Line energy,line tension and drop size

The relation between drop radius, r, the force to move the three phase contact line and the advancing and receding contact angles θ_A and θ_R is studied. To keep the line energy (energy per 2πr, also named line tension) independent of r, the modified Young equation predicts that the advancing and receding contact angles, θ_A and θ_R, change considerably with r. As shown by many investigators, θ_A and θ_R change negligibly, if at all, with r. We quantify recent evidences showing that the line energy is a function of the Laplace pressure and show that this way the modified Young equation is correct and still θ_A and θ_R should hardly change with r. According to our model, the small surface deformation associated with the unsatisfied normal component of the Young equation results in higher intermolecular interactions at the three phase contact line which corresponds to a higher retention force. This time increasing effect is supported by recent experiments.     

Shift of the Bragg position in grazing-incidence diffraction

The intensity distribution in grazing-incidence diffraction along the grazing exit angle, a f, has been generally studied assuming the fulfilment of the Bragg condition, both experimentally and theoretically. We consider deviations of the incidence angle and detector position (θ) from the exact Bragg angle, θ _B, as well as variation of the incidence angle with respect to the surface, α _i, and lattice mismatching of layered structures. The so-called surface peak is caused by refraction and appears at the fixed angular position of the critical angle of the total external reflection, α _c. Beside it an additional peak occurs, that is explained by fulfilling the Bragg condition of the lateral wave vector components of incident and diffracted beams. This corresponds to the intersection of the truncation rod and the Ewald sphere. Therefore its angular position in the diffracted scattering fan depends on both α_i and θ ? θ _B. This additional peak is only visible if α _i is below α _C or θ > θ _B. These considerations have been verified experimentally on an InP layer.     

Modification of wetting properties of CR39 by plasma source ion implantation

Plasma source ion implantation (PSII), a hybrid implantation technique between ion beams and immersion plasmas has been used to modify CR39 surfaces for improved wettability providing both advancing (θ_a) and receding (θ_r) contact angles below 5°. The modifications brought to the polymer surface structure have been characterized by X-ray photoelectron spectroscopy (XPS) and its combination with chemical derivatization (CD-XPS). Oxygen desorption has been observed in spite of the very hydrophilic surfaces. C_1s XPS peak has been displaced toward greater energies, while the opposite has been found for O_1s, both involving new components and strong modifications after ion implantation treatment. Strong evidences about the formation of new chemical functions, like OOH, COOH and CC, have been found and have provided an explanation for the increased wettability.     

Synthesis and characterization of superhydrophobic functionalized Cu(OH)2 nanotube arrays on copper foil

Superhydrophobic functionalized cupric hydroxide (Cu(OH)₂) nanotube arrays were prepared on copper foils via a facile alkali assistant surface oxidation technique. Thus nanotube arrays of Cu(OH)₂ were directly fabricated on the surface of copper foil by immersing in an aqueous solution of NaOH and (NH₄)₂S₂O₈. The wettability of the surface was changed from surperhydrophilicity to superhydrophobicity by chemical modification with 1H,1H,2H,2H-perfluorodecyltriethoxysilane (FAS). The morphologies, microstructures, crystal structure, chemical compositions and states, and hydrophobicity of the films on the copper foil substrates were analyzed by means of scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and water contact angle measurement. It was found that the rough structure of the surface helped to magnify the wettability. The static contact angle (CA) for water is larger than 160° and the contact angle hysteresis (CAH) is lower than 5° on the modified surface. The high roughness of the nanotube arrays along with the generated C-F chains by chemical modification contributed to the improved superhydrophobicity. The present research is expected to be significant in providing a new strategy for the preparation of novel multifunctional materials with potential industrial applications on copper substrates.     

Ordered oxygen overlayers on Cr(100) observed by leed and photoemission

Chemisorbed oxygen atoms on Cr(100) induce strong O(2p) derived surface resonances which are studied by angle resolved photoemission. Well ordered structures are observed after annealing (300°C). In the submonolayer range (θ_O < 1) a study of the symmetry and dispersion of the O(2p) derived features shows the two-dimensional Bloch character associated with either a c(2 × 2)-O surface at low coverages (θ_O?0.25) or a (1 × 1)-O structure at high coverages (θ_O?0.9). When combined with LEED observations and work function data this study indicates that both structures coexist around θ_O = 0.5 and chemisorbed oxygen is probably incorporated into the fourfold hollow sites. At θ_O > 1, the onset of oxidation is clearly shown in the valence band and core level spectra and the data support the existence of a thin spinel-like oxide layer.     

