Superhydrophobic electrospun POSS-PMMA copolymer fibres with highly ordered nanofibrillar and surface structures

A POSS-PMMA copolymer has been synthesised by conventional free-radical polymerisation reaction. Uniform electrospun fibres from this copolymer showed a water contact angle as high as 1651 with a sliding angle as low as 61. For the first time, we found that the electrospun fibres had a bundled nanofibril secondary structure with an ordered POSS morphology on the fibre surface.

Self-cleaning, superhydrophobic cotton fabrics with excellent washing durability, solvent resistance and chemical stability prepared from an SU-8 derived surface coating

Superhydrophobic cotton fabrics with a very low contact angle hysteresis were prepared using a single-pot coating solution comprising SU-8 (a negative photoresist), a fluorinated alkyl silane and silica nanoparticles. The fabric was treated using a dip-coating technique and subsequently cured under UV light. The coated fabric showed excellent superhydrophobicity with a water contact angle as high as 163° and a sliding angle as low as 2°. The coating was durable enough to withstand 100 laundry cycles. It also had excellent stability against long immersion times in organic solvents, and acid and base solutions.

Electrochemical formation of porous copper 7, 7, 8, 8-tetracyanoquinodimethane and copper 2, 3, 5, 6-tetrafluoro-7, 7, 8, 8-tetracyanoquinodimethane honeycomb surfaces with superhydrophobic properties

The electrochemical formation of highly porous CuTCNQ (TCNQ = 7,7,8,8-tetracyanoquinodimethane) and CuTCNQF4 (TCNQF4 = 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane) materials was undertaken via the spontaneous redox reaction between a porous copper template, created using a hydrogen bubbling template technique, and an acetonitrile solution containing TCNQ or TCNQF4. It was found that activation of the surface via vigorous hydrogen evolution that occurs during porous copper deposition and TCNQ mass transport being hindered through the porous network of the copper template influenced the growth of CuTCNQ and CuTCNQF4. This approach resulted in the fabrication of a honeycomb layered type structure where the internal walls consist of very fine crystalline needles or spikes. This combination of microscopic and nanoscopic roughness was found to be extremely beneficial for anti-wetting properties where superhydrophobic materials with contact angles as high as 177° were created. Given that CuTCNQ and CuTCNQF4 have shown potential as molecular based electronic materials in the area of switching and field emission, the creation of a surface that is moisture resistant may be of applied interest.

Superhydrophobic amorphous carbon/carbon nanotube nanocomposites

Superhydrophobic amorphous carbon/carbon nanotube nanocomposites are fabricated by plasma immersion ion implantation with carbon nanotube forests as a template. The microstructure of the fabricated nanocomposites shows arrays of carbon nanotubes capped with amorphous carbon nanoparticles. Contact angle measurements show that both advancing and receding angles close to 180° can be achieved on the nanocomposites. The fabrication here does not require patterning of carbon nanotubes or deposition of conformal coatings with low surface energy, which are usually involved in conventional approaches for superhydrophobic surfaces. The relationship between the observed superhydrophobicity and the unique microstructure of the nanocomposites is discussed. © 2009 American Institute of Physics.

Electrowetting control of Cassie-to-Wenzel Transitions in superhydrophobic carbon nanotube-based nanocomposites

The possibility of effective control of the wetting properties of a nanostructured surface consisting of arrays of amorphous carbon nanoparticles capped on carbon nanotubes using the electrowetting technique is demonstrated. By analyzing the electrowetting curves with an equivalent circuit model of the solid/liquid interface, the long-standing problem of control and monitoring of the transition between the "slippy" Cassie state and the "sticky" Wenzel states is resolved. The unique structural properties of the custom-designed nanocomposites with precisely tailored surface energy without using any commonly utilized low-surface-energy (e.g., polymer) conformal coatings enable easy identification of the occurrence of such transition from the optical contrast on the nanostructured surfaces. This approach to precise control of the wetting mode transitions is generic and has an outstanding potential to enable the stable superhydrophobic capability of nanostructured surfaces for numerous applications, such as low-friction microfluidics and self-cleaning.

Measurement studies on Superhydrophobic materials

Superhydrophobicity is directly related to the wettability of the surfaces. Cassie-Baxter state relating to geometrical configuration of solid surfaces is vital to achieving the Superhydrophobicity and to achieve Cassie-Baxter state the following two criteria need to be met: 1) Contact line forces overcome body forces of unsupported droplet weight and 2) The microstructures are tall enough to prevent the liquid that bridges microstructures from touching the base of the microstructures [1]. In this paper we discuss different measurements used to characterise/determine the superhydrophobic surfaces.

