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Polymethylmethacrylate/poly-tert-butylmethacrylate Janus nanoparticles were synthesized by the electrohydrodynamic co-jetting method. The Janus character of these nanoparticles was visualized through super-resolution imaging with Structured Illumination Microscopy. The Janus nanoparticles, and the corresponding homogeneous sets, were then morphologically characterized to assess their size, distribution, and concentrations. All nanoparticles presented high interfacial activity as measured by pendant drop tensiometry at water/decane interfaces. At high concentrations and compression states, the Janus nanoparticles exhibited higher interfacial activity than the homogeneous nanoparticles. This is in agreement with theoretical and experimental works in which Janus nanoparticles present higher interfacial activity than homogeneous nanoparticles.

The analysis of wetting properties of superhydrophobic surfaces may be a difficult task due to the restless behavior of drops on this type of surfaces and the limitations of goniometry for high contact angles. A method to validate the performance of superhydrophobic surfaces, rather than standard goniometry, is required. In this work, we used bouncing drop dynamics as a useful tool to predict the water repellency of different superhydrophobic surfaces. From bouncing drop experiments conducted over a wide range of superhydrophobic surfaces, we found that those surfaces with a proper roughness degree and homogeneous chemical composition showed higher water-repellency. We also conducted a drop condensation study at saturating conditions aimed to determine whether there is direct correlation between water repellency and condensation delay. We found that the drop condensation process is strongly related to the surface topography, as well as the intrinsic wettability. The condensation is promoted on rough surfaces but it is delayed on intrinsically hydrophobic surfaces. However, the differences found in condensation delay between the superhydrophobic surfaces explored in this study cannot be justified by their chemical homogeneity nor their efficiency as water repellent surfaces, separately.

One of the main challenges in cookware and baking industry is the fabrication of enhanced nonstick coatings including two main features: highly hydrophobic, resistant and durable. In general, life-long release coatings are prepared with a polymer-filler composite of several microns thickness deposited on food-compatible metals such as aluminum, stainless steel or aluminized steel, as the dimensions and functionality of the product. In this work we present several routes to fabricate water-repellent surfaces on aluminized steel as alternative to current nonstick coatings but with enhanced release properties and high durability. For this purpose, we explored two different strategies to directly create hierarchical texture on aluminized steel surfaces: sandblasting in combination to acid etching and single acid etching. The rough metal surfaces were further hydrophobized by using two different organic coatings: a Teflon film and a silane monolayer. The release properties were quantified through the study of the adhesion of water drops by means of sliding angle and contact angle measurements. We identified the most appropriate texturing process by assessing a balance between the water repellency properties and the lowest damage caused on the metal surface. This damage was quantified through thickness loss measurements of the aluminum layer. The durability of the samples was analyzed with Scotch-peeling test and next, with sliding angle measurements. We analyzed the roughness and morphology of the surface textures by contact profilometry and FE-SEM. The surface chemical composition was also analyzed by EDX. Our results pointed out to that the most durable repellent surfaces were those ones silanized. The combination of sandblasting and acid etching and the hydrophobization process with silane molecules enable to fabricate super-nonstick coatings on aluminized steel of high durability.

Titanium is extensively employed in biomedical devices, in particular as implant. The self-assembly of alkylphosphonates on titanium surfaces enable the specific adsorption of biomolecules to adapt the implant response against external stimuli. In this work, chemically-tailored cpTi surfaces were prepared by self-assembly of alkylphosphonate molecules. By bringing together attributes of two grafting molecules, aqueous mixtures of two alkylphosphonates were used to obtain mixed self-assembled films. Single self-assembled films were also altered by laser abrasion to produce chemically patterned cpTi surfaces. Both mixed and patterned self-assembled films were confirmed by AFM, ESEM and X-ray photoelectron spectroscopy. Water contact angle measurements also revealed the composition of the self-assembly films. Chemical functionalization with two grafting phosphonate molecules and laser surface engineering may be combined to guide the bone-like formation on cpTi, and the future biological response in the host.

