Controllable water permeation on a poly(N-isopropylacrylamide)-modified nanostructured copper mesh film

Water permeation is important for various applications in industry, agriculture, and daily life. However, most research mainly focuses on the static wettability on different surfaces, and the dynamic properties of the micro- and nanostructure-enhanced responsive wettability is lacking. And the relevant application research is rare, which still remains a challenge. Herein we report the temperature-controllable water permeation on a poly(N-isopropylacrylamide)-modified nanostructured copper mesh film. At low temperatures (below 25 degrees C), the film shows good water permeability because of the highly hydrophilic nature, and as a result, the water can easily penetrate through the film. At high temperatures (above 40 degrees C), it is impermeable to water because of the superhydrophobicity and the large negative capillary effect induced by the micro- and nanostructures. The excellent controllability of water permeation on this film may be convenient for use in many processes including filtration, water/oil separation, and so on. A detailed investigation indicates that the special nanostructures and the appropriate size of the microscale mesh pores not only influence the static contact angles of the mesh film, but also, more importantly, greatly improve the dynamic properties of wettability at different temperatures simultaneously, which plays a crucial role in the excellent controllability over water permeation on this film. This work may also provide interesting insight into the design of novel functional devices that are relevant to surface wettability.     

Control of wettability of molecularly thin liquid films by nanostructures

The patterning of liquid thin films on solid surfaces is very important in various fields of science and engineering related to surfaces and interfaces. A method of nanometer-scale patterning of a molecularly thin liquid film on a silicon substrate using the lyophobicity of the oxide nanostructures has recently been reported (Fukuzawa, K.; Deguchi, T.; Kawamura, J.; Mitsuya, Y.; Muramatsu, T.; Zhang, H. Appl. Phys. Lett. 2005, 87, 203108). However, the origin of the lyophobicity of the nanostructure with a height of around 1 nm, which was fabricated by probe oxidation, has not yet been clarified. In the present study, the change in thickness of the liquid film on mesa-shaped nanostructures and the wettability for the various combinations of the thickness of the liquid films and the height of ridge-shaped nanostructures were investigated. These revealed that lyophobicity is caused by a lowering of the intermolecular interaction between the liquid and silicon surfaces by the nanostructure and enables the patterning of a liquid film along it. The tendency of the wettability for a given liquid film and nanostructure size can be predicted by estimating the contributions of the intermolecular interaction and capillary pressure. In this method, the height of the nanostructure can control the wettability. These results can provide a novel method of nanoscale patterning of liquid thin films, which will be very useful in creating new functional surfaces.     

Characterization of electron-beam-modified surface coated clay fillers and their influence on physical properties of rubbers

A novel process of surface modification of clay filler has been developed by coating this with an acrylate monomer, trimethylol propane triacrylate (TMPTA) or a silane coupling agent, triethoxy vinyl silane (TEVS) followed by electron beam irradiation. Characterization of these surface modified fillers has been carried out by Fourier-transform infrared analysis (FTIR), electron spectroscopy for chemical analysis (ESCA), wettability by dynamic wicking method measuring the rise of a liquid through a filler-packed capillary tube and water flotation test, scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), thermogravimetric analysis (TGA), and X-ray diffraction (XRD). Presence of the acrylate and the silane coupling agent on the modified fillers has been confirmed from FTIR, ESCA, and EDX studies, which has also been supported by TGA studies. The contact angle measurement by dynamic wicking method suggests improvement in hydrophobicity of the treated fillers, which is supported by water flotation test especially in the case of silanized clay. However, XRD studies demonstrate that the entire modification process does not affect the bulk properties of the fillers. Finally, both unmodified and modified clay fillers have been incorporated in styrene butadiene rubber (SBR) and nitrile rubber (NBR). Rheometric and mechanical properties reveal that there is a definite improvement using these modified fillers specially in the case of silanized clay compared to the control sample, probably due to successful enhancement in interaction between the treated clay and the base polymer.     

Dynamics of wicking in silicon nanopillars fabricated with interference lithography and metal-assisted chemical etching

The capillary rise of liquid on a surface, or "wicking", has potential applications in biological and industrial processes such as drug delivery, oil recovery, and integrated circuit chip cooling. This paper presents a theoretical study on the dynamics of wicking on silicon nanopillars based on a balance between the driving capillary forces and viscous dissipation forces. Our model predicts that the invasion of the liquid front follows a diffusion process and strongly depends on the structural geometry. The model is validated against experimental observations of wicking in silicon nanopillars with different heights synthesized by interference lithography and metal-assisted chemical etching techniques. Excellent agreement between theoretical and experimental results, from both our samples and data published in the literature, was achieved.     

