Any review on the shape of a liquid droplet on top of a solid surface has to start with the pioneering work by P.S.Laplace and Sir Thomas Young almost two centuries ago [1, 2]. Young and Laplace set out to describe the phenomenon of “capillary action” in which the liquid inside a small capillary tube may rise several centimeters above the liquid outside the tube [3]. To understand this effect, two fundamental equations were derived by Young and Laplace. The first equation, known as the Laplace or Young-Laplace equation [1], relates the curvature at a certain point of the liquid surface to the pressure difference between both sides of the surface, and we consider it next in more detail. The second equation is Young’s equation [2], which relates the contact angle to the surface tensions involved.

The effect of plasma treatment on surface characteristics of polyethylene terephthalate films was investigated using helium and oxygenated-helium atmospheric plasmas. Sample exposure to plasma was conducted in a closed ventilation test cell inside the main plasma chamber with variable exposure times. The percent weigh loss of the samples showed an initial increase followed by decrease with extended exposure time, indicating a combined mechanism of etching and redeposition. The wettability as measured by the contact angle showed a sharp initial increase followed by a steady-state trend with increased exposure time, suggesting a change in surface functionality. Atomic force microscopy analysis revealed increase in surface roughness, as well as evidence of redeposition of etched volatiles. Functionality changes were measured using X-ray photoelectron spectroscopy and these changes were correlated to the new plasma-induced properties. © 2004 The Electrochemical Society. All rights reserved.

The polypropylene modification in CO₂ plasma mainly contributes to degradation, functionalization, and cross-linking. The degradation, whose rate is depending on CO₂ dissociation and oxygen atom formation, is a quite slow reaction and it is associated with surface topography alteration, especially of the amorphous phase of the polypropylene. The surface roughness increases with the treatment duration and the amorphous phase is more degraded than the crystallized part. The functionalization, corresponding to an increase of the surface energy (57.3 mJċ m ^{− 2} in 30 s), and to an oxidation (23 oxygen at.%) with the appearance of alcohol, ketone, and acid functions is a much faster phenomenon. Cross-linking takes also place during this type of treatment and will reinforce the stability of the modified surface.

Wettable surface of polymers (advanced wetting angle ∼10° and surface energy ∼ 60 ∼ 70 erg/cm²) have been accomplished by the ion assisted reaction, in which energetic ions are irradiated on polymer with blowing oxygen gas. The energies of ions are varied from 0.5 to 1.5 keV, doses 10¹⁴ to 10¹⁷ ions/cm², and blowing rate of oxygen 0 ∼ 8 ml/min. The wetting angles are increased when the wettable polymers were exposed in air, but are remained in pure water. Improvement of surface energy is mainly due to the polar force. Surface analysis shows hydrophilic functional groups such as CO, (CO)O, CO, etc., are formed without surface damage after the ion assisted reaction treatment. Comparisons between the conventional surface treatments and the ion assisted reaction are described in term of physical bombardment, surface damage, functional group, and chain mobility in polymer.

In order to illuminate the mechanisms of corona discharge treatment on ultra-high molecular weight polyethylene (UHMWPE) fibre, the effects of corona treatment power and time are discussed in detail. The surface-roughness and tensile-failure characteristics of the polyethylene fibre were determined by a scanning electron microscope (SEM). The photos from the SEM showed that the size and number of the micro-pits on the fibre surface increase with increase of corona power. The oxygen-containing groups on the fibre surface could be detected by Fourier-transform infrared attenuated total reflectance and also increased gradually with increase of corona power. The T-peel strength of composites increased from the corona treatment, and then showed a maximum value at a corona treatment time about 0.1 s with increase of treatment time. However, the tensile strength of the fibre was reduced with increase of corona power and the failure mechanism obviously changed after the treatment. The ballistic impact energy absorption of UHMWPE fibre/vinylester composite was obtained after fragment simulating projectiles (FSP) impact tests. After 6-kW corona treatment for 0.075 s, the impact energy absorbed by the laminate reached a maximum value. Copyright © 2003 Society of Chemical Industry