Colloidal interactions have been extensively studied due to the wide number of applications where colloids are present. In general, the electric double layer force and the van der Waals interaction dominate the net force acting between two colloids at large separation distances. However, it is well accepted that some other phenomena, especially those acting at short separation distances, might be relevant and induce substantial changes in the force profiles. Within these phenomena, those related to the surface contact angle, the hydration degree of the ions, or the pH, may dominate the force profiles features, not only at short distances. In this paper, we analyzed the effect of the pH and counterion type on the long-range as well as short-range forces between polystyrene colloidal particles by using the colloidal probe technique based on AFM. Our results confirm that the features of the force profiles between polystyrene surfaces are strongly affected by the pH and hydration degree of the counterions in solution. Additionally, we performed a study of the role of the pH on the wettability properties of hydrated and nonhydrated polystyrene sheets to scan the wettability properties of this material with pH. Contact angle measurements confirmed that the polystyrene surface is hydrophobic in aqueous solutions over the entire range of pHs investigated. These results are in good agreement with the features observed in the force profiles at low pH. At high pH, a short-range repulsion similar to the one observed for hydrophilic materials is observed. This repulsion scales with the pH, and it also depends on the hydration degree of the ions in solution. This way, the short-range forces between polystyrene surfaces may be tunable with the pH, and its origin does not seem to be related to the hydrophobicity of the material.

Fluoropolymer-based coatings are widely used for release applications. However, these hydrophobic surfaces do not reveal a significantly low adhesion. Water repellency incorporated to fluoropolymer coatings might enhance their release performance. In this work, we focused on the surface texturing of a well-known polytetrafluoroethylene (PTFE)-based coating. We explored as texturing routes: sanding, sandblasting and laser ablation. We examined the surface roughness with white light confocal microscopy and the surface morphology with environmental scanning electron microscopy (ESEM). Water-repellent fluoropolymer coatings were reproduced in all cases, although with different degree, parametrized with bounces of water drops (4&ndash, 5 &mu, L). Laser ablation enabled the lowest adhesion of coatings with 24 &plusmn, 2 bounces. This result and the current development of laser patterning for industry assure the incipient use of laser ablation for release coatings.

Aluminum-magnesium (Al-Mg) alloy and aluminum-coated steel (aluminized steel) are typically used for the manufacturing of baking trays and molds. For these applications, these materials must be modified to develop release and hydrophobic properties. With this aim, the bare substrates are typically coated with low-surface energy materials such as fluoropolymers, elastomers, or sol-gel layers. In this work, some alternative strategies to prepare these functional surfaces are presented. We used three-step processes involving (i) micro-texturing, (ii) nano layer deposition through immersion and electrodeposition, and (iii) hydrophobization. The raw substrates were sanded or sandblasted at the micro scale, accordingly. Texturization at the nano scale was achieved with a cerium layer formed by electrodeposition or solution immersion. The cerium layers were hydrophobized with fatty acids. The wetting properties of the samples were studied with tilting-plate and bouncing drop methods. We measured the surface roughness of the samples by contact profiling and analyzed their surface morphology using a field emission scanning electron microscope (FESEM). The elemental chemical composition of the samples was analyzed by energy-dispersive X-ray spectroscopy (EDX). The wettability results indicated that the best performance for the Al-Mg substrates was reached by sandblasting and later immersion in a cerium nitrate solution. For aluminized steel substrates, the best results were obtained with both electrodeposition and immersion methods using a cerium chloride solution., The authors were supported by the University of Cordoba (Spain), which financed this work through the Own Research Plan 2019. This research was partially financed by the State Research Agency (SRA) and European Regional Development Fund (ERDF) through the project MAT2017-82182-R.

