In situ formation and size control of gold nanoparticles into chitosan for nanocomposite surfaces with tailored wettability

The in situ formation of gold nanoparticles into the natural polymer chitosan is described upon pulsed laser irradiation. In particular, hydrogel-type films of chitosan get loaded with the gold precursor, chloroauric acid salt (HAuCl(4)), by immersion in its aqueous solution. After the irradiation of this system with increasing number of ultraviolet laser pulses, we observe the formation of gold nanoparticles with increasing density and decreasing size. Analytical studies using absorption measurements, atomic force microscopy, scanning electron microscopy, and X-ray photoelectron spectroscopy of the nanocomposite samples throughout the irradiation procedure reveal that under the specific irradiation conditions there are two competing mechanisms responsible for the nanoparticles production: the photoreduction of the precursor responsible for the rising growth of gold particles with increasing size and the subsequent photofragmentation of these particles into smaller ones. The described method allows the localized formation of gold nanoparticles into specific areas of the polymeric films, expanding its potential applications due to its patterning capability. The size and density control of the gold nanoparticles, obtained by the accurate increase of the laser irradiation time, is accompanied by the simultaneously controlled increase of the wettability of the obtained gold nanocomposite surfaces. The capability of tailoring the hydrophilicity of nanocomposite materials based on natural polymer and biocompatible gold nanoparticles provides new potentialities in microfluidics or lab on chip devices for blood analysis or drugs transport, as well as in scaffold development for preferential cells growth.     

Photoresponsive surfaces with controllable wettability

In this paper, current progress in the area of photoresponsive surfaces with controllable wettability is reviewed, including mainly surface conversion between wetting and anti-wetting, prepared from inorganic oxides (e.g., titanium dioxide, zinc oxide, and tungsten oxide) or/and photoactive organic molecules (e.g., azobenzene, and spiropyran), and movement of liquid droplets driven by molecular machines (e.g., molecular shuttles such as rotaxanes). Photoresponsive controllable wettability originates from a transition between the bistable states of photoresponsive materials. The exploration of the basic mechanisms provides a basis for the construction of novel smart responsive surfaces.     

Thermosensitive copolymer coatings with enhanced wettability switching

Expanded cross-linked copolymers of poly(N-isopropylacrylamide) (PNiPAAm) and poly(acrylic acid) (PAAc) of varying monomer ratios were grafted from a crystalline silicon surface. Surface-tethered polymerization was performed at a slightly basic pH, where electrostatic repulsion among acrylic acid monomer units forces the network into an expanded polymer conformation. The influence of this expanded conformation on switchability between a hydrophilic and a hydrophobic state was investigated. Characterization of the copolymer coating was carried out by means of X-ray photoelectron spectroscopy (XPS) ellipsometry, and diffuse reflectance IR. Lower critical solution temperatures (LCSTs) of the copolymer grafts on the silicon surfaces were determined by spectrophotometry. Temperature-induced wettability changes were studied using sessile drop contact angle measurements. The surface topography was investigated by atomic force microscopy (AFM) in Milli-Q water at 25 and 40 degrees C. The reversible attachment of a fluorescently labeled model protein was studied as a function of temperature using a fluorescence microscope and a fluorescence spectrometer. Maximum switching in terms of the contact angle change around the LCST was observed at a ratio of 36:1 PNiPAAm to PAAc. The enhanced control of biointerfaces achieved by these coatings may find applications in biomaterials, biochips, drug delivery, and microfluidics.     

Water microdroplets on molecularly tailored surfaces: correlation between wetting hysteresis and evaporation mode switching

The evaporation of water microdroplets from solid surfaces was studied using digital contact angle analysis techniques. An inclusive trend for the evaporation process, that is, a switch from the initial constant contact area to the subsequent constant contact angle mode was observed for all surfaces examined, including mixed self-assembled monolayers (SAMs) on gold and "conventional" surfaces such as silicon wafers, polycarbonate, and Teflon. More importantly, it has been shown that the change in contact angle during the evaporation process (i.e., evaporation hysteresis, delta theta(evap), the difference between the initial and "equilibrated" contact angle) correlates well with the wetting hysteresis determined directly (i.e., measuring the advancing and receding contact angles on these surfaces by changing the drop volume). The comparison between mixed SAM surfaces and conventional solids revealed that the evaporation/wetting hysteresis is dominated by the roughness (from nanometer to micrometer scale) rather than the chemical heterogeneity of the surface. The evaporation rates of water microdroplets on these surfaces were also monitored and modeled.     