These lecture notes discuss some theoretical approaches for the prediction of the structure, thermodynamics, and dynamics of polymers at interfaces, with emphasis on self-consistent field (SCF) methods. We begin with simple models for the conformational statistics of unperturbed chains and derive the Edwards diffusion equation for a Gaussian thread in a field. We then describe a simple lattice-based approach for a polymer melt at a flat interface and results from its application. Next, we discuss mixing energetics in the lattice model and outline an extension of the lattice-based SCF theory to treat copolymers at interfaces. Correspondences are pointed out between lattice-based and continuous SCF approaches, the latter making use of the Edwards diffusion equation. As an example of continuous formulations we present Helfand and Tagami’s elegant analytical solution for a flat interface between two immiscible polymers in the limit of very large molecular weights. Following Fredrickson et al., we outline a general fieldtheoretic approach for the mesoscopic modelling of inhomogeneous polymer systems. Using a symmetric diblock copolymer as an example, we show how a saddle point approximation reduces this formalism to a SCF theory and discuss the phase diagram obtained through continuous SCF by Matsen and Schick. As an example of scaling considerations, we derive expressions for the chain length dependence of the long period of the lamellar phase of the diblock copolymer. The latter part of the notes focusses on applications and comparisons with experiment. We discuss the structure of polymer/polymer and solid/polymer interfaces in the presence of diblock copolymers. We then briefly review a hierarchical theoretical/simulation approach for exploring adhesion at a solid/polymer interface strengthened by chains terminally grafted to the solid.

Surfaces and interfaces exhibit a rich variety of phase transitions. While some of these phase transitions also occur in the bulk, others involve coupling between surface and bulk degrees of freedom; consequently the surface phase diagram may be rather complex even for simple Ising like systems. In these lectures I will introduce the generic 4-dimensional surface phase diagram (bulk and surface couplings, bulk and surface fields) of Ising like systems and discuss bulk vs. surface criticality. I will start with a review of surface thermodynamics and scaling of interfaces with emphasis on wetting phenomena. Then Landau mean-field theory is used to calculate the global surface phase diagram. The effects of thermal fluctuations are discussed using the capillary wave Hamiltonian: The correlation functions are calculated using Ornstein-Zernike theory for systems with short and long-range forces. Finally, I will comment on the status of the renormalization group results for 3-dimensional short-range critical wetting that are at odds with the results of simulations of the Ising model and of a recent experiment.

Static and dynamic contact angles of aqueous solutions of three surfactants--anionic sodium dodecyl sulfate (SDS), cationic dodecyltrimethylammonium bromide (DTAB), and nonionic pentaethylene glycol monododecyl ether (C(₁₂)E(₅))-were measured in the pre- and micellar concentration ranges on polymer surfaces of different surface free energy. The influence of the degree of substrate hydrophobicity, concentration of the solution, and ionic/nonionic character of surfactant on the drop spreading was investigated. Evaporation losses due to relatively low humidity during measurements were taken into account as well. It was shown that, in contrast to the highly hydrophobic surfaces, contact angles for ionic surfactant solutions on the moderately hydrophobic surfaces strongly depend on time. As far as the nonionic surfactant is considered, it spreads well over all the hydrophobic polymer surfaces used. Moreover, the results obtained indicate that spreading (if it occurs) in the long-time regime is controlled not only by the diffusive transport of surfactant to the expanding liquid-vapor interface. Obviously, another process involving adsorption at the expanding solid-liquid interface (near the three-phase contact line), which goes more slowly than diffusion, has to be active.

The interfacial forces which determine the interaction between a liquid and solid surface have been investigated under dynamic conditions of evaporation. The evaporation characteristics of probe liquids and their influence on the droplet of the liquid on a solid substrate have been investigated. The changes in mass, contact angle, solid–liquid contact radius during evaporation of droplets (3-90 mg) of water on glass, polycarbonate and PTFE substrates and droplets of methyl alcohol on polycarbonate, polypropylene, PTFE and high density polyethylene substrates have been examined. The evolution of contact angle and contact radius with the progress of evaporation has been investigated for each droplet-substrate system in order to identify the common trend. In the systems of water droplets on polycarbonate and glass, the contact radius remained constant with the progress of evaporation but such behavior was not observed in the case of methyl alcohol on polycarbonate, polypropylene, PTFE and high density polyethylene.