Dynamic wettability of wood surface modified by acidic dyestuff and fixing agent

Acidic dyestuffs can bring brilliant colors to the wood and fixing agents can avoid the color loss. They could change the surface wettability of wood, which impact the gluing process of veneers. In condition of the higher moisture content of wood, the rare veneers, the veneers dyed by acidic dyestuffs and the dyed veneers fixed by Chitosan were glued respectively by one-component wet-curing isocyanate adhesive and the contact angles (θ) of the different gluing interfaces were measured. The dynamic wettability of these gluing interfaces was characterized by both the contact angle θ and the spreading-penetration parameter (K) calculated by θ. The results showed that the θ-values decreased significantly with the extension of time and the initial contact angles (θ_i) decreased with the moisture contents of veneers increasing, but the variation of the balance contact angles (θ_e) was reversed with θ_i. When the moisture contents of veneers were same, the variation of θ of the rare veneers was minimal and the variation of θ of the fixed veneers was maximal. The K-values of these gluing interfaces all decreased significantly with the moisture contents of veneers increasing, but the variations of K were different. The wetting model describing the dynamic wetting process was established on the basis of these variations.     

Universality in the dependence of the drop contact angle on liquid-solid interactions and temperature obtained by the density functional theory

A nonlocal density functional theory is employed to calculate the contact angles of nano- and macrodrops on smooth solid surfaces in wide ranges of temperature and parameters of the Lennard-Jones potentials representing the fluid-fluid and fluid-solid interactions. For both types of drops, simple linear dependencies of the contact angle on the fluid-solid energy parameter ? _fs was found for various temperatures and hard core fluid-solid parameters σ _fs . Expressions are suggested that relate the contact angle θ to the parameters of the interaction potentials and temperature. The most intriguing feature was that for each considered σ _fs there is a value ? _fs ⁰ of ? _fs for which the contact angle θ = θ ₀ becomes independent of temperature and of σ _fs . It is shown that ? _fs = ? _fs ⁰ divides the materials for which θ increases from those for which θ decreases with increasing temperature.     

Complete wetting characteristics of micro/nano dual-scale surface by plasma etching to give nanohoneycomb structure

A variety of flat superhydrophilic surfaces have been fabricated for biological and industrial applications. We report here the preparation of a simple and inexpensive non-polar curved superhydrophilic surface. This surface has dual-scale surface roughness, on both micro- and nanoscales. Curved surfaces with a near-zero water contact angle and ‘complete wetting’ are demonstrated. By using a conventional plasma etching process, which creates microscale irregularity on an aluminum surface, followed by an anodization process which further modifies the plasma etched surface by creating nanoscale structures, we generate a surface having irregularities on two-scales. This surface displays a semi-permanent superhydrophilic property (if the surface has no damage by the exterior failure), having a near-zero contact angle with water drops. We further report a simple and inexpensive curved (i.e., non-planar) superhydrophilic structure with a near-zero contact angle. The dual-scale character of the surface increases the capillary force effect and reduces the energy barriers of the nanostructures.     

The effect of nanoparticles on the surface hydrophobicity of polystyrene

The surface hydrophobicity of polystyrene-nanoparticle nanocomposites has been investigated as a function of the nanoparticle content. The addition of hydrophobically coated nanoparticles in polystyrene increased the contact angle θ of a water drop with respect to that on polystyrene surface due to change of surface composition and/or surface roughness. When the nanoparticles dispersed well in the polymer, cos θ decreased linearly with increasing amount of nanoparticles indicating a composite surface consisting of smooth polystyrene regions and rough nanoparticle regions. In case of formation of nanoparticle aggregates in polystyrene, cos θ decreased sharply at a critical concentration of nanoparticles. The observed behaviour was modeled in terms of a transition from Wenzel regime to Cassie-Baxter regime at a critical roughness length scale below which the Laplace pressure prevented the penetration of the water drop into the surface undulations. We argue that multiple length scales are needed below the critical roughness length scale to increase the contact angle further by decreasing the fraction of surface area of solid material (increasing the fraction of surface area of air) underlying the water drop.     