pH responsive surfaces with nanoscale topography

We report the preparation of nanostructured adaptive polymer surfaces by diffusion of an amphihilic block copolymer toward the interface. The surface segregation of a diblock copolymer, polystyrene‐block‐poly(acrylic acid) (PS‐b‐PAA), occurred when blended with high molecular weight polystyrene employed as a matrix. On annealing, the polymer surfaces changed both the chemical composition and the hydrophilicity depending on the environment and pH, respectively. By exposure to either water vapor or air, the surface wettability varied between hydrophilic and hydrophobic. In addition, surface enrichment on diblock copolymer by water vapor annealing led to self‐assembly occurring at the interface. Hence, nanostructured domains can be observed by AFM in liquid media. Moreover, the PAA segments placed at the interface respond to pH and can switch from an extended hydrophilic state at basic pH values to a collapsed hydrophobic state in acidic media. Accordingly, the surface morphology changed from swelled micelles to nanometer size holes. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2982–2990, 2010     

Nanostructuring of a polymeric substrate with well-defined nanometer-scale topography and tailored surface wettability

This study demonstrates a simple and highly reproducible method for fabricating well-defined nanostructured polymeric surfaces with aligned nanoembosses or nanofibers of controllable aspect ratios, showing remarkable structural similarity with interesting natural biostructures such as the wing surface of Cicada orni and the leaf surface of Lotus. Our studies on the present biomimetic surfaces revealed that the wetting property of the nanostructured surface of a given chemical composition could be systematically controlled by rendering nanometer-scale roughness. The nanofabricating method we developed can be readily extended to other thermoplastic polymeric materials (e.g., light-emitting polymers, conducting polymers, block copolymers, liquid crystalline polymers), and it could be applied to developing a new generation of optical and electronic devices.     

Fabrication and characterization of plasma processed surfaces with tuned wettability

Engineered surfaces with controlled hydrophilic/ hydrophobic character have been fabricated by tailoring the substrate topography and chemistry. In this method, the substrate to be treated was first coated by a photoresist, which was then surface-roughened using SF6 plasma etching. The resulting rough texture was then transferred to the underlying silicon surface by over-etching of the photoresist. At this point, the topographically modified surface was modified chemically by controlled deposition of a thin polymer layer using plasma processing. In this way, both the surface texture and the surface chemistry could be varied independently, producing surfaces with variable wetting character, including super-hydrophilicity and super-hydrophobicity, depending on the choice of plasma polymer deposited. Chemical characterization demonstrates a correlation between the surface chemistry and the wettability of the samples after etching. The surface elementary composition contained more C-F groups as the measured contact angle increased, indicating that the change of wettability is due to both the roughness and the surface energy of the deposited photoresist. In the case of materials deposited on the plasma-treated rough surfaces, the strengthening of the wetting character is only due to the created surface roughness, as XPS analyses showed no significant chemical difference as compared to the flat polymer.     

Droplet motion on designed microtextured superhydrophobic surfaces with tunable wettability

Superhydrophobic surfaces have shown promising applications in microfluidic systems as a result of their water-repellent and low-friction properties over the past decade. Recently, designed microstructures have been experimentally applied to construct wettability gradients and direct the droplet motion. However, thermodynamic mechanisms responsible for the droplet motion on such regular rough surfaces have not been well understood such that at present specific guidelines for the design of tunable superhydrophobic surfaces are not available. In this study, we propose a simple but robust thermodynamic methodology to gain thorough insight into the physical nature for the controllable motion of droplets. On the basis of the thermodynamic calculations of free energy (FE) and the free-energy barrier (FEB), the effects of surface geometry of a pillar microtexture are systematically investigated. It is found that decreasing the pillar width and spacing simultaneously is required to lower the advancing and receding FEBs to effectively direct droplets on the roughness gradient surface. Furthermore, the external energy plays a role in the actuation of spontaneous droplet motion with the cooperation of the roughness gradient. In addition, it is suggested that the so-called "virtual wall" used to confine the liquid flow along the undesired directions could be achieved by constructing highly advancing FEB areas around the microchannels, which is promising for the design of microfluidic systems.     