Superhydrophobic Polymers

Superhydrophobic polymers are particularly attractive materials, as they combine low cost, ease of processing, and compatibility with a variety of applications. Surfaces that display the Cassie–Baxter wetting state are particularly attractive for their self-cleaning properties. In this chapter, a brief overview of the wetting principles will be followed by an account of several techniques currently used to impart superhydrophobicity onto polymer surfaces. Surface roughness and surface structure will be the focus of this chapter, with an emphasis on topographies that exhibit microscale or nanoscale features arranged in hierarchical order.

Superhydrophobic fabrics for oil-water separation based on the metal organic charge transfer complex CuTCNAQ

This work reports on the fabrication of a superhydrophobic nylon textile based on the organic charge transfer complex CuTCNAQ (TCNAQ = 11,11,12,12-tetracyanoanthraquinodimethane). The nylon fabric that is metallized with copper undergoes a spontaneous chemical reaction with TCNAQ dissolved in acetonitrile to form nanorods of CuTCNAQ that are intertwined over the entire surface of the fabric. This creates the necessary micro and nanoscale roughness that is required for the Cassie-Baxter state thereby achieving a superhydrophobic/superoleophilic surface without the need for a fluorinated surface. The material is characterised with SEM, FT-IR and XPS spectroscopy and investigated for its ability to separate oil and water in two modes, namely under gravity and as an absorbent. It is found that the fabric can separate dichloromethane, olive oil and crude oil from water and in fact reduce the water content of the oil during the separation process. The fabric is reusable and tolerant to conditions such as seawater, hydrochloric acid and extensive time periods on the shelf. Given that CuTCNAQ is a copper based semiconductor may also open up the possibility of other applications in areas such as photocatalysis and antibacterial applications.

Characterisation of microstructure and evaluation of optical and EPR properties of superhydrophobic copper dodecanoate films

Copper dodecanoate films prepared by emulsion method exhibit superhydrophobic property with water contact angle of 155 degrees and sliding angle of <2 degrees. The films have been characterised by using X-ray diffraction, field emission scanning electron microscopy and Fourier transform infrared spectroscopy techniques. Surface microstructure of copper dodecanoate consists of numerous microscale papillas of about 6-12 mu m in length with a diameter in the range of 360-700 nm. The superhydrophobicity of the films is due to their dual micronano surface morphology. The wetting behaviour of the film surface was studied by a simple water immersion test. The results show that copper dodecanoate film retained superhydrophobic property even after immersing in water for about 140 h. The optical absorption spectrum exhibits two broadbands centred at 388 and 630 nm that have been assigned to B-2(1g) -> E-2(g) and B-2(1g) -> B-2(2g) transitions of Cu2+ ions, respectively. The electron paramagnetic resonance spectrum exhibits two resonance signals with effective g values at g(parallel to)approximate to 2.308 and g(perpendicular to) approximate to 2.071, which suggests that the unpaired electron occupies d(x2-y2) orbital in the ground state. Copyright (C) 2011 John Wiley & Sons, Ltd.

Surface modification of textured silicon and its wetting behaviour

Textured silicon (Si) substrate were prepared using various texturing methods both chemical and physical and their water contact angle, surface topography and Raman spectra were studied and investigated. The effect of plasma and chemical treatment on micro/nanostructure and roughness of the surface with and without deposition of Octadecyltrichlorosilane (ODTS, Cl3Si (CH3)(17)), self-assembled monolayer (SAM) is investigated for achieving higher water contact angle (theta(c)). The importance of synergism of texturing with deposition of ODTS SAM in preparing superhydrophobic silicon surfaces has been discussed. It is shown that superhydrophobic silicon surfaces can be achieved on silicon surfaces by coating with ODTS, irrespective of whether it is textured or not, polished or unpolished, provided a chemical treatment is given to the surface prior to the ODTS coating.

Control of wettability of carbon nanotube array by reversible dry oxidation for superhydrophobic coating and supercapacitor applications

In this thesis, dry chemical modification methods involving UV/ozone, oxygen plasma, and vacuum annealing treatments are explored to precisely control the wettability of CNT arrays. By varying the exposure time of these treatments the surface concentration of oxygenated groups adsorbed on the CNT arrays can be controlled. CNT arrays with very low amount of oxygenated groups exhibit a superhydrophobic behavior. In addition to their extremely high static contact angle, they cannot be dispersed in DI water and their impedance in aqueous electrolytes is extremely high. These arrays have an extreme water repellency capability such that a water droplet will bounce off of their surface upon impact and a thin film of air is formed on their surface as they are immersed in a deep pool of water. In contrast, CNT arrays with very high surface concentration of oxygenated functional groups exhibit an extreme hydrophilic behavior. In addition to their extremely low static contact angle, they can be dispersed easily in DI water and their impedance in aqueous electrolytes is tremendously low. Since the bulk structure of the CNT arrays are preserved during the UV/ozone, oxygen plasma, and vacuum annealing treatments, all CNT arrays can be repeatedly switched between superhydrophilic and superhydrophobic, as long as their O/C ratio is kept below 18%.