The relationship between the adhesion work, the wettability and composition of the surface layer in the systems polymer/aqueous solution of anionic surfactants and alcohol mixtures

Measurements of advancing contact angle (θ) were carried out on polytetrafluoroethylene (PTFE) and polymethylmethacrylate (PMMA) for aqueous solution of sodium dodecyl sulfate (SDDS) mixtures with methanol, ethanol and propanol in the range of SDDS concentration from 10⁻⁵ to 10⁻² M, and for sodium hexadecyl sulfonate (SHS) with the same alcohols at the SHS concentration ranging from 10⁻⁵ to 8 × 10⁻⁴ M at 293 K. The concentration of methanol, ethanol and propanol used for measurements varied from 0 to 21.1, 11.97 and 6.67 M, respectively. On the basis of the contact angles the critical surface tension of PTFE and PMMA wetting was determined by using for this purpose the relationship between the adhesion and the surface tension and cos θ and surface tension both at constant alcohol and surfactant concentration, respectively. The obtained contact angles were also used in the Young Dupre’ equation for calculations of the adhesion work of aqueous solution of mixtures of anionic surfactants and short chain alcohols to PTFE and PMMA surface. The adhesion work calculated in this way was compared to that of the particular components of aqueous solution to these surfaces determined on the basis of the surface tension components and parameters of the surface tension of the surface active agents, water, PTFE and PMMA from van Oss et al. equation. The calculated adhesion work was discussed in the light of the concentration of surface active agents at polymer-water and water-air interface determined from Lucassen-Reynders, Gibbs and Guggenheim-Adam equations.     

Laser-induced periodic surface structures on polymers for formation of gold nanowires and activation of human cells

Frequently observed coherent structures in laser-surface processing are ripples, also denoted as laser-induced periodic surface structures (LIPSS). For polyethylene terephthalate (PET) and polystyrene (PS), LIPSS can be induced by irradiation with linearly polarized ns-pulsed UV laser light. Under an angle of incidence of θ, their lateral period is close to the laser wavelength λ divided by (n _eff ? sinθ). Here, n _eff is the effective refractive index which is 1.32 and 1.23 for PET and PS, respectively. We describe potential applications of LIPSS for alignment and activation of human cells cultivated on polymer substrates, as well as for formation of separated gold nanowires which show pronounced surface plasmon resonances, e.g., at 775 nm for PET.     

Osteoblast cell response to a CO2 laser modified polymeric material

Lasers are an efficient technology, which can be applied for the surface treatment of polymeric biomaterials to enhance insufficient surface properties. That is, the surface chemistry and topography of biomaterials can be modulated to increase the biofunctionality of that material. By employing CO₂ laser patterning and whole area processing of nylon 6,6 this paper details how the surface properties were significantly modified. Samples, which had undergone whole area processing, followed the current theory in which the advancing contact angle, θ, with water decreased and the polar component, γ^p, increased upon an increase in surface roughness. For the patterned samples it was observed that θ increased and γ^P decreased. This did not follow the current theory and can be explained by a mixed-state wetting regime. By seeding osteoblast cells onto the samples for 24 h and 4 days the laser surface treatment gave rise to modulated cell response. For the laser whole area processing, θ and γ^P correlated with the observed cell count and cover density. Owed to the wetting regime, the patterned samples did not give rise to any correlative trend. As a result, CO₂ laser whole area processing is more likely to allow one to predict biofunctionality prior to cell seeding. Moreover, for all samples, cell differentiation was evidenced. On account of this and the modulation in cell response, it has been shown that laser surface treatment lends itself to changing the biofunctional properties of nylon 6,6.     

Dual path surface reconstruction in the H/Ni (110) system

Reconstruction of a Ni (110) surface under the influence of adsorbed hydrogen atoms can proceed in two different ways: Below 180 K a 2×1 lattice-gas structure with θ_H = 1.0 transforms cooperatively into a two-dimensional 1×2 structure by additional uptake of hydrogen up to θ_H = 1.5. At higher temperatures, activated local transformation into a more stable one-dimensional structure starts already at low coverages.     

