John T. Simpson

Optically transparent, mechanically durable, nanostructured superhydrophobic surfaces enabled by spinodally phase-separated glass thin films

We describe the formation and properties of atomically bonded, optical quality, nanostructured thin glass film coatings on glass plates, utilizing phase separation by spinodal decomposition in a sodium borosilicate glass system. Following deposition via magnetron sputtering, thermal processing and differential etching, these coatings are structurally superhydrophilic (i.e., display anti-fogging functionality) and demonstrate robust mechanical properties and superior abrasion resistance. After appropriate chemical surface modification, the surfaces display a stable, non-wetting Cassie-Baxter state and exhibit exceptional superhydrophobic performance, with water droplet contact angles as large as 172°. As an added benefit, in both superhydrophobic and superhydrophilic states these nanostructured surfaces can block ultraviolet radiation and can be engineered to be anti-reflective with broadband and omnidirectional transparency. Thus, the present approach could be tailored toward distinct coatings for numerous markets, such as residential windows, windshields, specialty optics, goggles, electronic and photovoltaic cover glasses, and optical components used throughout the US military.

Monolithic Graded-Refractive-Index Glass-based Antireflective Coatings: Broadband/Omnidirectional Light Harvesting and Self-Cleaning Characteristics

A revolutionary impact on the performance of many optical systems and components can come from the integrative design of multifunctional coatings. Such coatings should be mechanically robust, and combine user-defined optical and wetting functions with scalable fabrication formulations. By taking cues from the properties of some natural biological structures, we report here the formation of low-refractive index antireflective glass films that embody omni-directional optical properties over a wide range of wavelengths, while also possessing specific wetting capabilities. The coatings comprise an interconnected network of nanoscale pores surrounded by a nanostructured silica framework. These structures result from a novel fabrication method that utilizes metastable spinodal phase separation in glass-based materials. The approach not only enables design of surface microstructures with graded-index antireflection characteristics, where the surface reflection is suppressed through optical impedance matching between interfaces, but also facilitates self-cleaning ability through modification of the surface chemistry. Based on near complete elimination of Fresnel reflections (yielding >95% transmission through a single-side coated glass) and corresponding increase in broadband transmission, the fabricated nanostructured surfaces are found to promote a general and an invaluable ∼3–7% relative increase in current output of multiple direct/indirect bandgap photovoltaic cells. Moreover, these antireflective surfaces also demonstrate superior resistance against mechanical wear and abrasion. Unlike conventional counterparts, the present antireflective coatings are essentially monolithic, enabling simultaneous realization of graded index anti-reflectivity, self-cleaning capability, and mechanical stability within the same surface. The concept represents a fundamental basis for development of advanced coated optical quality products, especially where environmental exposure is required.

Nanocone array glass

We report a novel method of producing ordered arrays of glass nanocones with precisely controlled height, lattice constant and aspect ratio. As with nanochannel glass, fibre drawing, bundling and redrawing are used to produce structured glass composite material. The surface of the composite is etched to form nanocones through a differential etching process. The lattice constant of the arrays ranges from 40 µm to 1.6 µm, while the aspect ratio of the nanocones is varied from 0.4 to 13 by simple changes in the chemistry of the hydrofluoric acid etching solution.

Superhydrophobic ceramic coatings enabled by phase-separated nanostructured composite TiO2-Cu2O thin films.

By exploiting phase-separation in oxide materials, we present a simple and potentially low-cost approach to create exceptional superhydrophobicity in thin-film based coatings. By selecting the TiO2-Cu2O system and depositing through magnetron sputtering onto single crystal and metal templates, we demonstrate growth of nanostructured, chemically phase-segregated composite films. These coatings, after appropriate chemical surface modification, demonstrate a robust, non-wetting Cassie-Baxter state and yield an exceptional superhydrophobic performance, with water droplet contact angles reaching to ~172° and sliding angles <1°. As an added benefit, despite the photo-active nature of TiO2, the chemically coated composite film surfaces display UV stability and retain superhydrophobic attributes even after exposure to UV (275 nm) radiation for an extended period of time. The present approach could benefit a variety of outdoor applications of superhydrophobic coatings, especially for those where exposure to extreme atmospheric conditions is required.

Measurement of Hydrodynamic Frictional Drag on Superhydrophobic Flat Plates in High Reynolds Number Flows

In this paper, we report the characterization of large-scale superhydrophobic surfaces for hydrodynamic drag reduction in boundary layer flows using a high-speed towing tank system. For making superhydrophobic surfaces, flat aluminum plates (4 ft × 2 ft × 3/8 in, with sharpened leading/trailing edges) were prepared and coated with nano-structured hydrophobic particles. The static and dynamic contact angle measurements indicate that the coated surfaces correspond to a de-wetting (Cassie) state with air retained on the nano-structured surfaces. Hydrodynamic drag of the large-area superhydrophobic plates was measured to cover turbulent flows (water flow speeds up to 30 ft/s, Reynolds number in the range of 105 −107 ) and compared with that of an uncoated bare aluminum control plate. Results show that an acceptable drag reduction was obtained up to ∼30% in the early stage of the turbulent regime which is due to reduced shear forces on the plates because of the lubricating air layer on the surface. However, in a fully developed turbulent flow regime, an increase in drag was measured which is mainly attributed to the amplified surface roughness due to the protrusions of air bubbles formed on the surface. Meanwhile, a qualitative observation suggests that the air bubbles are prone to be depleted during several runs of the high shear-rate flows, as revealed by streak lines of depleted air bubbles. This suggests that the superhydrophobic coating is unstable in maintaining the de-wetted state under dynamic flow conditions and that the increased drag results from the inherent surface roughness of the coating layer where the de-wetted state collapses to a wetted (Wenzel) state due to the depletion of air bubbles. However, it was also observed that the air bubbles would reform on the surface, with the same properties as a dry surface immersed in water, while the plate was kept statically immersed in water for 12 hours, suggesting that the superhydrophobic coating retains static stability for a de-wetted state. The experimental results illustrate that drag reduction is not solely dependent on the superhydrophobicity of a surface (e.g., contact angle and air fraction), but the morphology and stability of the surface air layer are also critical for the design and use of superhydrophobic surfaces for large-scale hydrodynamic drag reduction, especially in turbulent flow regimes.Copyright

