The Wenzel and Cassie-Baxter equations depending on the extent of liquid/solid interfacial contact area were generally used to estimate water contact angles on superhydrophobic surfaces. In this study, a simple method is proposed on the criterion to use the Wenzel and Cassie-Baxter equations to evaluate the contact angle results on superhydrophobic surfaces. In this method, the difference between the theoretical (geometric) and experimental contact angle-dependent Wenzel roughness parameter, Delta r(w), and Cassie-Baxter solid/liquid contact area fraction, Delta f(s)(CB) were determined, and the validity of these equations was evaluated. We used the data of eight recent publications where the water drop sits on square and cylindrical pillar structured superhydrophobic model surfaces. We evaluated the contact angle results of 166 patterned samples with our method. We also found that the effect of contact angle error margins was low to vary these parameters. In general, the use of the Wenzel equation was found to be wrong for most of the samples (74% of the samples for cylindrical and 58% for square pillar patterned surfaces), and the deviations from the theory were also high for the remaining (26% for cylindrical and 42% for square) samples, and it is concluded that the Wenzel equation cannot be used for superhydrophobic surfaces other than a few exceptions, especially for cylindrical patterns. For the Cassie-Baxter equation, two situations are possible: for positive Delta f(s)(CB), there is only a partial contact of the drop with the top solid surface, and, for negative Delta f(s)(CB), the penetration of the drop in between the pillars is possible, and thus the liquid drop is in contact with the lateral sides of the pillars. We found that 65% of the samples containing cylindrical pillars (52-77% with error margins) and 44% of the samples containing square pillars (38-50% with error margins) resulted in negative Delta f(s)(CB)(red) values. In addition, large deviations of experimental water contact angle results, theta r(e) from the theoretical theta r(CB) were also determined for most of the samples, indicating that the Cassie-Baxter equation should be applied to superhydrophobic surfaces with caution.

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In this study, we prepared thin films by blending ethylene vinyl acetate copolymers (EVA) containing 12-33 (wt.%) vinyl acetate (VA) with polyvinyl acetate (PVAc) and high density polyethylene homopolymers. Large area micropatterns having controlled protrusion sizes were obtained by phase-separation especially for the PVAc/EVA-33 blends using dip coating. These surfaces were characterized by XPS and contact angle measurements. A reasonably linear relation was found between the VA content on the surface (wt.%) obtained from XPS analysis and the VA content in bulk especially for PVAc/EVA-33 blend surfaces. PE segments were more enriched on the surface than that of the bulk for pure EVA copolymer surfaces similar to previous reports and VA enrichment was found on the EVA/HDPE blend surfaces due to high molecular weight of HDPE. Water θe decreased with the increase in the VA content on the blend surface due to the polarity of VA. A good agreement was obtained between γs-and atomic oxygen surface concentration with the increase of VA content. The applicability of Cassie-Baxter equation was tested and found that it gave consistent results with the experimental water contact angles for the case where VA content was lower than 55 wt.% in the bulk composition. © 2011 Elsevier B.V. All rights reserved

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In this study, the effect of drop volume on contact angle (CA) values and also on the applicability of the Cassie-Baxter equation is experimentally investigated. To do this, dimethyldichlorosilane (DMDCS) coated different sized square pillar surfaces with varying f CB s (geo) values were used. Varying water drop volumes between 0.5 ml and 19 ml were used to measure CA's on square pillar surfaces with different pattern sizes changing from 8 mm to 40 mm. It was found that experimental CA values remained constant for each drop volume, indicating that increase or decrease in drop volume had no significant effect on experimentally measured CA values of square pillar surfaces with varying pattern sizes and f CB s (geo) values. When the relationship between the applicability of the Cassie-Baxter equation and the drop volume was investigated, it was also found that variation in volume of the drop did not cause a significant change in deviations between the theory and the experiments. Dq CB values remained almost constant for all samples at varying drop volumes.

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Flat and rough thin films were prepared by dip coating using LDPE, PVAc, and EVA polymers containing 12-40% VA contents. Surface free energy of flat films was determined by measuring contact angles. Surface atomic composition was investigated by XPS at 0 and 60 take-off angles. XPS results show that hydrophobic PE component was found to enrich at the near-surface region for all EVA samples for a depth of $ 5 nm for both flat and rough surfaces, whereas hydrophilic VA component was enriched on the surface when VA < 18% for only at 10 nm depth. The difference between the XPS results of the flat and rough surfaces was not significant for EVA samples except EVA-33 surface where the atomic oxygen content decreased 15-20% for rough surfaces. Contact angle hysteresis values for the rough samples were much larger than that of the flat samples for LDPE and EVA-12 surfaces due to the presence of partial trapping of air pockets on these rough surfaces. A good agreement was obtained between surface concentration of atomic oxygen in the 5 nm outermost layer and c À S surface free energy component especially for the samples having high VA contents.

Wettability is one of the surface characteristics that is controlled by the chemical composition and roughness of a surface. A number of investigations have explored the relationship between water contact angle and surface free energy of polymeric coatings with the settlement (attachment) and adhesion strength of various marine organisms. However, the relationship between the contact angle hysteresis and fouling-release property is generally overlooked. In the present work, coatings were prepared by using commercial hydrophobic homopolymer and copolymer polyolefins, which have nearly the same surface free energy. The effects of contact angle hysteresis, wetting hysteresis, and surface free energy on the fouling-release properties for sporelings of the green alga Ulva from substrates were then examined quantitatively under a defined shear stress in a water channel. The ease of removal of sporelings under shear stress from the polymer surfaces was in the order of PP&gt;HDPE&gt;PPPE&gt;EVA-12 and strongly and positively correlated with contact angle and wetting hysteresis; i.e., the higher the hysteresis, the greater the removal.