Relaxation time of a Brownian rotator in a potential with nonparabolic barriers

The extension of the Kramers theory of the escape rate of a Brownian particle from a potential well to the entire range of damping proposed by Mel’nikov and Meshkov [V.I. Mel’nikov, S.V. Meshkov, J. Chem. Phys. 85 (1986) 1018] is applied to the inertial rotational Brownian motion of a fixed axis rotator in a potential V(θ)=−K₁cos2θ−K₂cos4θ, where θ is the angle specifying the orientation of the rotator and K₁ and K₂ are constants. It is shown that in the neighbourhood of K₁∼4K₂ (flat barrier), the Mel’nikov-Meshkov method must suitably be adapted so that the effect of a nonparabolic barrier top can be correctly accounted for in the calculation of the relaxation time. The results obtained are compared with numerical calculations of the longest relaxation time (inverse smallest nonvanishing eigenvalue) using a matrix continued fraction algorithm and reasonable agreement is obtained for K₁≥4K₂ and all values of the dissipation parameter.     

Influence of (phospho)lipases on properties of mica supported phospholipid layers

The effect of enzymes: lipase from Candida cylindracea (L_Cc), phospholipase A₂ from hog pancreas (PLA₂) and phospholipase C from Bacillus cereus (PLC) to modulate wetting properties of solid supported phospholipid bilayers was studied via advancing and receding contact angle measurements of water, formamide and diiodomethane, and calculation of the surface free energy and its components from van Oss et al. (LWAB) and contact angle hysteresis (CAH) approaches. Simultaneously, topography of the studied layers was determined by Atomic Force Microscopy (AFM). The investigated lipid bilayers were transferred on mica plates from subphase of pure water by means of Langmuir-Blodgett and Langmuir-Schaefer techniques. The investigated phospolipid layers were: saturated DPPC (1,2-dipalmitoyl-sn-glycero-3-phosphocholine), unsaturated DOPC (1,2-dioleoyl-sn-glycero-3-phosphocholine), and their mixture DPPC/DOPC. The obtained results revealed that the lipid membrane degradation by the enzymes caused increase in its surface free energy due to the amphiphilic hydrolysis products, which may accumulate in the lipid bilayer. In result activity of the enzymes may increase and then break down the bilayer structure takes place. It is likely that after dissolution of the hydrolysis reaction products in the bulk phase, patches of bare mica surface are accessible, which contribute to the apparent surface free energy changes. Comparison of AFM images and the free energy changes of the layers gives better insight into changes of their properties. The observed gradual increase in the layer surface free energy allows controlling of the hydrolysis process to obtain the surfaces of defined properties.     

Rovibrational spectrum and potential energy surface of the N2-N2O van der Waals complex

The rovibrational spectrum of the N₂-N₂O van der Waals complex has been recorded in the N₂O ν₁ region (∼1285 cm⁻¹) using a tunable diode laser spectrometer to probe a pulsed supersonic slit jet. The observed transitions together with the data observed previously in the N₂O ν₃ region are analyzed using a Watson S-reduced asymmetric rotor Hamiltonian. The rotational and centrifugal distortion constants for the ground and excited vibrational states are accurately determined. The band-origin of the spectrum is determined to be 1285.73964(14) cm⁻¹. A restricted two-dimensional intermolecular potential energy surface for a planar structure of N₂-N₂O has been calculated at the CCSD(T) level of theory with the aug-cc-pVDZ basis sets and a set of mid-bond functions. With the intermolecular distance fixed at the ground state value R = 3.6926 Å, the potential has a global minimum with a well depth of 326.64 cm⁻¹ at θ_N2 = 11.0° and θ_N2O = 84.3° and has a saddle point with a barrier height of 204.61 cm⁻¹ at θ_N2 = 97.4° and θ_N2O = 92.2°, where θ_N2(θ_N2O) is the enclosed angle between the N-N axis (N-N-O axis) and the intermolecular axis.     

