface before coalescing into a film, has been shown to increase the heat transfer efficiency and water collection ability of many surfaces. Numerous efforts have been made to create surfaces which can promote dropwise condensation, including superhydrophobic surfaces on which water droplets are highly mobile. However, the challenge with using such surfaces in condensing environments is that hydrophobic coatings can degrade and/or water droplets on superhydrophobic surfaces transition from the mobile Cassie to the wetted Wenzel state over time and condensation shifts to a less-effective filmwise mechanism. To meet the need for a heat-transfer surface that can maintain stable dropwise condensation, we designed and fabricated a hybrid superhydrophobic-hydrophilic surface. An array of hydrophilic needles, thermally connected to a heat sink, was forced through a robust superhydrophobic polymer film. Condensation occurs preferentially on the needle surface due to differences in wettability and temperature. As the droplet grows, the liquid drop on the needle remains in the Cassie state and does not wet the underlying superhydrophobic surface. The water collection rate on this surface was studied using different surface tilt angles, needle array pitch values, and needle heights. Water condensation rates on the hybrid surface were shown to be 4 times greater than for a planar copper surface and twice as large for silanized silicon or superhydrophobic surfaces without hydrophilic features. A convection-conduction heat transfer model was developed; predicted water condensation rates were in good agreement with experimental observations. This type of hybrid superhydrophobic-hydrophilic surface with a larger array of needles is low-cost, robust, and scalable and so could be used for heat transfer and water collection applications.

Ratchetlike slip angle anisotropy on printed superhydrophobic surfaces.

The fabrication and properties of superhydrophobic surfaces that exhibit ratchet-like anisotropic slip angle behavior is described. The surface is composed of arrays of poly(dimethylsiloxane) (PDMS) posts fabricated by a type of 3D printing. By controlling the dispense parameters, regular arrays of asymmetric posts were deposited such that the slope of the posts was varied from 0 to 50 relative to the surface normal. Advancing and receding contact angles as well as slip angles were measured as a function of the post slope and droplet volume. Ratchetlike slip angle anisotropy was observed on surfaces composed of sloped features. The maximum slip angle difference (for a 180° tilt angle variation) was 32° for 20 μL droplets on surfaces with posts fabricated with a slope of 50°. This slip angle anisotropy is attributed to an increase in the triple contact line (TCL) length as the droplet is tilted in a direction against the post slope whereas the TCL decreases continuously when the drop travels in a direction parallel to the post slope. The increasing length of the TCL creates an increased energy barrier that accounts for the higher slip angles in this direction.

Photodefinable carbon films: Electrical properties

Abstract Carbon images were prepared by the thermal decomposition of photodefined novalac resist (HPR-206) patterns. The electrical resistivity of the films decreased over 18 orders of magnitude as the pyrolysis temperature was increased to 1050°C. The electrical characteristics of the pyrolyzed photoresist patterns (carbon images) undergo a series of transitions over this temperature range; from insulating, to semiconducting, to semimetallic states. These properties may be understood in terms of the tunneling of charge carriers between isolated, conductive regions in the film where trigonal bonding dominates. This is the first example of the direct lithography of semiconducting and semimetallic features.

Catalytic, Self-Cleaning Surface with Stable Superhydrophobic Properties: Printed Polydimethylsiloxane (PDMS) Arrays Embedded with TiO2 Nanoparticles

Maintaining the long-term stability of superhydrophobic surfaces is challenging because of contamination from organic molecules and proteins that render the surface hydrophilic. Reactive oxygen species generated on a photocatalyst, such as TiO2, could mitigate this effect by oxidizing these contaminants. However, incorporation of such catalyst particles into a superhydrophobic surface is challenging because the particles become hydrophilic under UV exposure, causing the surface to transition to the Wenzel state. Here we show that a high concentration of hydrophilic TiO2 catalytic nanoparticles can be incorporated into a superhydrophobic surface by partially embedding the particles into a printed array of high aspect ratio polydimethylsiloxane posts. A stable Cassie state was maintained on these surfaces, even under UV irradiation, because of the significant degree of hierarchical roughness. By printing the surface on a porous support, oxygen could be flowed through the plastron, resulting in higher photooxidation rates relative to a static ambient. Rhodamine B and bovine serum albumin were photooxidized both in solution and after drying onto these TiO2-containing surfaces, and the effects of particle location and plastron gas composition were studied in static and flowing gas environments. This approach may prove useful for water purification, medical devices, and other applications where Cassie stability is required in the presence of organic compounds.

Gold wire bonding onto flexible polymeric substrates

As part of a program to develop very thin, low cost packages using available technology, copper clad polymeric materials were examined as potential substrates for high temperature wire bonded chip-on-flex circuits. New thermoplastic flex and a PTFE/woven glass substrate were evaluated along with polyimides using high temperature copper laminate adhesives and adhesiveless constructions. Initial wire bond pull tests indicated all the materials were suitable for high speed gold wire bonding. Similarly, conventional glob top encapsulants were found to adhere to each of the 13 substrates tested; experimental UV curable glob top materials were found to adhere well to polyester and PTFE substrates, but not to polyimides or polyether imides. Electrical test vehicles were constructed of gold wire bonded daisy chain chips on low cost polyimide substrates. Temperature cycling and thermal shock data showed no increase in circuit resistance for packages using commercial encapsulant formulations as well as using a formulation with high CTE and high modulus.