An overview is presented of a series of papers published during the last decade which show that the conventional thermodynamic approach to liquid—solid adhesion requires some fundamental changes. It is pointed out that it has been a long-neglected fact that adsorption, as generally measured in adsorption isotherms, is actually surface excess, so that it can, in principle, be negative as well as positive. As a result, the free energy of adsorption, AF, can be positive as well as negative. Small amounts of water vapor adsorbing onto previously evacuated poly (tetrafluoroethylene) could, in principle, therefore be increasing the free energy of the low-energy polymer surface. It is further pointed out that from the strictly thermodynamic point of view, changing the free energy of a surface by adsorption of the vapor of a liquid does not necessarily change the contact angle. Resulting changes in contact angle can, however, theoretically occur from changes in the intermolecular force interaction term (proposed work of adhesion), such as those terms proposed by Good and Girifalco, Fowkes and others, where such changes would be speculative. In addition, it is pointed out that an accurate thermodynamic representation of liquid-solid adhesion should take into account the shape of the drop to be deposited (or drop that has been detached), as well as the resulting contact angle. An equation is presented for the free energy of adhesion of a spherical drop.

The surface chemistry and surface energetics of materials are important to the performance of many products and processes—sometimes in as yet unrecognized ways. This review is written for the researcher interested in exploring the nature of surfaces and their relation to processes involving spreading, wetting, liquid penetration and adhesion. Researchers concerned with many types of products including pharmaceuticals, printing and the making of composite materials should have interest in this topic. More specifically, this work is a review of the literature concerning the surface free energy of solids. Both theoretical approaches for understanding the surface free energy of solids are explored and contrasted, as are experimental methods for measuring surface free energy of solids. Experimental methods that offer insight into the chemical nature of surfaces but do not measure surface free energy are also discussed as these two subjects are intertwined.

When we place a liquid drop on a clean, planar, solid surface, we can observe a contact angle θ _E , which is precisely the angle contained in Young’s formula. Quite often, though, the surface is marred by defects that are

• either chemical (stains, blotches, blemishes)

• or physical (surface irregularities).

Capillarity is the study of the interfaces between two immiscible liquids, or between a liquid and air. The interfaces are deformable: they are free to change their shape in order to minimize their surface energy. The field was created in the early part of the 19th century by Pierre Simon de Laplace (1749–1827) and Thomas Young (1773–1829). Henri Bouasse wrote a wonderful account of developments in capillarity in a book he published in 1924.1 This discipline enables us to understand the games water can play to break the monotony of a rainy day or the tricks it performs while washing dishes. On a more serious note, capillarity plays a major role in numerous scientific endeavors (soil science, climate, plant biology, surface physics, and more), as well as in the chemical industry (product formulation in pharmacology and domestics, the glass industry, automobile manufacturing, textile production, etc.).

Based on the Corona process and a substitution of air with specific gaseous mixtures into the discharge area, the newly developed surface treatment ALDYNE™ offers both high level improvement and high flexibility to film converters. By grafting nitrogen-based chemical functions, it confers to the treated surface excellent properties such as high surface energy and high adhesion of coatings.

The effect of oxygen and ammonia plasma treatments on changes of the surface properties of linear high-density polyethylene (HDPE) was studied. Surface energies of the polymer substrates were evaluated by contact angle measurements using Lifshitz-van der Waals acid-base approach. The surface energy of untreated HDPE is mainly contributed by Lifshitz-van der Waals interactions. After 5 min of plasma treatment, hydrogen bonds are formed on the surface, which is reflected in predominant acid-base interactions. The SEM results obtained demonstrate considerable changes of the surface roughness due to different types of the plasma gas used. Evolution of oxygen- or amino-containing moieties was detected by XPS and ATR FT IR. The prepared polyethylene surfaces were used as a basic support for further fabrication of novel hybrid biocomposite sandwich structures.

