Bioinspired Anti-fouling Coating on Hydrophobic Surfaces

Thesis (Master's)--University of Washington, 2016-06

Low-density polyethylene superhydrophobic surface by control of its crystallization behavior

A simple and inexpensive method for forming a low-density polyethylene (LDPE) superhydrophobic surface by controlling the crystallization behavior of LDPE by adjusting the crystallization time and nucleation rate has been proposed. The resulting porous surface, with hierarchical micro- and nanostructures on the beautiful floral designs, has a water contact angle of 173.0degrees +/- 2.5degrees.

AFM study of forces between silicon oil and hydrophobic - hydrophylic surfaces in aqueous solutions

An investigation has been made of the interactions between silicone oil and various solid substrates immersed in aqueous solutions. Measurements were made using an atomic force microscope (AFM) using the colloid-probe method. The silicone oil drop is simulated by coating a small silica sphere with the oil, and measuring the force as this coated sphere is brought close to contact with a flat solid surface. It is found that the silicone oil surface is negatively charged, which causes a double-layer repulsion between the oil drop and another negatively charged surface such as mica. With hydrophilic solids, this repulsion is strong enough to prevent attachment of the drop to the solid. However, with hydrophobic surfaces there is an additional attractive force which overcomes the double-layer repulsion, and the silicone oil drop attaches to the solid. A "ramp" force appears in some, but not all, of the data sets. There is circumstantial evidence that this force results from compression of the silicone oil film coated on the glass sphere.

Effect of wettability and surface roughness on ice-adhesion strength of hydrophilic, hydrophobic and superhydrophobic surfaces

The anti-icing properties of hydrophilic, hydrophobic and superhydrophobic surfaces/coatings were evaluated using a custom-built apparatus based on zero-degree cone test method. The ice-adhesion reduction factor (ARF) of these coatings has been evaluated using bare aluminium alloy as a reference. The wettability of the surfaces was evaluated by measuring water contact angle (WCA) and sliding angle. It was found that the ice-adhesion strength (tau) on silicone based hydrophobic surfaces was similar to 43 times lower than compared to bare polished aluminium alloy indicating excellent anti-icing property of these coatings. Superhydrophobic coatings displayed poor anti-icing property in spite of their high water repellence. Field Emission Scanning Electron Microscope reveal that Silicone based hydrophobic coatings exhibited smooth surface whereas the superhydrophobic coatings had a rough surface consisting of microscale bumps and protrusions superimposed with nanospheres. Both surface roughness and surface energy play a major role on the ice-adhesion strength of the coatings. The 3D surface roughness profiles of the coatings also indicated the same trend of roughness. An attempt is made to correlate the observed ice-adhesion strength of different surfaces with their wettability and surface roughness. (C) 2014 Elsevier B.V. All rights reserved.

Super-hydrophobicity of silica nanoparticles modified with vinyl groups

Super-hydrophobic films with vinyl-modified silica nanoparticles (V-SiOx-NPs) were successfully prepared. The rough surface, which was composed of microstructures of disordered V-SiOx-NPs and nanostructures on the surface of V-SiOx-NPs, rather than the chemical composition devoted to the super-hydrophobicity of film. The relationship between contact angle and diameter of V-SiOx-NPs was then investigated. The sessile contact angles (CA) of films with 150-1600nm V-SiOx-NPs were around 166 regardless the diameter, while the film with 85 nm V-SiOx-NPs had the lowest CA of about 158. The packing manner of V-SiOx-NPs determined the air fraction on the surface and then the CA.