Dynamics of thin liquid films on surfaces with a time-periodic wettability

The dynamics of thin liquid films on surfaces whose wettability changes in a time-periodic manner are examined in this work. A nonlinear evolution equation based on the lubrication approximation is used to describe the film height, and attractions due to van der Waals forces are incorporated. Film wettability is varied through an imposed sinusoidal modulation of the Hamaker constant. A linear stability analysis predicts that if the mean Hamaker constant is negative, disturbances at the film surface will eventually decay regardless of the amplitude and frequency of the oscillation. However, numerical solution of the evolution equation shows that the film can rupture at a given frequency if the amplitude is sufficiently large. The associated characteristic wavelength can be predicted from results for constant-wettability surfaces if an appropriate effective Hamaker constant is used. For positive mean Hamaker constants, film rupture can be accelerated, delayed, or prevented depending on how the Hamaker constant changes early in the oscillation cycle. The effects of spatial gradients in wettability are also considered, and it is found that oscillation can delay but not prevent rupture. Inclusion of short-range repulsive forces leads to the formation of droplet-like structures separated by ultra-thin films, but this can be prevented by sufficiently large and slow oscillations of the Hamaker constant. The results of this work may find use in applications that make use of surfaces whose wettability can be controlled by external stimuli.     

Nanopattern transfer and wettability modification of regularly structured metallic and polymeric surfaces with replication

The hexagonally arranged close-packed concave nanotexture of the master surface of nanoporous alumina has been imprinted several times on aluminum films and gold films by thermal evaporation and on polystyrene films by spin coating. The degradation of the nanotextures with replica pattern transfer has been monitored by measuring the topology and the wettability of duplicated films. The trough-to-crest height of the topography decreases while the wettability of the nanotexture increases significantly as replication goes on. Air fractions calculated with measured water contact angles decrease substantially with replication although they also depend strongly on the materials and the shapes of duplicating nanotextures.     

Solution-assisted assembly of organic semiconducting single crystals on surfaces with patterned wettability

Two efficient approaches to assembling organic semiconducting single crystals are described. The methods rely on solvent wetting and dewetting on substrates with patterned wettability to selectively direct the deposition or removal of organic crystals. Substrates were functionalized with different self-assembled monolayers (SAMs) to achieve the desired wettabilities. The assembly of different organic crystals over centimeter-squared areas on Au, SiO2, and flexible plastic substrates was demonstrated. By designing line features on the substrate, the alignment of crystals, such as CuPc needles, was also achieved. As a demonstration of the potential application of this assembly approach, arrays of single-crystal organic field-effect transistors were fabricated by patterning organic single crystals directly onto and between transistor source and drain electrodes.     

Preparation and photocatalytic wettability conversion of TiO2-based superhydrophobic surfaces

We present here a facile method for the preparation of TiO2-based superhydrophobic surfaces. It consists of two steps: (1) roughening of the TiO2 surface with a rf (radio frequency) plasma with CF4 as an etchant and (2) modification of the roughened TiO2 surface with an octadodecylphosphonic acid (ODP) monolayer. Plasma etching caused the thinning of the TiO2 film but at the same time enhanced its surface roughness. A discontinuous wedgelike surface microtexture was formed after etching for 30 s, which, after modification with a monolayer of ODP, showed Cassie-type water super-repellency with a contact angle (CA) hysteresis smaller than 2 degrees . The state of water super-repellency (water CA >165 degrees) could be converted to the state of superhydrophilicity (water CA approximately 0 degrees) by means of ultraviolet (UV) illumination as a result of the photocatalytic decomposition of the ODP monolayer by TiO2. Readsorption of ODP molecules leads directly to the recovery of water super-repellency.     