Objectives To evaluate the effect of different Self-Assembled Films (SAFs) on the development of calcium-phosphate (Ca/P) biomimetic layers on commercially pure titanium (cpTi) and the final cell adhesion on these coatings. Materials and methods A total of five different surfaces were evaluated. Alkyl phosphonate Self-Assembled Films (SAFs) with three different ending groups (methyl [–CH 3 ], carboxyl [–COOH], and phosphonate [–PO(OH) 2 ]) were used to cover ultra-polished cpTi surfaces. These functionalized surfaces were compared with a hydroxylated ultra-polished cpTi surface. A biomimetic Ca/P layer was deposited on each surface by precipitation. A control cpTi sample with no precipitates was introduced in the study. Topography (AFM), morphology (ESEM), chemistry (XPS, EDX), crystallography (XRD), wettability (dynamic contact angle), layer thickness (WLCM), percolation (fluid retention) and cell response analysis were used for surface characterization. Results XRD showed the formation of hydroxyapatite (HA) in the four biomimetic coatings. The Ca/P ratios obtained by XPS in the four biomimetic coatings showed similar values (≈1.40) corresponding to amorphous hydroxyapatite. The water wettability of the biomimetic coatings was similar but the surface morphology was different. The thickest biomimetic coating with lower percolation threshold and greater cell adhesion was obtained on the carboxyl-terminated SAF. The biomimetic coatings improved the cell adhesion but it was further improved by the presence of underlying SAFs that bond the coating to cpTi surface. Conclusions The use of SAFs chemically stabilizes the biomimetic precipitates and guarantees higher cell adhesion than in absence of SAFs. The apatite nucleation and growth depended on the underlying SAF. Biomimetic coatings on hydroxylated surface increases cell adhesion but on SAFs functionalized surfaces achieve higher cell response. The SAFs with carboxyl ending group promoted the formation of thick and interconnected biomimetic coatings, with low fluid retention and a very significant cell response.

The design of durable superhydrophobic coatings for metal surfaces is a subject of interest and research. Galvanized steel is one of the most used metallic materials for components of automobiles, building structures and roofing. In spite of its wide number of applications, galvanized steel has been scarcely modified to reach superhydrophobicity. The main reason for this is that galvanized steel is essentially a zinc-coated steel surface and most of the strategies to prepare superhydrophobic coatings on metal substrates require partial removal of the surface material. For this reason, providing a non-aggressive strategy to create superhydrophobic galvanized steel (or other metal coated materials) is an important challenge. With this aim, we propose in this paper a methodology based on a two-step texturing process (sandblasting and “soft” acid-etching) followed by a fluoropolymer deposition as a non-invasive strategy to produce water repellent surfaces on this material. The roughness of the samples was analyzed by confocal microscopy and FE-SEM imaging, the surface chemical composition by EDX and the wettability properties by contact angle measurements. Our results show that both texturing methods are necessary to create hierarchically micro/nano-structured surfaces on galvanized steel. This structure induces superhydrophobic properties once the metal is subsequently Teflon-coated. Sandblasting introduces a micro-scale texture, while soft acid-etching incorporates nano-asperities.

Several ways to produce superhydrophobic metal surfaces are presented in this work. Aluminum was chosen as the metal substrate due to its wide use in industry. The wettability of the produced surface was analyzed by bouncing drop experiments and the topography was analyzed by confocal microscopy. In addition, we show various methodologies to measure its durability and anti-icing properties. Superhydrophobic surfaces hold a special texture that must be preserved to keep their water-repellency. To fabricate durable surfaces, we followed two strategies to incorporate a resistant texture. The first strategy is a direct incorporation of roughness to the metal substrate by acid etching. After this surface texturization, the surface energy was decreased by silanization or fluoropolymer deposition. The second strategy is the growth of a ceria layer (after surface texturization) that should enhance the surface hardness and corrosion resistance. The surface energy was decreased with a stearic acid film. The durability of the superhydrophobic surfaces was examined by a particle impact test, mechanical wear by lateral abrasion, and UV-ozone resistance. The anti-icing properties were explored by studying the ability to repeal subcooled water, freezing delay, and ice adhesion.

Complete understanding of colloidal assembly is still a goal to be reached. In convective assembly deposition, the concentration gradients developed in evaporating drops or reservoirs are usually significant. However, collective diffusion of charge-stabilized particles has been barely explored. The balance between convective and diffusive flows may dictate the particle dynamics inside evaporating colloidal drops. In this work we performed in situ counting of fluorescent particles in the vicinity of the triple line of evaporating sessile drops by using confocal laser scanning microscopy. We used particles of different sizes, with different charge response over the pH scale and we focused on charged and nearly uncharged particles. Two substrates with different receding contact angles were used. Binary colloidal mixtures were used to illustrate simultaneously the accumulation of particles with two different charge states at the triple line. The deposition rate close to the triple line was different depending on the electric state of the particle, regardless of the substrate used.

