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This research was supported by the project MAT2017-82182-R funded by the State Research Agency (SRA) of Spain and European Regional Development Fund (ERDF). Funding for open access charge: Universidad de Granada / CBUA, Hypothesis: Ice adhesion to rigid materials is reduced with low energy surfaces of high receding contact angles. However, their adhesion strength values are above the threshold value to be considered as icephobic materials. Surface deformability is a promising route to further reduce ice adhesion. Experiments: In this work, we prepared elastomer surfaces with a wide range of elastic moduli and hydrophobicity degree and we measured their ice adhesion strength. Moreover, we also explored the deicing performance of oil-infused elastomeric surfaces. The ice adhesion was characterized by two detachment modes: tensile and shear. Findings: The variety of elastomeric surfaces allowed us to simultaneously analyze the ice adhesion dependence with deformability and contact angle hysteresis. We found that the impact of these properties depends on the detachment mode, being deformability more important in shear mode and hydrophobicity more relevant in tensile mode. In addition, oil infusion further reduces ice adhesion due to the interfacial slippage. From an optimal balance between deformability and hydrophobicity, we were able to identify surfaces with super-low ice adhesion., MAT2017-82182-R State Research Agency (SRA), European Regional Development Fund (ERDF), Universidad de Granada / CBUA

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.

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.

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.

In this article, a compilation of results on direct force measurements between colloidal particles in monovalent salts carried out with the colloidal probe technique based on Atomic Force Microscopy was presented. The interaction forces between similar and dissimilar particles was studied and it was concluded that, in general, these force profiles may be satisfactorily quantified by the DLVO theory down to distances of few nanometers. However, in the specific case where the charge of one of the involved particle is close to neutral, it was found that the surface potential of this particle may change its sign depending on the sign of charge of the opposite particle. In this respect, the assumption that the surface potential of a particle is a property only related to the particle surface features and the bulk properties is called into question. Microsc. Res. Tech. 80:144-152, 2017. © 2016 Wiley Periodicals, Inc.

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.

Hypothesis Wettability of solid surfaces is mostly probed with sessile drops rather than bubbles because this method is readily followed out. This recurrent use may lead to a misleading connection of certain phenomena to the hydrophobicity/hydrophilicity of materials. For instance, the Cassie-Baxter regime and the wicking effect are generally associated only to hydrophobic and hydrophilic surfaces, respectively. However, the same phenomenology should be observed when air bubbles (underwater conditions) in contact with solid surfaces are used instead. In particular, one might expect that rough-hydrophilic surfaces become superaerophobic due to the appearance of a hybrid dewetting regime, like the Cassie-Baxter regime described for rough-hydrophobic surfaces. Otherwise, rough-hydrophobic surfaces might become superaerophilic due to air-wicking. Experiments To elucidate this issue, in this work, we analyzed the wettability of surfaces with very different intrinsic contact angle and roughness degree. The analysis was performed with both Sessile Drop and Captive Bubble methods. Findings Our results with captive bubbles for rough-hydrophilic surfaces revealed phenomena only explained by the occurrence of a transition from the Wenzel regime to an “inverse” Cassie-Baxter regime. In addition, our results with captive bubbles for rough-hydrophobic surfaces showed evidences of air percolation through the interconnected asperities. This effect reminds the wicking effect reproduced on rough-hydrophilic surfaces, responsible for superhydrophilicity.

Interactions involving charged particles in the presence of multivalent ions are relevant in wide-range of phenomena, including condensation of nucleic acids, cement hardening, or water treatment. Here, we study such interactions by combining direct force measurements with atomic force microscopy (AFM) and aggregation studies with time-resolved light scattering for particles originating from the same colloidal suspension for the first time. Classical DLVO theory is found to be only applicable for monovalent and divalent ions. For ions of higher valence, charge inversion and additional non-DLVO attractive forces are observed. These attractive forces can be attributed to surface charge heterogeneities, which leads to stability ratios that are calculated from direct force measurements to be higher than the experimental ones. Ion-ion correlations are equally important as they induce the charge inversion in the presence of trivalent or tetravalent ions, and they enhance the surface charge heterogeneities. Such heterogeneities therefore play an essential role in controlling interactions in particle suspensions containing multivalent ions.