Polypropylene electrets 20-μm thick obtained in a corona discharge were studied. After the electrets were charged, they were put into a vacuum chamber at various pressures and the electret surface potential was measured over a 1-h period. A desorption from the electrets is suggested to explain the results obtained.

Of the several techniques available for the surface modification, plasma processing has proved to be very appropriate. The low temperature plasma is a soft radiation source and it affects the material only over a few hundred Å deep, the bulk properties remaining unaffected. Plasma surface treatment also offers the advantage of greater chemical flexibility. PET films are widely used for packaging and electrical insulation. The studies of adhesion and printability properties are important. In the present study PET films are treated in air plasma for different time of treatment. The improvement in adhesion is studied by measuring T-peel and Lap shear strength. In addition, printability of plasma treated PET films is studied by cross test method. It has been found that printability increases considerably for plasma treatment of short duration. Therefore it is interesting to study the surface composition and morphology by contact angle measurement, ESCA and AFM. Surface energy and surface roughness can be directly correlated to the improvement in above-mentioned surface related properties. It has been found that the surface oxidation occurs containing polar functional groups such as CO, COO. A correlation of all such observations from different techniques gives a comprehensive picture of the structure and surface composition of plasma treated PET films.

The influence of the gas mixture of oxygen and nitrogen on the treatment efficiency distribution is investigated. The treatment efficiency is evaluated by contact angle measurement on polypropylene (PP) samples placed in varying distance from the coplanar barrier discharge electrode module. A planar electrode operated with 4 kHz signal and power of typically 10–21 W is used for treatment. A strong variation of contact angle as a function of distance from the CDB electrode surface is observed for samples treated 4 s in nitrogen discharge. Contact angle changes within 0.3 mm from 37.9 to 62.5° and it reaches 94.1° for 1.5-mm distance. It is already very close to the value of 103° measured on untreated PP. Much smaller treatment depth is obtained for mixture of nitrogen and oxygen. The experiments are performed without gas flow.fferent plasma treatments in a rf

Polymers such as rubbers generally have low surface energy, thus high hydrophobicity and inherent low bondability. An atmospheric pressure ejected plasma (APEP) source is developed for pre-treatments of polymers to overcome these intractable properties and improve the adhesion ability between polymers as environmental-friendly and simple alternative methods to conventional treatments in spite of several limitations until now. Proper operational conditions are found by T-peel tests performed with various plasma parameters and high peel strength up to 3.5 kgf/cm is achieved at those conditions. Optical emission spectroscopy revealed that the amount of oxygen radicals and gas temperatures are found to be higher at proper conditions in T-peel tests and Fourier transform infrared spectroscopy using attenuated total reflection. Scanning electron microscopy is used for the measurement of surface composition and morphology of pre-treated polymer specimen. These results established the advantage of pre-treatments by APEP source in proper operation conditions when compared to the conventional treatments in terms of improvement of the adhesion ability between polymers.

The barrier solutions presently available on the market all have their drawbacks, e.g. cost, water-sensitivity, opacity or perceived environmental bad-will. At the same time there is a trend to use more plastic-based packaging materials for different applications, e.g. as replacements for metal and glass containers. This situation has stimulated the industry to provide new, more efficient barrier solutions. The innovations go along five major lines: (a) thin, transparent vacuum-deposited coatings; (b) new barrier polymers as discrete layers; (c) blends of barrier polymers and standard polymers; (d) organic barrier coatings; and (e) nanocomposite materials. This paper provides a comprehensive review of the different approaches, outlining the principle behind each barrier technology, its performance, its potential and the companies developing and producing the materials. Copyright © 2003 John Wiley & Sons, Ltd.
https://onlinelibrary.wiley.com/doi/abs/10.1002/pts.621

Described is a method of treating or coating homogeneously at least a portion of the surface of a material selected from metallic materials having a thickness of less than 100 mum and/or polymeric materials. The method of the present invention comprises exposing at least a portion of the surface of the material to an atmospheric plasma generated by an indirect plasmatron. In the method of the present invention, the surface of the material may undergo at least one of an increase in surface tension, a surface grafting, a surface cleaning and a surface sterilization.