The oxidation state of the surfaces of titanium-based biomaterials strongly depends on their previous history. This factor affects the titanium wettability and it probably conditions the success of the implanted biomaterials. However, the separate role of the pollution and oxidation states of metallic titanium surfaces remains still controversial. To elucidate this, it is required to standardize the initial surface state of titanium in terms of roughness and surface chemistry, and then, to monitor its wettability after the corresponding treatment. In this work, we studied finely polished surfaces of commercially pure titanium (cpTi) which were subjected to cleaning surface treatments. X-Photoelectron spectroscopy was used to characterize the surface chemistry and the oxide film thickness. The contact angle hysteresis in underwater conditions was measured with the growing/shrinking captive bubble method, which allowed for mimicking the real conditions of implantable devices. The water wettability of smooth...

The interfacial activity of 3.5 nm homogeneous (HPs) and amphiphilic Janus gold nanoparticles (JPs) was characterized by pendant drop tensiometry for water/air and water/decane interfaces. This technique requires a smaller quantity of nanoparticles than the traditional Langmuir balance technique. The direct deposition at the interface of the nanoparticles dispersed in a spreading solvent also requires smaller quantities of sample than does adsorption from the bulk. From the growing and shrinking of the pendant drops, the interfacial activity of the nanoparticles can be evaluated and compared within a wide range of area per particle. In this work, the JPs exhibited a higher interfacial activity than did the HPs in all cases. A hard disk model fits the piecewise compression isotherm of the HPs, yet this model underestimates the interactions between the JPs adsorbed at the interface.

Surface functionalization based on organophosphonate molecules and Direct Laser Patterning (DLP) technique both allow to design chemically patterned titanium surfaces devoted to biomaterial engineering. Ultrapolished surfaces of commercially pure titanium were modified with 16-phosphonohexadecanoic acid and octadecylphosphonic acid. The DLP technique with a green pulsed laser was applied to selectively desorb the organophosphonate molecules on the functionalized titanium surfaces. Three regimes of laser ablation were found on the bare titanium surfaces as the ratio between the spot diameter and the interspot distance. Finally, the organophosphonate functionalized titanium surfaces subjected to DLP revealed different wettability domains with minimum impact on the roughness, validated by XPS, AFM and ESEM.

We study the pattern formation induced by drying colloidal suspensions and polymer solutions in a vertical Hele-Shaw cell immersed in a reservoir. The contact line speed is controlled by pumping out the solution from the reservoir. At low capillary number stick–slip motion of the receding contact line can be observed for silica suspensions. Periodic strips spontaneously form during drying. We study the strip periodicity and deposit morphology as a function of the receding velocity and pH of the solution. In the same conditions, dried polymer films are almost flat.

In order to produce well-ordered structures via evaporation, it is essential to control the evaporation flux, solute concentration, interaction between the solute and the substrate, etc. During the drying of particle suspensions, the particle deposition process can be dictated by electrostatic and van der Waals forces. However, the complex physics involved in the drying of colloidal particle suspensions and the erratic contact line dynamics of evaporating sessile drops complicate the analysis of the problem. In this work, we propose a new methodology based on shrinking sessile drops to standardize the contact line dynamics of evaporating drops, but with no observable evaporation (macroscopic scale). We used a microinjector to decrease the drop volume through a small hole drilled in the substrate. Unlike drying drops, with our methodology the particle concentration in the drop bulk remained constant during the entire process and the macroevaporation was negligible. We probed the arrangement of nanoparticles at driven receding contact lines, with low capillary numbers and at time scales shorter than during free evaporation. The electrostatic double layer interactions were modified by diluting the nanoparticles in buffer solutions at different pH values. We also examined the impact of the wettability contrast between the substrate and the particle on the deposit morphology. We found that the ring-like deposits formed at driven contact lines might be suppressed with strongly interacting particles.