In this article, a compilation of results on direct force measurements between colloidal particles in monovalent salts carried out with the colloidal probe technique based on Atomic Force Microscopy was presented. The interaction forces between similar and dissimilar particles was studied and it was concluded that, in general, these force profiles may be satisfactorily quantified by the DLVO theory down to distances of few nanometers. However, in the specific case where the charge of one of the involved particle is close to neutral, it was found that the surface potential of this particle may change its sign depending on the sign of charge of the opposite particle. In this respect, the assumption that the surface potential of a particle is a property only related to the particle surface features and the bulk properties is called into question. Microsc. Res. Tech. 80:144-152, 2017. © 2016 Wiley Periodicals, Inc.

Force profiles and aggregation rates involving positively and negatively charged polystyrene latex particles are investigated in monovalent electrolyte solutions, whereby the counterions are varied within the Hofmeister series. The force measurements are carried out with the colloidal probe technique, which is based on the atomic force microscope (AFM), while the aggregation rates are measured with time-resolved multiangle light scattering. The interaction force profiles cannot be described by classical DLVO theory, but an additional attractive short-ranged force must be included. An exponential force profile with a decay length of about 0.5 nm is consistent with the measured forces. Furthermore, the Hamaker constants extracted from the measured force profiles are substantially smaller than the theoretical values calculated from dielectric spectra. The small surface roughness of the latex particles (below 1 nm) is probably responsible for this deviation. Based on the measured force profiles, the aggregation rates can be predicted without adjustable parameters. The measured absolute aggregation rates in the fast regime are somewhat lower than the calculated ones. The critical coagulation concentration (CCC) agrees well with the experiment, including the respective shifts of the CCC within the Hofmeister series. These shifts are particularly pronounced for the positively charged particles. However, the consideration of the additional attractive short-ranged force is essential to quantify these shifts correctly. In the slow regime, the calculated rates are substantially smaller than the experimental ones. This disagreement is probably related to surface charge heterogeneities.

Force profiles as well as aggregation and deposition rates are studied for asymmetrically charged particles and surfaces in aqueous electrolytes theoretically. Interactions are calculated within the Derjaguin, Landau, Verwey, and Overbeek (DLVO) theory, whereby the electrostatic part is modeled at Poisson–Boltzmann (PB) level. Unequally charged surfaces are examined, from the symmetric system, where both surfaces are equally charged, to fully asymmetric systems, where the surfaces are oppositely charged. Charged-neutral systems, where one surface is charged and the other is neutral, emerge as an essential scenario. In this case, the choice of boundary conditions used for solving the PB equation is crucial, whereby constant charge and constant potential boundary conditions lead to either fully repulsive or fully attractive forces. Consequently, charge regulation has a major influence on particle aggregation and deposition rates too. In the charge-neutral case, substantial shifts in the critical coagulation concentration (CCC) are observed when the regulation properties are changed. In the presence of multivalent ions, these systems behave similarly to the symmetrically charged ones. The CCC decreases with the square of the valence in weakly charged systems, while unrealistically high charge densities are needed to recover the classical Schulze–Hardy limit, which predicts a sixth power dependence on valence.

Interaction forces between carboxylate colloidal latex particles of about 2 μm in diameter immersed in aqueous solutions of monovalent salts were measured with the colloidal probe technique, which is based on the atomic force microscope. We have systematically varied the ionic strength, the type of salt, and also the surface charge densities of the particles through changes in the solution pH. Based on these measurements, we have accurately measured the dispersion forces acting between the particles and estimated the apparent Hamaker constant to be (2.0 ± 0.5) × 10-21 J at a separation distance of about 10 nm. This value is basically independent of the salt concentration and the type of salt. Good agreement with Lifshitz theory is found when roughness effects are taken into account. The combination of retardation and roughness effects reduces the value of the apparent Hamaker constant and its ionic strength dependence with respect to the case of ideally smooth surfaces. Swiss National Science Foundation CM1101

Forces between positively and negatively charged colloidal particles across aqueous salt solutions containing multivalent ions are measured directly with the atomic force microscope (AFM). The measurements are interpreted quantitatively with Poisson-Boltzmann (PB) theory. Thereby, the surface potentials and regulation properties of the particle surfaces are extracted from symmetric measurements between the same types of particles. This information is used to predict force profiles in the asymmetric situations involving different types of particles without any adjustable parameters. These predictions turn out to be very accurate, which demonstrates that the mean-field PB theory is reliable down to distances of about 5 nm. While various reports in the literature indicate that this theory should fail due to neglect of ion correlations, such effects seem important only at higher concentrations and smaller distances.