A Novel Method for Surface Free-Energy Determination of Powdered Solids

Interfacial solid/liquid interactions play a crucial role in wetting, spreading, and adhesion processes. In the case of a flat solid surface, contact angle measurements are commonly utilized for the determination of the solid surface free energy and its components. However, if such a surface cannot be obtained, then the contact angle can not be measured directly. Usually methods based on imbibition of probe liquids into a thin porous layer or column are applied. In this paper a novel method, also based on the capillary rise, is proposed for the solid surface free-energy components determination. Actually, it is a modification of the thin column wicking method; similar theoretical background can be applied together with that appropriate for the capillary rise method of liquid surface tension determination. The proposed theoretical approach and procedure are verified by using single glass capillaries, and then alumina and ground glass powders were used for the method testing. Thus obtained surface free-energy components for these solids, for both glass and alumina, agree well with the literature values.     

Wettability transition induced transformation and entrapment of polymer nanostructures in cylindrical nanopores

We apply the concept of wettability transition to manipulate the morphology and entrapment of polymer nanostructures inside cylindrical nanopores of anodic aluminum oxide (AAO) membranes. When AAO/polystyrene (PS) hybrids, i.e., AAO/PS nanorods or AAO/PS nanotubes, are immersed into a polyethylene glycol (PEG) reservoir above the glass transition temperature of PS, a wettability transition from wetting to nonwetting of PS can be triggered due to the invasion of the more wettable PEG melt. The wettability transition enables us to develop a nondestructive method to entrap hemispherically capped nanorods inside nanopores. Moreover, we can obtain single nanorods with the desired aspect ratio by further dissolving the AAO template, in contrast to the drawbacks of nonuniformity or destructiveness from the conventional ultrasonication method. In the case of AAO/PS nanotubes, the wettability transition induced dewetting of PS nanotube walls results in the disconnection and entrapment of nonwetting PS domains (i.e., nanospheres, nanocapsules, or capped nanorods). Moreover, PEG is then washed to recover the pristine wettability of PS on the alumina surface; further annealing of the PS nanospheres inside AAO nanopores under vacuum can generate some unique nanostructures, particularly semicylindrical nanorods.     

Bubble transfer on wettability-heterogeneous surfaces

Researches have investigated the formation, transportation and spreading of bubble on solid surface with specific wettability. However, bubble transfer on wettability-heterogeneous surfaces has been rarely reported, which also plays significant role in water electrolysis, heat transfer, micro-bubble collection, etc. In this work, we carefully investigate the behavior of bubble transfer from the aerophobic or aerophilic region to the superaerophilic region through fabricating the wettability-heterogenous surfaces. Surface energy was elucidated to be transformed to the kinetic energy during bubble transfer process. Theoretical analysis on the average velocity of bubble transfer was consistent with the experimental results. The influence of wettability of solid substrate, bubble volume and superaerophilic stripe width on bubble transfer are carefully investigated. Moreover, wettability-heterogeneous surfaces were explored to be applied in micro-CO₂ bubble collection and H₂ bubble removement in water splitting.     

润湿性表面强化冷凝传热的研究进展

固体表面的润湿特性对冷凝传热具有重要的影响。本文分析了冷凝传热的机理,介绍了现阶段对不同冷凝方式的判定方法,总结了不同润湿性表面的制备方法,概述了蒸汽在亲水表面、疏水表面和组合表面上的冷凝传热性能,总结了该领域目前存在的问题。本文为利用表面润湿性强化传热提供了较为系统的综述,为强化冷凝传热提供思路。     

Dynamic and reversible electrowetting with low voltage on the dimethicone infused carbon nanotube array in air