Owing to contact angle hysteresis, the contact angle that a sessile drop adopts on a surface can be quite different depending on the process of drop formation. This is particularly noticeable for receding contact angle because it is most susceptible to the details of the measuring method. We performed low-rate dynamic contact angle experiments with steadily moving contact lines and millimeter-size drops in the very low-capillary number regime. We employed a quadratic volumetric flow rate ( V ∝ t 3 ) to achieve the steady motion of contact lines such as happens in the Wilhelmy balance. The values of receding contact angle provided with the quadratic flow rate were stable and time-independent over a larger area of the polymer surfaces studied. Next, we monitored receding sessile drops with equal initial volume but different static contact angle on the same surface. This procedure allowed us to scan the contact angle hysteresis range up to the minimum observable value of contact angle. We probed with distilled water the different response of surfaces of polymer (PMMA, PC and PTFE) and metal oxide (titanium). We found two behaviors according to the substrate employed: a constant value of receding contact angle regardless of the static contact angle and a decrease of receding contact angle as the static contact angle decreased.

Currently, there is no conclusive evidence regarding the global equilibrium condition of vibrated drops. However, it is well-known that vibration of sessile drops effectively reduces the contact angle hysteresis. In this work, applying a recent methodology for evaluating the most-stable contact angle, we examined the impact of the type of excitation signal (random signal versus periodical signal) on the values of the most-stable contact angle for polymer surfaces. Using harmonic signals, the oscillation frequency affected the postvibration contact angle. Instead, the white noise signal enabled sessile drops to relax regardless of their initial configuration. In spite of that, the values of most-stable contact angle obtained with different signals mostly agreed. We concluded that not only the amount of relaxation can be important for relaxing a sessile drop but also the rate of relaxation. Together with receding contact angle, most-stable contact angle, measured with the proposed methodology, was able to capture the thermodynamic changes of "wetted" polymer surfaces.

After the impact of the great review of M. Strobel and C. S. Lyons on contact angle measurements, we discuss some claims of the authors. The Wilhelmy method is not generally "the best technique for measuring the contact angle hysteresis" as the authors claimed. Otherwise, we think that, even though equilibrium contact angle is an "unattainable" angle, the most-stable contact angle obtained from the system relaxation is experimentally accessible. The most-stable contact angle is energetically significant for evaluating quantitatively the surface energy value of rough, chemically homogeneous surfaces from the Wenzel equation, and the average surface energy of smooth, chemically heterogeneous surfaces from the Cassie equation. The most-stable contact angle, the advancing contact angle and the receding contact angles enable the thermodynamic description of the range of contact angle hysteresis and the distribution of metastable system configurations.

In order to characterize a solid surface, the commonly used approach is to measure the advancing and receding contact angles, i.e., the contact angle hysteresis. However, often an estimate of the average wettability of the solid–liquid system is required, which involves both the dry and wetted states of the surface. In this work, we measured advancing and receding contact angles on six polymer surfaces (polystyrene, poly(ethylene terephthalate), poly(methyl methacrylate), polycarbonate, unplasticized poly(vinyl chloride), and poly(tetrafluoroethylene)) with water, ethylene glycol and formamide using the sessile drop and captive bubble methods. We observed a general disagreement between these two methods in the advancing and receding contact angles values and the average contact angle determined separately by each method, although the contact angle hysteresis range mostly agreed. Surface mobility, swelling or liquid penetration might explain this behaviour. However, we found that the 'cross' averages of th...

Texturization of surfaces is usually advantageous in biomaterial engineering. However, the details of the textured surfaces can be more determining on cell adhesion and proliferation, rather than their roughness degree. Titanium is extensively used as a dental implant material in the human body. In this paper, the effect of four surface treatments on commercially pure titanium has been evaluated. These treatments were polishing (pTi); hydrofluoric acid (HF) etching (eTi); Al2O3 blasting (bTi); Al2O3 blasting + HF etching (beTi). Roughness and fractal dimensions were obtained from atomic force microscopy. Wettability was measured using water sessile drops. Morphology and surface chemical composition were analyzed with scanning electron microscopy and energy dispersive X-ray (EDX). MG-63 cell cultures were performed at different times (180 min, 24 h, 48 h, 72 h). Lowest roughness was found in pTi samples followed by eTi, bTi and beTi samples. Etching generated surfaces with the highest fractal dimension and negative skewness. Young contact angles were similar except for pTi and bTi surfaces. Silicon and aluminum traces were found in pTi and bTi samples, respectively. Cell adhesion (≤24 h) was greater on bTi and beTi surfaces. After 48 h, cell proliferation, mediated by specific morphologies, was improved in eTi samples followed by beTi surfaces. For the same surface chemistry, cell growth was driven by topography features.