Nanostructured metal oxides as adsorbents and photocatalysts

This research underlines the extensive application of nanostructured metal oxides in environmental systems such as hazardous waste remediation and water purification. This study tries to forge a new understanding of the complexity of adsorption and photocatalysis in the process of water treatment. Sodium niobate doped with a different amount of tantalum, was prepared via a hydrothermal reaction and was observed to be able to adsorb highly hazardous bivalent radioactive isotopes such as Sr2+ and Ra2+ions. This study facilitates the preparation of Nb-based adsorbents for efficiently removing toxic radioactive ions from contaminated water and also identifies the importance of understanding the influence of heterovalent substitution in microporous frameworks. Clay adsorbents were prepared via a two-step method to remove anionic and non-ionic herbicides from water. Firstly, layered beidellite clay was treated with acid in a hydrothermal process; secondly, common silane coupling agents, 3-chloro-propyl trimethoxysilane or triethoxy silane, were grafted onto the acid treated samples to prepare the adsorption materials. In order to isolate the effect of the clay surface, we compared the adsorption property of clay adsorbents with ƒ×-Al2O3 nanofibres grafted with the same functional groups. Thin alumina (£^-Al2O3) nanofibres were modified by the grafting of two organosilane agents 3-chloropropyltriethoxysilane and octyl triethoxysilane onto the surface, for the adsorptive removal of alachlor and imazaquin herbicides from water. The formation of organic groups during the functionalisation process established super hydrophobic sites along the surfaces and those non-polar regions of the surfaces were able to make close contact with the organic pollutants. A new structure of anatase crystals linked to clay fragments was synthesised by the reaction of TiOSO4 with laponite clay for the degradation of pesticides. Based on the Ti/clay ratio, these new catalysts showed a high degradation rate when compared with P25. Moreover, immobilized TiO2 on laponite clay fragments could be readily separated out from a slurry system after the photocatalytic reaction. Using a series of partial phase transition methods, an effective catalyst with fibril morphology was prepared for the degradation of different types of phenols and trace amount of herbicides from water. Both H-titanate and TiO2-(B) fibres coated with anatase nanocrystal were studied. When compared with a laponite clay photocatalyst, it was found that anatase dotted TiO2-(B) fibres prepared by a 45 h hydrothermal treatment followed by calcination were not only superior in performance in photocatalysis but could also be readily separated from a slurry system after photocatalytic reactions. This study has laid the foundation for the development of the ability to fabricate highly efficient nanostructured solids for the removal of radioactive ions and organic pollutants from contaminated water. These results now seem set to contribute to the development of advanced water purification devices in the future. These modified nanostructured materials with unusual properties have broadened their application range beyond their traditional use as adsorbents, to also encompass the storage of nuclear waste after concentrating from contaminated water.

Surface modification of alumina nanofibres for the selective adsorption of alachlor and imazaquin herbicides

The effective removal of pollutants using a thermally and chemically stable substrate that has controllable absorption properties is a goal of water treatment. In this study, the surfaces of thin alumina (γ-Al2O3) nanofibres were modified by the grafting either of two organosilane agents, 3-chloro-propyl-triethoxysilane (CPTES) and octyl-triethoxysilane (OTES). These modified materials were then trialed as absorbents for the removal of two herbicides, alachlor and imazaquin from water. The formation of organic groups during the functionalisation process established super hydrophobic sites on the surfaces of the nanofibres. This super hydrophobic group is a kind of protruding adsorption site which facilitates the intimate contact with the pollutants. OTES grafted substrate were shown to be more selective for alachlor while imazaquin selectivity is shown by the CPTES grafted substrate. Kinetics studies revealed that imazaquin was rapidly adsorbed on CPTES-modified surfaces. However, the adsorption of alachlor by OTES grafted surface was achieved more slowly.

The BAD project: data mining, database and prediction of protein adsorption on surfaces

Protein adsorption at solid-liquid interfaces is critical to many applications, including biomaterials, protein microarrays and lab-on-a-chip devices. Despite this general interest, and a large amount of research in the last half a century, protein adsorption cannot be predicted with an engineering level, design-orientated accuracy. Here we describe a Biomolecular Adsorption Database (BAD), freely available online, which archives the published protein adsorption data. Piecewise linear regression with breakpoint applied to the data in the BAD suggests that the input variables to protein adsorption, i.e., protein concentration in solution; protein descriptors derived from primary structure (number of residues, global protein hydrophobicity and range of amino acid hydrophobicity, isoelectric point); surface descriptors (contact angle); and fluid environment descriptors (pH, ionic strength), correlate well with the output variable-the protein concentration on the surface. Furthermore, neural network analysis revealed that the size of the BAD makes it sufficiently representative, with a neural network-based predictive error of 5% or less. Interestingly, a consistently better fit is obtained if the BAD is divided in two separate sub-sets representing protein adsorption on hydrophilic and hydrophobic surfaces, respectively. Based on these findings, selected entries from the BAD have been used to construct neural network-based estimation routines, which predict the amount of adsorbed protein, the thickness of the adsorbed layer and the surface tension of the protein-covered surface. While the BAD is of general interest, the prediction of the thickness and the surface tension of the protein-covered layers are of particular relevance to the design of microfluidics devices.