Unremitting efforts have been intensively making for pursuing the goal of the reversible transition of electrowetting owing to its vital importance to many practical applications, but which remains a major challenge for carbon nanotubes due to the irreversible electrochemical damage. Herein, we proposed a subtly method to prevent the CNT array from electrochemical damage by using liquid medium instead of air medium to form a liquid/liquid/solid triphase system. The dimethicone dynamically refills in CNT arrays after removing of voltage that makes the surface back to hydrophobic, which is an elegant way to not only decrease energy dissipation in electrowetting process but also obtain extra energy in reversible dewetting process. Repeated cycles of in situ experiments showed that more than four reversible electrowetting cycles could be achieved in air. It worth mention that the in situ reversible electrowetting voltage of the dimethicone infused CNT array has been lowered to 2 V from 7 V which is the electrowetting voltage for the pure CNT array. The surface of the dimethicone infused CNT array can maintain hydrophobicity with a contact angle of 145.6° after four cycles, compared with 148.1° of the initial state. Moreover, a novel perspective of theoretical simulations through the binding energy has been provided which proved that the charged CNTs preferred binding with water molecules thereby replacing the dimethicone molecules adsorbed on the CNTs, whereas reconnected with dimethicone after removing the charges. Our study provides distinct insight into dynamic reversible electrowetting on the nanostructured surface in air and supplies a way for precise control of wettability in surface chemistry, smart phase-change heat transfer enhancement, liquid lenses, microfluidics, and other chemical engineering applications.     

Physico-chemical mechanisms governing the adherence of starch granules on materials with different hydrophobicities

The factors influencing the adherence of starch were examined to improve the understanding of the mechanisms affecting soiling and cleanability. Therefore an aqueous suspension of starch granules was sprayed on four model substrates (glass, stainless steel, polystyrene and PTFE) and dried, and the substrates were cleaned using a radial-flow cell. The morphology of the soiled surfaces and the substrate chemical composition were also characterized. By influencing droplet spreading and competition between granule-substrate and granule-granule interfaces regarding the action of capillary forces, substrate wettability affected the shape and compactness of the adhering aggregates, the efficiency of shear forces upon cleaning, and finally the adherence of soiling particles. The rate of drying had an influence explained by the duration left to capillary forces for acting. X-ray photoelectron spectroscopy demonstrated the presence of macromolecules, mainly polysaccharides, which were adsorbed from the liquid phase, or carried by the retracting water film and deposited at the granule-substrate interface. These macromolecules acted as an adhesive joint, the properties of which seemed to be influenced by the detailed history of drying and subsequent exposure to humidity. In summary, the substrate surface energy affects the adherence of starch aggregates by different mechanisms which are all linked together: suspension droplet spreading, action of capillary forces, direct interaction with starch particles and interfacial macromolecules.     

Review of non-reactive and reactive wetting of liquids on surfaces

Wettability is a tendency for a liquid to spread on a solid substrate and is generally measured in terms of the angle (contact angle) between the tangent drawn at the triple point between the three phases (solid, liquid and vapour) and the substrate surface. A liquid spreading on a substrate with no reaction/absorption of the liquid by substrate material is known as non-reactive or inert wetting whereas the wetting process influenced by reaction between the spreading liquid and substrate material is known as reactive wetting. Young's equation gives the equilibrium contact angle in terms of interfacial tensions existing at the three-phase interface. The derivation of Young's equation is made under the assumptions of spreading of non-reactive liquid on an ideal (physically and chemically inert, smooth, homogeneous and rigid) solid, a condition that is rarely met in practical situations. Nevertheless Young's equation is the most fundamental starting point for understanding of the complex field of wetting. Reliable and reproducible measurements of contact angle from the experiments are important in order to analyze the wetting behaviour. Various methods have been developed over the years to evaluate wettability of a solid by a liquid. Among these, sessile drop and wetting balance techniques are versatile, popular and provide reliable data. Wetting is affected by large number of factors including liquid properties, substrate properties and system conditions. The effect of these factors on wettability is discussed. Thermodynamic treatment of wetting in inert systems is simple and based on free energy minimization where as that in reactive systems is quite complex. Surface energetics has to be considered while determining the driving force for spreading. Similar is the case of spreading kinetics. Inert systems follow definite flow pattern and in most cases a single function is sufficient to describe the whole kinetics. Theoretical models successfully describe the spreading in inert systems. However, it is difficult to determine the exact mechanism that controls the kinetics since reactive wetting is affected by a number of factors like interfacial reactions, diffusion of constituents, dissolution of the substrate, etc. The quantification of the effect of these interrelated factors on wettability would be useful to build a predictive model of wetting kinetics for reactive systems.     

Particle-surface capillary forces with disjoining pressure

A new, atomic force microscopy (AFM) based experimental setup for the continuous acquisition of friction force data as a function of humidity has been developed. The current model of interactions between wet contacts under the influence of capillary effects, has been amended to include a vertical component due to the disjoining pressure and takes into account the influence of liquid films adsorbed on the surface. This is a 'switching' model, i.e. the contact between nanometer-sized sphere and a flat surface can exist in two distinct states due to capillary bridge formation/destruction as the humidity is varied. The model has been qualitatively verified on samples of differing wettability produced by UV-ozone treatment of polystyrene (PS). Results of AFM analysis of the friction vs. vapor pressure curves collected from the surface are presented. Correlation between important surface properties such as wettability, adsorption, and contact angle and friction force under varying humidity were found and discussed.     