The purpose of this article is to present some important advances in the imaging techniques currently used in the characterization of bitumen and bituminous emulsions. Bitumen exhibits some properties, such as a black colour and a reflecting surface at rest, which permit the use of optical techniques to study the macroscopic behaviour of asphalt mixes in the cold mix technology based on emulsion use. Imaging techniques allow monitoring in situ the bitumen thermal sensitivity as well as the complex phenomenon of emulsion breaking. Evaporation-driven breaking was evaluated from the shape of evaporating emulsion drops deposited onto non-porous and hydrophobic substrates. To describe the breaking kinetics, top-view images of a drying emulsion drop placed on an aggregate sheet were acquired and processed properly. We can conclude that computer-aided image analysis in road pavement engineering can elucidate the mechanism of breaking and curing of bituminous emulsion.

Since de Gennes coined in 1992 the term Janus particle (JP), there has been a continued effort to develop this field. The purpose of this review is to present the most relevant theoretical and experimental results obtained so far on the surface activity of amphiphilic JPs at fluid interfaces. The surface activity of JPs at fluid-fluid interfaces can be experimentally determined using two different methods: the classical Langmuir balance or the pendant drop tensiometry. The second method requires much less amount of sample than the first one, but it has also some experimental limitations. In all cases collected here the JPs exhibited a higher surface or interfacial activity than the corresponding homogeneous particles. This reveals the significant advantage of JPs for the stabilization of emulsions and foams.

A Langmuir-type pendant drop film balance has been applied in the study of protein monolayers at the water−air interface in a comparative study of adsorbed and spread β-casein layers. Trurnit's method for spreading proteins at the air−water interface has been modified and thoroughly adapted to the requirements of the pendant drop technique. Adsorbed β-casein layers have been obtained by means of double coaxial capillary that enables a subphase exchange, once the desired amount of protein attains the interface. Precisely, this becomes one of the most practical aspects of this technique, allowing a direct comparison between spread and adsorbed layers. Moreover, it provides an alternative to conventional spreading methods for obtaining protein layers and promises to be specially useful in the study of globular protein monolayers, which are very difficult to obtain with conventional methods. Comparison between spread and adsorbed π−A isotherms and static elasticity offers an excellent concordance, which incre...

Electric properties of crude oil/water interface play an important role in many industrial applications such as the enhanced oil recovery and road construction. The understanding of the stability mechanism of bitumen-in-water emulsions is of paramount importance in the cold technology of road construction. The stability (or instability) of the emulsion directly affects the transport, the storage and the application on rocks of bitumen emulsions, whereas it has an indirect influence in the final adhesion bitumen–rock. The high values of electrophoretic mobility found for bitumen particles at high pH as well as the charge inversion at low pH are explained by the presence of ionizable surface groups on the bitumen surface. The elevated surface charge density of the spherical bitumen particles brings about that they can be considered as a model system for verifying the electrophoretic relaxation effect experimentally as well as studying the validity of certain standard electrokinetic theories for spherical colloidal particles. Accordingly, the zeta potential was calculated by using different methods such as the classical models (Booth and Overbeek), the exact computation (O'Brien and White) and recent theories (Ohshima). The Hamaker constant of bitumen in water was computed by means of the Lifshitz theory and the simple spectral method from the dielectric responses of alkanes. The stability results suggest that the bitumen dispersion does conform the DLVO theory. In contrast, Non-DLVO forces (such as the “hydrophobic” force) were not observed in this system.