Solvent fuming dual-responsive switching of both wettability and solid-state luminescence in silole film

A multiresponsive switcher on both wettability and solid-state luminescence has great application potentials in novel smart devices. In this paper, a silole molecule of 1,2,3,4,5-hexaphenylsilole (HPS) was chosen to prepare thin films by spin-coating, and a solvent fuming dual-responsive switcher combining photoluminescent behavior and wettability was successfully achieved by changing the mode of solid-state molecular packing. This study suggests that HPS and other silole derivatives have a promising future for use in dual- and multifunctional switches in new technological applications.     

Using light intensity to control reaction kinetics and reversibility in photomechanical crystals

4-Fluoro-9-anthracenecarboxylic acid (4F-9AC) is a thermally reversible (T-type) photomechanical molecular crystal. The photomechanical response is driven by a [4 + 4] photodimerization reaction, while the photodimer dissociation determines the reset time. In this paper, both the chemical kinetics of dimer dissociation (using a microscopic fluorescence-recovery-after-photobleaching experiment) and mechanical reset dynamics (by imaging bending microneedles) for single 4F-9AC crystals are measured. The dissociation kinetics depend strongly on the initial concentration of photodimer, slowing down and becoming nonexponential at high dimer concentrations. This dose-dependent behavior is also observed in the mechanical response of bending microneedles. A new feature in the photomechanical behavior is identified: the ability of a very weak control beam to suppress dimer dissociation after large initial dimer conversions. This phenomenon provides a way to optically control the mechanical response of this photomechanical crystal. To gain physical insight into the origin of the nonexponential recovery curves, the experimental results are analyzed in terms of a standard first-order kinetic model and a nonlinear Finke–Watzky (FW) model. The FW model can qualitatively reproduce the transition from exponential to sigmoidal recovery with larger initial conversions, but neither model can reproduce the suppression of the recovery in the presence of a weak holding beam. These results highlight the need for more sophisticated theories to describe cooperative phenomena in solid-state crystalline reactions, as well as demonstrating how this behavior could lead to new properties and/or improved performance in photomechanical materials.

The chemical and mechanical recovery rates of crystalline 4-fluoro-9-anthracenecarboxylic acid, a thermally reversible photomechanical material, can be controlled by both the intensity of the photodimerization pulse and the use of a weak hold beam.     

Polyelectrolyte-surfactant complexes and their influence on the wettability of different polymer surfaces

A novel method to modify the wettability of polymer surfaces is presented. It was found that the surface properties of polymers with different surface-free energies—polyamide 6.6, polypropylene, polyethylene and polystyrene—can be easily changed by a simple modification with premixed polyelectrolyte-surfactant complexes (PSCs). The modification effect can be significantly affected by the complex properties which are influenced by the type of surfactant and polyanion and their charge ratio in a mixture. Complexes having positive charge and low surface tension are most effective. All the complexes investigated show an interaction with polymer surfaces; however, the most effective modification was obtained with hydrophobic substrates such as polypropylene and polystyrene. In contrast to modification with the ‘pure surfactant’, the modification with PSC is persistent also after rinsing.     

Enhancement of surface wettability via the modification of microtextured titanium implant surfaces with polyelectrolytes

Micrometer- and submicrometer-scale surface roughness enhances osteoblast differentiation on titanium (Ti) substrates and increases bone-to-implant contact in vivo. However, the low surface wettability induced by surface roughness can retard initial interactions with the physiological environment. We examined chemical modifications of Ti surfaces [pretreated (PT), R(a) ≤ 0.3 μm; sand blasted/acid etched (SLA), R(a) ≥ 3.0 μm] in order to modify surface hydrophilicity. We designed coating layers of polyelectrolytes that did not alter the surface microstructure but increased surface ionic character, including chitosan (CHI), poly(L-glutamic acid) (PGA), and poly(L-lysine) (PLL). Ti disks were cleaned and sterilized. Surface chemical composition, roughness, wettability, and morphology of surfaces before and after polyelectrolyte coating were examined by X-ray photoelectron spectroscopy (XPS), contact mode profilometry, contact angle measurement, and scanning electron microscopy (SEM). High-resolution XPS spectra data validated the formation of polyelectrolyte layers on top of the Ti surface. The surface coverage of the polyelectrolyte adsorbed on Ti surfaces was evaluated with the pertinent SEM images and XPS peak intensity as a function of polyelectrolyte adsorption time on the Ti surface. PLL was coated in a uniform thin layer on the PT surface. CHI and PGA were coated evenly on PT, albeit in an incomplete monolayer. CHI, PGA, and PLL were coated on the SLA surface with complete coverage. The selected polyelectrolytes enhanced surface wettability without modifying surface roughness. These chemically modified surfaces on implant devices can contribute to the enhancement of osteoblast differentiation.     