The means by which plasma treatment enhances the adhesion of polymer materials, remains obscure. Thus far, two possible mechanisms have been proposed: an increase in surface energy, and the anchor effects imparted by plasma etching. Independently from these mechanisms, reactions between free radicals, generated by plasma irradiation and adhesives are also likely to affect the adhesive properties of polymer materials. Free radicals generated on polyethylene (PE) by glow-discharge plasma were exposed to air and converted to peroxide. The peroxides were converted back to free radicals with the application of heat, and then graft polymerization was initiated, by adding a hydrophilic monomer such as acrylic acid. The peroxides formed by the reaction between free radicals and the oxygen in air was detected by chemiluminescence (CL). In this work, plasma-treated PE surfaces were bonded to aluminum boards, using epoxy resin as an intermediate adhesive and then subjected to a series of peeling tests. The sample with the highest peeling strength also had the highest level of CL-detected peroxides. These findings suggest that the free radicals generated by plasma treatment influence the adhesive properties of the polymer materials.

The rate of production and the spatial distribution of ozone in the negative DC corona discharge are predicted with a numerical model. The results are compared to prior experimental data and to results previously presented by the authors for the positive corona discharge. In agreement with experimental data, ozone production rate in the negative corona is an order of magnitude higher than in the positive corona. The model reveals that this significant difference is due to the effect of discharge polarity on the number of energetic electrons in the corona plasma. The number of electrons is one order of magnitude greater and the chemically reactive plasma region extends beyond the ionization region in the negative corona. The paper also extends our prior modeling effort to lower velocities where the Joule heating reduces ozone production. The magnitude of the reduction is characterized by a new dimensionless parameter referred to as the electric Damkohler's third number(Da_III–e).

The properties of an ac dielectric-barrier corona discharge in argon under atmospheric pressure were studied and the results of testing of this type of gas discharge in the low-temperature treatment of polymer films and fabrics for the purpose of enhancement of their wettability were reported.

Different plasma treatments in a rf discharge of Ar, He, or N₂ are used to etch, cross-link, and activate polymers like PC, PP, EPDM, PE, PS, PET and PMMA. Due to the numerous ways a plasma interacts with the polymer surface, the gas type and the plasma conditions must be adjusted on the polymer type to minimize degradation and aging effects. Wetting and friction properties of polymers can be improved by a simple plasma treatment, demonstrated on PC and EPDM, respectively. However, the deposition of ultra-thin layers by plasma enables the adjustment of wetting properties, using siloxane-based or fluorocarbon films, and further reduction of the friction coefficient, applying siloxane or a-C:H coatings. Nevertheless, the adhesion of plasma-deposited coatings should be regarded, which can be enhanced by depositing a graded layer.

Effects of the exposure of ultraviolet (UV) excimer light on the physicochemical surface properties of polymer films were investigated by contact angle measurements and X-ray photoelectron spectroscopy (XPS). The UV light at wavelength of 172 nm was exposed to polyethylene (PE), polyimide (PI), and polytetrafluoroethylene (PTFE) films in ambient air. The advancing and receding contact angles of water on the unexposed and UV-exposed films were determined by the sessile drop and the Wilhelmy methods as a measure of the wettability. For the PE and PI films, remarkable decrease in the water contact angle was accomplished by the UV exposure of several or several 10 s. The XPS data showed that such increase in the wettability was attributed to the increased atomic oxygen concentration at the film surfaces. The wettability of the PTFE film did not change due to the UV exposure. When the UV-exposed PE and PI films were stored in ambient air, the increase in the water contact angle, i.e. the hydrophobic recovery, was observed over a time scale of several days. It was suggested that the gasification of the low-molecular weight oxidized materials as well as the reorientation and the migration of polymer chains in the oxidized surface layer was responsible for the hydrophobic recovery in air. The UV exposure was also attempted to the PI film being covered with a metal mesh to prepare the film having both non-exposed and UV-exposed surface regions. The differences in the advancing and receding contact angles between the both regions were observed on the continuous weight recording at constant interfacial moving velocity by the Wilhelmy method. The Wilhelmy method in combination with the UV lithography technique enabled the simultaneous evaluation of the wettabilities of the treated and untreated surfaces.