It is well-established that the equilibrium contact angle in a thermodynamic framework is an "unattainable" contact angle. Instead, the most-stable contact angle obtained from mechanical stimuli of the system is indeed experimentally accessible. Monitoring the susceptibility of a sessile drop to a mechanical stimulus enables to identify the most stable drop configuration within the practical range of contact angle hysteresis. Two different stimuli may be used with sessile drops: mechanical vibration and tilting. The most stable drop against vibration should reveal the changeless contact angle but against the gravity force, it should reveal the highest resistance to slide down. After the corresponding mechanical stimulus, once the excited drop configuration is examined, the focus will be on the contact angle of the initial drop configuration. This methodology needs to map significantly the static drop configurations with different stable contact angles. The most-stable contact angle, together with the advancing and receding contact angles, completes the description of physically realizable configurations of a solid-liquid system. Since the most-stable contact angle is energetically significant, it may be used in the Wenzel, Cassie or Cassie-Baxter equations accordingly or for the surface energy evaluation.

We model an infinitely long liquid bridge confined between two plates chemically patterned by stripes of same width and different contact angle, where the three-phase contact line runs, on average, perpendicular to the stripes. This allows us to study the corrugation of a contact line in the absence of pinning. We find that, if the spacing between the plates is large compared to the length scale of the surface patterning, the cosine of the macroscopic contact angle corresponds to an average of cosines of the intrinsic angles of the stripes, as predicted by the Cassie equation. If, however, the spacing becomes of order the length scale of the pattern there is a sharp crossover to a regime where the macroscopic contact angle varies between the intrinsic contact angle of each stripe, as predicted by the local Young equation. The results are obtained using two numerical methods, Lattice Boltzmann (a diffuse interface approach) and Surface Evolver (a sharp interface approach), thus giving a direct comparison of two popular numerical approaches to calculating drop shapes when applied to a non-trivial contact line problem. We find that the two methods give consistent results if we take into account a line tension in the free energy. In the lattice Boltzmann approach, the line tension arises from discretisation effects at the diffuse three phase contact line., Comment: 17 pages, 6 figures, accepted for publication in Langmuir

Contact angle variability, leading to errors in interpretation, arises from various sources. Contact angle hysteresis (history-dependent wetting) and contact angle multiplicity (corrugation of three-phase contact line) are irrespectively the most frequent causes of this uncertainty. Secondary effects also derived from the distribution of chemical defects on solid surfaces, and so due to the existence of boundaries, are the known "stick/jump-slip" phenomena. Currently, the underlying mechanisms in contact angle hysteresis and their connection to "stick/jump-slip" effects and the prediction of thermodynamic contact angle are not fully understood. In this study, axial models of smooth heterogeneous surface were chosen in order to mitigate contact angle multiplicity. For each axial pattern, advancing, receding and equilibrium contact angles were predicted from the local minima location of the system free energy. A heuristic model, based on the local Young equation for spherical drops on patch-wise axial patterns, was fruitfully tested from the results of free-energy minimization. Despite the very simplistic surface model chosen in this study, it allowed clarifying concepts usually misleading in wetting phenomena.

Objective: To compare the effect of self-etching primers and phosphoric acid on the wettability and roughness of smear layer-covered and smear layer-free dentin. Materials and Method: Three self-etching primers (Clearfil SE Bond, AdheSE, and Xeno III) and 10% (w/w) phosphoric acid (H3PO4) solution were evaluated. The substrates were midcoronal dentin with and without smear layer. For each liquid, pH, density, and surface tension were determined. Water wettability of dentin and roughness were measured before and after each etching. Wettability of self-etching primers and phosphoric acid was measured on untreated dentin. Results: Water wettability increased after acid conditioning similarly for all the liquids used. On smear layer-covered surfaces, self-etching primers achieved a comparable wetting but with greater contact angles than phosphoric acid. However, on smear layer-free surfaces, the increasing sequence of contact angle was Clearfil SE < AdheSE < Xeno III < Phosphoric acid. The treatment with phosphoric acid (lowest pH) produced the highest roughness increase on both dentin substrates. The roughening effect of the self-etching adhesives was more evident for AdheSE and Xeno III. Conclusions: Self-etching primers and phosphoric acid promote similar water wettability increase. However, self-etching primers provided lower dentin roughness increase than pretreatment with phosphoric acid. The presence of smear layer did not affect the results of self-etching and phosphoric acid treatments. © 2007 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 2008