Time dependent superhydrophobicity of drag reducing surfaces

Air can be trapped on the crevices of specially textured hydrophobic surfaces immersed in water. This heterogenous state of wetting in which the water is in contact with both the solid surface and the entrapped air is not stable. Diffusion of air into the surrounding water leads to gradual reduction in the size and numbers of the air bubbles. The sustainability of the entrapped air on such surfaces is important for many underwater applications in which the surfaces have to remain submersed for longer time periods. In this paper we explore the suitability of different classes of surface textures towards the drag reduction application by evaluating the time required for the disappearance of the air bubbles under hydrostatic conditions. Different repetitive textures consisting of holes, pillars and ridges of different sizes have been generated in silicon, aluminium and brass by isotropic etching, wire EDM and chemical etching respectively. These surfaces were rendered hydrophobic with self-assembled layer of fluorooctyl trichlorosilane for silicon and aluminium surfaces and 1-dodecanethiol for brass surfaces. Using total internal reflection the air bubbles are visualized with the help of a microscope and time lapse photography. Irrespective of the texture, both the size and the number of air pockets were found to decrease with time gradually and eventually disappear. In an attempt to reverse the diffusion we explore the possibility of using electrolysis to generate gases at the textured surfaces. The gas bubbles are nucleated everywhere on the surface and as they grow they coalesce with each other and get pinned at the texture edges.

Orientational order as the origin of the long-range hydrophobic effect

The long range attractive force between two hydrophobic surfaces immersed in water is observed to decrease exponentially with their separation-this distance-dependence of effective force is known as the hydrophobic force law (HFL). We explore the microscopic origin of HFL by studying distance-dependent attraction between two parallel rods immersed in 2D Mercedes Benz model of water. This model is found to exhibit a well-defined HFL. Although the phenomenon is conventionally explained by density-dependent theories, we identify orientation, rather than density, as the relevant order parameter. The range of density variation is noticeably shorter than that of orientational heterogeneity. The latter is comparable to the observed distances of hydrophobic force. At large separation, attraction between the rods arises primarily from a destructive interference among the inwardly propagating oppositely oriented heterogeneity generated in water by the two rods. As the rods are brought closer, the interference increases leading to a decrease in heterogeneity and concomitant decrease in free energy of the system, giving rise to the effective attraction. We notice formation of hexagonal ice-like structures at the onset of attractive region which suggests that metastable free energy minimum may play a role in the origin of HFL. (C) 2015 AIP Publishing LLC.

Effect of absolute pressure on flow through a textured hydrophobic microchannel

The potential of textured hydrophobic surfaces to provide substantial drag reduction has been attributed to the presence of air bubbles trapped on the surface cavities. In this paper, we present results on water flow past a textured hydrophobic surface, while systematically varying the absolute pressure close to the surface. Trapped air bubbles on the surface are directly visualized, along with simultaneous pressure drop measurements across the surface in a microchannel configuration. We find that varying the absolute pressure within the channel greatly influences the trapped air bubble behavior, causing a consequent effect on the pressure drop (drag). When the absolute pressure within the channel is maintained below atmospheric pressure, we find that the air bubbles grow in size, merge and eventually detach from the surface. This growth and subsequent merging of the air bubbles leads to a substantial increase in the pressure drop. On the other hand, a pressure above the atmospheric pressure within the channel leads to gradual shrinkage and eventual disappearance of trapped air bubbles. We find that in this case, air bubbles do cause reduction in the pressure drop with the minimum pressure drop (or maximum drag reduction) occurring when the bubbles are flush with the surface. These results show that the trapped air bubble dynamics and the pressure drop across a textured hydrophobic microchannel are very significantly dependent on the absolute pressure within the channel. The results obtained hold important implications toward achieving sustained drag reduction in microfluidic applications.