Bioinspired construction on aluminum alloy surfaces with stable super‐hydrophobicity and their resulting wettability

The bioinspired leaf‐like super‐hydrophobic surfaces on aluminum alloy were fabricated by means of a facile method using anodic oxidation. The surface morphologies, compositions, and wettability were investigated with SEM, XPS, and contact angle measurement, respectively. The SEM showed hierarchical microstructures and nanostructures, the static contact angle was about 167.7 ± 1.2°, and sliding angle was 5°. The super‐hydrophobic phenomenon of the prepared surface was analyzed with Cassie theory, and it is found that only about 3% of the water surface is contacted with the metal substrate and the remaining 97% is contacted with the air cushion. Copyright © 2011 John Wiley & Sons, Ltd.     

Several surfaces with special wettability: Influence on spreading and motion of W/O emulsion droplets

Physical and chemical modifications were made on the surface of the aluminum sheet to change the surface properties and superhydrophobic–hydrophilic wettability gradient surface was made on the perspex surface by using microstructure-pattering technique and self-assembled-monolayer method. By using high-speed video camera system and optical tensiometer, this paper discusses the influence of special surfaces with different wettability on spreading and motion of water, oil, and W/O emulsion droplets both experimentally and theoretically. In addition, the paper also discusses the influence of the superhydrophobic–hydrophilic wettability gradient on fluidity of W/O emulsion droplets and the coalescence process of droplets. The results showed that the contact angle of W/O emulsion droplets on the modified surfaces was related to the water and oil distribution at the three-phase line. On the wettability gradient surface, the droplet moved spontaneously when the droplet was located at the junction of the gradient. A quasi-steady theoretical model was used to analyze the driving and resistant forces acting on a droplet to improve the understanding of the self-transport behavior of the droplets.     

Size-selective deposition and sorting of lyophilic colloidal particles on surfaces of patterned wettability

A highly parallelizable means of positioning or sorting particles in a size-selective manner into arrays is demonstrated based on the placement of particle suspensions on surfaces of patterned wettability and the subsequent evaporation of the suspending solvent. The method relies on creating lyophilic features of dimensions similar to or greater than those of the particles to be arrayed and smaller than those of the particles to be excluded. As the contact line recedes, it fills lyophilic features, creating discrete fluid elements that mimic the underlying lyophilic pattern. The fluid elements have aspect ratios dictated by the contact angle. By adjusting the size of the lyophilic features, the heights of the fluid elements can be adjusted to sequester or exclude particles based on their diameter. The principal interest of this work is its broad applicability. No prior understanding of the particle properties is needed except for the size of the particle and its ability to be suspended in a solvent.     

Strain-controlled switching of hierarchically wrinkled surfaces between superhydrophobicity and superhydrophilicity

Recent years have witnessed intense interest in multifunctional surfaces that can be designed to switch between different functional states with various external stimuli including electric field, light, pH value, and mechanical strain. The present paper is aimed to explore whether and how a surface can be designed to switch between superhydrophobicity and superhydrophilicity by an applied strain. Based on well-established theories of structure buckling and solid-liquid contact, we show that this objective may be achieved through a hierarchically wrinkled surface. We derive general recursive relations for the apparent contact angle at different levels of the hierarchical surface and investigate the thermodynamic stability of different contact states. Our study may provide useful guidelines for the development of multifunctional surfaces for many technological applications.