Processing of loose carbon nanotubes into isolated, high density submicron channels

Loose multi-wall carbon nanotubes (MWNTs) were processed into a bundle of 19,600 individual channels with an individual channel diameter of 0.4 microm using a fiber drawing process. First, a powder of sodium silicate solution containing purified MWNTs was created. A glass capillary tube was filled with the powder and drawn into fibers. The fibers were cut into segments, bundled and redrawn multiple times to create fibers with multiple channels containing MWNTs. This processing approach created thousands of uniformly ordered channels containing dispersed MWNTs in a glass matrix while simultaneously aligning the MWNTs. The bulk resistivity of the MWNT-silicate channel has been improved by 38% after two consecutive draws as a result of the increased MWNT fraction.

Characterization of Superhydrophobic Surfaces for Anti-icing in a Low-Temperature Wind Tunnel

In this study, a closed loop low-temperature wind tunnel was custom-built and uniquely used to investigate the anti-icing mechanism of superhydrophobic surfaces in regulated flow velocities, temperatures, humidity, and water moisture particle sizes. Silica nanoparticle-based hydrophobic coatings were tested as superhydrophobic surface models. During tests, images of ice formation were captured by a camera and used for analysis of ice morphology. Prior to and after wind tunnel testing, apparent contact angles of water sessile droplets on samples were measured by a contact angle meter to check degradation of surface superhydrophobicity. A simple peel test was also performed to estimate adhesion of ice on the surfaces. When compared to an untreated sample, superhydrophobic surfaces inhibited initial ice formation. After a period of time, random droplet strikes attached to the superhydrophobic surfaces and started to coalesce with previously deposited ice droplets. These sites appear as mounds of accreted ice across the surface. The appearance of the ice formations on the superhydrophobic samples is white rather than transparent, and is due to trapped air. These ice formations resemble soft rime ice rather than the transparent glaze ice seen on the untreated sample. Compared to untreated surfaces, the icing film formed on superhydrophobic surfaces was easy to peel off by shear flows.Copyright

All-weather long-wavelength infrared free-space optical communications

ORNL is developing a high-speed, full-duplex all weather communications link for ranges up to 5 kilometers. To accomplish this project, we have constructed an RF-driven waveguide CO2 laser and a dielectric-waveguide Stark modulator. The 10-micron wavelength was selected for its ability to penetrate smoke, fog, and rain. The modulator is based on the Stark shift of NH2D (deuterated ammonia). The laser is driven by a 60 MHz RF amplifier at a power level of approximately 50 watts. The resonator cavity of the laser is formed by a 2.4 mm internal diameter ceramic waveguide with external optics. The RF electrodes are formed from aluminum heatsink extrusions that also provide cooling for the discharge. Details of the laser design will be presented.

Superhydrophobic Surfaces Properties for Anti-Icing

In this paper, the iceophobic properties of superhydrophobic surfaces are compared to those of uncoated aluminum and steel plate surfaces as investigated under dynamic flow conditions by using a closed loop low-temperature wind tunnel. Superhydrophobic surfaces were prepared at the Oak Ridge National Laboratory by coating aluminum and steel plates with nano-structured hydrophobic particles. The contact angle and contact angle hysteresis measured for these surfaces ranged from 165–170° and 1–8°, respectively. The superhydrophobic plates along with uncoated control ones were exposed to an air flow of 12 m/s and 20°F with micron-sized water droplets in the icing wind tunnel and the ice formation and accretion were probed by using high speed cameras for 90 seconds. Results show that the developed superhydrophobic coatings significantly delay the ice formation and accretion even with the impingement of accelerated super-cooled water droplets, but there is a time scale for this phenomenon which has a clear relation with contact angle hysteresis of the samples. Among the different superhydrophobic coating samples, the plate having the lowest contact angle hysteresis showed the most pronounced iceophobic effects, while the correlation between static contact angles and the iceophobic effects was not evident. The results suggest that the key parameter for designing iceophobic surfaces is to retain a low contact angle hysteresis, rather than to have only a low contact angle, which can result in more efficient anti-icing properties in dynamic flow conditions.Copyright

Spatial heterodyne interferometry techniques and applications in semiconductor wafer manufacturing

Spatial heterodyning is an interferometric technique that allows a full complex optical wavefront to be recorded and quickly reconstructed with a single image capture. Oak Ridge National Laboratory (ORNL) has combined a high-speed, image capture technique with a Fourier reconstruction algorithm to produce a method for recovery of both the phase and magnitude of the optical wavefront. Single frame spatial heterodyne interferometry (SHI) enables high-speed inspection applications such as those needed in the semiconductor industry. While the wide range of materials on wafers make literal interpretation of surface topology difficult, the wafers contain multiple copies of the same die and die-to-die comparisons are used to locate defects in high-aspect-ratio structures such as contacts, vias, and trenches that are difficult to detect with other optical techniques. Metrology with SHI has also been investigated by ORNL, in particular the use of SHI to perform metrology of line widths and heights on photolithographic masks for semiconductor wafer production. Several types of masks are currently in use with phase shifting techniques being employed to extend the wafer printing resolution. With the ability to measure the phase of the wavefront, SHI allows a more complete inspection and measurement of the phase shifting regions.