Short time spreading and wetting of offset printing liquids on model calcium carbonate coating structures

Spreading of oils and water on porous and pre-saturated model carbonate coating structures was studied with high speed video imaging. The short-time data were complemented with long time absorption and wicking experiments. The results indicate a strong dependence between surface structural features of the pigment tablets and water spreading at short times, both in non-saturated and water pre-saturated cases, while the oil spreading is mainly dependent on the liquid properties. Sodium polyacrylate dispersant on pigment surfaces is shown to contribute to water spreading and absorption. On pre-saturated structures the liquid-liquid interactions are dominant and the majority of results support spreading according to the molecular kinetic model. The evidence supports the hypothesis of S. Rousu, P. Gane, and D. Eklund, ["Influence of coating pigment chemistry and morphology on the chromatographic separation of offset ink constituents," in The Science of Papermaking Transactions of the 12th Fundamental Research Symposium, FRC The Pulp & Paper Fundamental Research Society, Oxford, UK, 2001, p. 1115] that at long times the oils absorb into the porous structure at a rate proportional to the ratio of viscosity and surface tension, provided there is no sorptive action with the binder. A combination of nanosized pores and large surface area is useful for providing sufficient absorption capability for carbonate based coatings.     

Wicking in twisted yarns

This paper investigated vertical wicking in twisted yarns. A mathematical model was developed based on a capillary penetration mechanism. By using a macroscopic force balance approach, the wicking time was derived as a function of the capillary rise of the liquid. Packing of fibers in the yarn was assumed to be uniform. In order to validate our model, a series of experiments was conducted on polyester yarns. The results showed a good agreement between the experimental data and the theoretical predictions. The influence of twist level of the yarn on the capillary flow was also investigated.     

Capillary rise of liquids over a microstructured solid surface

The location of the triple line as a function of time has been recorded for a series of organic liquids, with various surface tension to viscosity ratios, wicking upward a rough Cu(6)Sn(5)/Cu intermetallic (IMC) substrate. The complex topographical features of such an IMC rough surface are characterized by surface porosity and surface roughness. A theoretical model for wicking upward a rough surface has been established by treating the rough IMC surface as a two-dimensional porous medium featuring a network of open microtriangular grooves. The model is verified against experimental data. The study confirms that the kinetics of capillary rise of organic liquids in a nonreactive flow regime over a porous surface having arbitrary but uniformly distributed topographical features involves (i) surface topography metrics (i.e., permeability, tortuosity/porosity, and geometry of the microchannel cross section); (ii) wicking features (i.e., contact angle and filling factor); and (iii) physical properties of liquids (i.e., surface tension and viscosity). An excellent agreement between theoretical predictions and experimentally obtained data proves, for a selected filling factor η, validity of the analytically established model. Scaled data sets show that, for a given rough surface topography, (i) wicking kinetics of considered liquids depend on properties of liquids, that is, surface tension to viscosity ratios and contact angles; (ii) the filling factor for all tested liquids is an invariant, offering good prediction within the range of ~0.9-1.0. The distance of the wicking front versus square root of time relationship was well established throughout the whole considered wicking evolution time.     

Monodisperse rutile microspheres with ultrasmall nanorods on surfaces: Synthesis, characterization, luminescence, and photocatalysis

This work demonstrates the process of building optoelectrically cooperative surface wetting in smart and precise way. The superhydrophobic photosensitive film is constructed with TiO(2) nanotube arrays. Compared with conventional organic dyes, CdS quantum dots (QDs) as sensitizer layer are modified on TiO(2) nanotubes surface to improve photosensitivity of the composited surface in visible light region, which offer the benefit for designing and fabricating solid state hetero-junction devices. ITO glass is introduced as top electrode to apply electrical and optical stimuli and the patterned wetting is instantly obtained with masking light through ITO. The optoelectrically cooperative wettability conversion occurred on superhydrophobic TiO(2) nanotube surface at critical voltage of 12 V, which was decreased by 18 V comparing with only using electric stimulus. This study provides potential applications for TiO(2) nanotube arrays to the associated research of liquid reprography, location-controlled microfluidic device and lab-on-chip.     