An Atomistic-Continuum Hybrid Simulation Of Fluid Flows Over Superhydrophobic Surfaces

Recent experiments have found that slip length could be as large as on the order of 1 mu m for fluid flows over superhydrophobic surfaces. Superhydrophobic surfaces can be achieved by patterning roughness on hydrophobic surfaces. In the present paper, an atomistic-continuum hybrid approach is developed to simulate the Couette flows over superhydrophobic surfaces, in which a molecular dynamics simulation is used in a small region near the superhydrophobic surface where the continuum assumption is not valid and the Navier-Stokes equations are used in a large region for bulk flows where the continuum assumption does hold. These two descriptions are coupled using the dynamic coupling model in the overlap region to ensure momentum continuity. The hybrid simulation predicts a superhydrophobic state with large slip lengths, which cannot be obtained by molecular dynamics simulation alone.

An atomistic-continuum hybrid simulation of fluid flows over superhydrophobic surfaces

Recent experiments have found that slip length could be as large as on the order of 1 mu m for fluid flows over superhydrophobic surfaces. Superhydrophobic surfaces can be achieved by patterning roughness on hydrophobic surfaces. In the present paper an atomistic-continuum hybrid approach is developed to simulate the Couette flows over superhydrophobic surfaces in which a molecular dynamics simulation is used in a small region near the superhydrophobic surface where the continuum assumption is not valid and the Navier-Stokes equations are used in a large region for bulk flows where the continuum assumption does hold. These two descriptions are coupled using the dynamic coupling model in the overlap region to ensure momentum continuity. The hybrid simulation predicts a superhydrophobic state with large slip lengths which cannot be obtained by molecular dynamics simulation alone.

Formation of a supported hybrid bilayer membrane on gold: A sterically enhanced hydrophobic effect

Adsorption of a monolayer of didecanoyl-L-alpha-phosphatidylcholine (DDPC) from dispersions of small unilamellar vesicles onto hydrophobic surfaces was investigated by mean of cyclic voltammetry and impedance spectroscopy. The hydrophobic surfaces were self-assembled monolayers of 2-mereapto-3-n-octylthiophene (MOT) on gold. One characteristic of the MOT monolayer is its permeability to organic molecules in aqueous solution, thus providing a more energetically favorable hydrophobic surface for the addition of phospholipid vesicles. The kinetics of the lipid monolayer formation were followed by measuring the time-dependent interfacial capacitance. Unusual values of thickness and capacitance of the MOT/ DDPC bilayers were observed. An interdigitating conformation of the bilayer structure was proposed to interpret the experimental results, The horseradish peroxidase reconstituted into the bilayer demonstrated the expected protein activity, showing practical use in research and in biosensor application.

Protecting group and switchable pore-discriminating adsorption properties of a hydrophilic-hydrophobic metal-organic framework

Formed by linking metals or metal clusters through organic linkers, metal-organic frameworks are a class of solids with structural and chemical properties that mark them out as candidates for many emerging gas storage, separation, catalysis and biomedical applications. Important features of these materials include their high porosity and their flexibility in response to chemical or physical stimuli. Here, a copper-based metal-organic framework has been prepared in which the starting linker (benzene-1,3,5-tricarboxylic acid) undergoes selective monoesterification during synthesis to produce a solid with two different channel systems, lined by hydrophilic and hydrophobic surfaces, respectively. The material reacts differently to gases or vapours of dissimilar chemistry, some stimulating subtle framework flexibility or showing kinetic adsorption effects. Adsorption can be switched between the two channels by judicious choice of the conditions. The monoesterified linker is recoverable in quantitative yield, demonstrating possible uses of metal-organic frameworks in molecular synthetic chemistry as 'protecting groups' to accomplish selective transformations that are difficult using standard chemistry techniques.