Surface magnetism of Sc-substituted Ba-M hexaferrites

A technique of simultaneous gamma-ray, x-ray, and electron Mössbauer spectroscopy is used to study the magnetic structure of the surface layer with direct comparison to the magnetic structure inside single crystal samples of hexagonal Ba-M ferrites, in which part of the iron ions have been replaced by diamagnetic Sc ions (chemical formula BaFe_12?δ Sc_δO₉). It is found that when the diamagnetic Sc ions are introduced into the crystal lattice of BaFe_12?δ Sc_δO₁₉ at concentrations (x=0.4 and 0.6) far below the level at which the collinear magnetic structure inside the sample is destroyed, a macroscopic layer of thickness ～300 nm develops on the surface, in which the magnetic moments of the iron ions are oriented noncollinearly with respect to the moments inside the sample. The deviation 〈θ〉 of the magnetic moments in BaFe_11.6Sc_0.4O₁₉ was 10° ± 62° for x=0.4, and when the Sc concentration was raised to 0.6, the angle 〈θ〉 increased to 17° ± 62°. The noncollinear magnetic structure in the surface layer in these crystals develops because of further reduction in the energy of the exchange interactions owing to the presence of a “defect,” such as the surface. For the first time, therefore, an anisotropic surface layer whose magnetic properties differ from those in the interior of a sample has been observed experimentally in ferromagnetic crystals, as predicted by Néel [L. Néel, Phys. Radium. 15, 225 (1954)].     

Super-hydrophobicity and oleophobicity of silicone rubber modified by CF4 radio frequency plasma

Owing to excellent electric properties, silicone rubber (SIR) has been widely employed in outdoor insulator. For further improving its hydrophobicity and service life, the SIR samples are treated by CF₄ radio frequency (RF) capacitively coupled plasma. The hydrophobic and oleophobic properties are characterized by static contact angle method. The surface morphology of modified SIR is observed by atom force microscope (AFM). X-ray photoelectron spectroscopy (XPS) is used to test the variation of the functional groups on the SIR surface due to the treatment by CF₄ plasma. The results indicate that the static contact angle of SIR surface is improved from 100.7° to 150.2° via the CF₄ plasma modification, and the super-hydrophobic surface of modified SIR, which the corresponding static contact angle is 150.2°, appears at RF power of 200 W for a 5 min treatment time. It is found that the super-hydrophobic surface ascribes to the coaction of the increase of roughness created by the ablation action and the formation of [-SiF_x(CH₃)_2−x-O-]_n (x = 1, 2) structure produced by F atoms replacement methyl groups reaction, more importantly, the formation of [-SiF₂-O-]_n structure is the major factor for super-hydrophobic surface, and it is different from the previous studies, which proposed the fluorocarbon species such as C-F, C-F₂, C-F₃, CF-CF_n, and C-CF_n, were largely introduced to the polymer surface and responsible for the formation of low surface energy.     

Surface modification of polypropylene and compatibilization of interfaces in incompatible blends of polypropylene with polystyrene by plasma of CO2

The effect of surface modification of polypropylene (PP) film is induced by CO₂ plasma in this study. The change in chemical structures on the surface of PP film is characterized by X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FT-IR). The polarity of modified surface of PP film is investigated by contact angle method. The compatibilization of interfaces between polypropylene and polystyrene phases in incompatible blends is studied by the treatment of plasma of CO₂. Transition layer thickness is measured by small angle light scattering (SALS).     

Fabrication of superhydrophobic polyurethane/organoclay nano-structured composites from cyclomethicone-in-water emulsions

Nano-structured polyurethane/organoclay composite films were fabricated by dispersing moisture-curable polyurethanes and fatty amine/amino-silane surface modified montmorillonite clay (organoclay) in cyclomethicone-in-water emulsions. Cyclomethicone Pickering emulsions were made by emulsifying decamethylcyclopentasiloxane (D₅), dodecamethylcyclohexasiloxane (D₆) and aminofunctional siloxane polymers with water using montmorillonite particles as emulsion stabilizers. Polyurethane and organoclay dispersed emulsions were spray coated on aluminum surfaces. Upon thermosetting, water repellent self-cleaning coatings were obtained with measured static water contact angles exceeding 155° and low contact angle hysteresis (<8°). Electron microscopy images of the coating surfaces revealed formation of self-similar hierarchical micro- and nano-scale surface structures. The surface morphology and the coating adhesion strength to aluminum substrates were found to be sensitive to the relative amounts of dispersed polyurethane and organoclay in the emulsions. The degree of superhydrophobicity was analyzed using static water contact angles as well as contact angle hysteresis measurements. Due to biocompatibility of cyclomethicones and polyurethane, developed coatings can be considered for specific bio-medical applications.