Determination of contact angles on microporous particles using the thin-layer wicking technique

The properties of particle-stabilized emulsions, especially with regard to phase inversion, are very dependent on the contact angle that the particles experience at the oil-water interface. For the very small particles used for such emulsions (often a few tens of nm), it is impossible to measure this contact angle directly. Its value could be calculated if it were possible to determine the components of the solid surface free energy. To establish a method suitable for such particles, we have investigated the imbibition of five probe liquids into a porous bed of silica (commercial TLC plates) using the thin-layer wicking technique. For all liquids, the difference between wicking rate for bare plates and for those pre-contacted with the vapors is large but it is not due to an advancing angle effect on bare plates. Our analysis shows that it is due to the diversion of flowing liquid into blind pores which are already filled in the pre-contacted case. Thus a new model is proposed describing wicking in a porous medium with very small blind pores by introducing a parameter into the Washburn equation that corrects for this capillary condensation effect. The parameter needed is determined independently using gravimetric adsorption measurements. When this modified Washburn equation is used, the difference between advancing and receding contact angle is actually quite small. When the averages are used as the Young's contact angles, values for the surface energy components of silica are obtained that are completely consistent between the five liquids and have magnitudes expected for this type of silica surface.     

The influence of pore wettability on the dynamics of imbibition and drainage

Using large-scale molecular-dynamic (MD) simulations, we have shown previously that the classical Lucas–Washburn equation commonly employed to describe capillary imbibition and drainage should be modified to include dynamic contact-angle effects. In addition, we have demonstrated how these effects can be accounted for using the molecular-kinetic theory of dynamic wetting. In a further publication, we presented theoretical arguments and experimental evidence that the velocity of wetting depends on the intrinsic wettability of the solid surface in such a way that there exists an optimum contact angle at which the velocity of wetting is a maximum. Here, we combine these ideas to show how the maximum speeds of capillary imbibition and drainage are affected both by the pore wettability and the pressures used to drive capillary displacement. In particular, we introduce the concept of dynamic wetting transitions (DWTs) and discuss how these limit displacement efficiency and can be manipulated by controlling pore wettability. The results of this work may be beneficial in optimising the performance of capillary processes such as those involved in oil recovery.     

Importance of capillary forces in the assembly of carbon nanotubes in a polymer colloid lattice

We highlight the significance of capillary pressure in the directed assembly of nanorods in ordered arrays of colloidal particles. Specifically, we discuss mechanisms for the assembly of carbon nanotubes at the interstitial sites between latex polymer particles during composite film formation. Our study points to general design rules to be considered to optimize the ordering of nanostructures within such polymer matrices. In particular, gaining an understanding of the role of capillary forces is critical. Using a combination of electron microscopy and atomic force microscopy, we show that the capillary forces acting on the latex particles during the drying process are sufficient to bend carbon nanotubes. The extent of bending depends on the flexural rigidity of the carbon nanotubes and whether or not they are present as bundled ensembles. We also show that in order to achieve long-range ordering of the nanotubes templated by the polymer matrix, it is necessary for the polymer to be sufficiently mobile to ensure that the nanotubes are frozen into the ordered network when the film is formed and the capillary forces are no longer dominant. In our system, the polymer is plasticized by the addition of surfactant, so that it is sufficiently mobile at room temperature. Interestingly, the carbon nanotubes effectively act as localized pressure sensors, and as such, the study agrees well with previous theoretical predictions calculating the magnitude of capillary forces during latex film formation.     

Simulation of pool boiling of nanofluids by using Eulerian multiphase model

In the present work, a new simulation of nanofluid/vapor two-phase flow inside the 2-D rectangular boiling chamber was numerically investigated. The Eulerian–Eulerian approach used to predict the boiling curve and the interaction between two phases. The surface modification during pool boiling of silica nanofluid represented by surface roughness and wettability is put into the account in this simulation. New closure correlations regarding the nucleation sites density and bubble departure diameter during boiling of silica nanofluid were inserted to extend the boiling model in this work. Besides, the bubble waiting time coefficient which involved in quenching heat flux under heat flux partitioning HFP model was corrected to improve the results of this study. The numerical results validated with experimental works in the literature, and they revealed good agreements for both pure water and nanofluids. The results found that when improving the heat flux partitioning model HFP by considering the surface modification of nucleate pool boiling parameters, it will give more mechanistic sights compared to the classical model, which is used for predicting of boiling heat transfer of pure liquid.