The effect of oxidation using UV/ozone and oxygen plasma treatments is highly reversible as long as the O/C ratio of the CNT arrays is kept below 18%. At O/C ratios higher than 18%, the effect of oxidation is no longer reversible. This irreversible oxidation is caused by irreversible changes to the CNT atomic structure during the oxidation process. During the oxidation process, CNT arrays undergo three different processes. For CNT arrays with O/C ratios lower than 40%, the oxidation process results in the functionalization of CNT outer walls by oxygenated groups. Although this functionalization process introduces defects, vacancies and micropores opening, the graphitic structure of the CNT is still largely intact. For CNT arrays with O/C ratios between 40% and 45%, the oxidation process results in the etching of CNT outer walls. This etching process introduces large scale defects and holes that can be obviously seen under TEM at high magnification. Most of these holes are found to be several layers deep and, in some cases, a large portion of the CNT side walls are cut open. For CNT arrays with O/C ratios higher than 45%, the oxidation process results in the exfoliation of the CNT walls and amorphization of the remaining CNT structure. This amorphization process can be implied from the disappearance of C-C sp2 peak in the XPS spectra associated with the pi-bond network.

The impact behavior of water droplet impinging on superhydrophobic CNT arrays in a low viscosity regime is investigated for the first time. Here, the experimental data are presented in the form of several important impact behavior characteristics including critical Weber number, volume ratio, restitution coefficient, and maximum spreading diameter. As observed experimentally, three different impact regimes are identified while another impact regime is proposed. These regimes are partitioned by three critical Weber numbers, two of which are experimentally observed. The volume ratio between the primary and the secondary droplets is found to decrease with the increase of Weber number in all impact regimes other than the first one. In the first impact regime, this is found to be independent of Weber number since the droplet remains intact during and subsequent to the impingement. Experimental data show that the coefficient of restitution decreases with the increase of Weber number in all impact regimes. The rate of decrease of the coefficient of restitution in the high Weber number regime is found to be higher than that in the low and moderate Weber number. Experimental data also show that the maximum spreading factor increases with the increase of Weber number in all impact regimes. The rate of increase of the maximum spreading factor in the high Weber number regime is found to be higher than that in the low and moderate Weber number. Phenomenological approximations and interpretations of the experimental data, as well as brief comparisons to the previously proposed scaling laws, are shown here.

Dry oxidation methods are used for the first time to characterize the influence of oxidation on the capacitive behavior of CNT array EDLCs. The capacitive behavior of CNT array EDLCs can be tailored by varying their oxygen content, represented by their O/C ratio. The specific capacitance of these CNT arrays increases with the increase of their oxygen content in both KOH and Et4NBF4/PC electrolytes. As a result, their gravimetric energy density increases with the increase of their oxygen content. However, their gravimetric power density decreases with the increase of their oxygen content. The optimally oxidized CNT arrays are able to withstand more than 35,000 charge/discharge cycles in Et4NBF4/PC at a current density of 5 A/g while only losing 10% of their original capacitance.

Physicochemical characteristics and droplet impact dynamics of superhydrophobic carbon nanotube arrays.

The physicochemical and droplet impact dynamics of superhydrophobic carbon nanotube arrays are investigated. These superhydrophobic arrays are fabricated simply by exposing the as-grown carbon nanotube arrays to a vacuum annealing treatment at a moderate temperature. This treatment, which allows a significant removal of oxygen adsorbates, leads to a dramatic change in wettability of the arrays, from mildly hydrophobic to superhydrophobic. Such change in wettability is also accompanied by a substantial change in surface charge and electrochemical properties. Here, the droplet impact dynamics are characterized in terms of critical Weber number, coefficient of restitution, spreading factor, and contact time. Based on these characteristics, it is found that superhydrophobic carbon nanotube arrays are among the best water-repellent surfaces ever reported. The results presented herein may pave a way for the utilization of superhydrophobic carbon nanotube arrays in numerous industrial and practical applications, including inkjet printing, direct injection engines, steam turbines, and microelectronic fabrication.

A topography/chemical composition gradient polystyrene surface: Toward the investigation of the relationship between surface wettability and surface structure and chemical composition

In this paper, we have prepared of a topography/chemical composition gradient polystyrene (PS) surface, i.e., an orthogonal gradient surface, to investigate the relationship between surface wettability and surface structure and chemical composition. The prepared surface shows a one-dimensional gradient in wettability in the x, y, and diagonal directions, including hydrophobic to hydrophilic, superhydrophobic to hydrophobic, superhydrophobic to superhydrophilic gradients, and so forth.

Sheets of Large Superhydrophobic Metal Particles Self Assembled on Water by the Cheerios Effect

A copper-rich cereal: Superhydrophobic copper particles show a very large Cheerios effect and rapidly self-assemble into robust sheets on the surface of water. These sheets can support objects (including water drops, see photo) placed on them, even though the irregular geometry of the particles means that they contain macroscopic holes.