Different methods used to determine the surface energy of solids from the contact angles of different liquids were compared considering their theoretical background, and multicomponent approaches were applied to polymers and surface-treated polymers containing only C, H, O and N. These methods involve different approximations and give different results regarding surface energy, supporting the view that none of them provides absolute values having the accuracy expected for thermodynamic parameters and their use in computing quantities such as the work of adhesion and interfacial energy. Nevertheless they ranked the surface polarity in the same order, which was also the order simply provided by the water contact angle. A multivariate analysis of works of adhesion deduced from measured contact angles for a set of liquids on different solids may be a relevant alternative to deterministic approaches for ranking surfaces and deciphering the factors which govern their behavior. As the acid-base interactions are involved in surface energy and are due to specific chemical functions, the relationship between the water contact angle and the surface composition was examined, using surface-oxidized polypropylene as a model case. The cosine of the water contact angle was found to correlate with the “surface” oxygen concentration determined by XPS. However, this correlation may be misleading. Actually the surfaces showing the highest oxidation and the highest apparent hydrophilicity should be regarded as covered with a layer of adsorbed compounds, rather than belonging to a defined solid phase.

A review is presented on the surface preparation of polymers and composites using atmospheric pressure plasmas. This is a promising technique for replacing traditional methods of surface preparation by abrasion. With sufficient exposure to the plasma afterglow, polymer and composite surfaces are fully activated such that when bonded and cured with epoxy adhesives, they undergo 100% cohesive failure in the adhesive. Depending on the material, the lap shear strength and crack delamination resistance (GIC) can be increased several fold over that achieved by either solvent wiping or abrasion. In some cases, a plasma-responsive layer must be incorporated into the top resin layer of the composite to achieve maximum bond strength to the adhesive. Adhesion does not correlate well with water contact angle or surface roughness. Instead it correlates with the fraction of the polymer surface sites that are oxidized and converted into active functional groups, as determined by x-ray photoelectron spectroscopy and infrared spectroscopy.

Knowledge of the surface free energy of solids is important to understanding a number of processes involving wetting and adhesion to solid surfaces. The measurement of surface free energy has been a subject of active interest for at least 50 years. Despite the importance of the problem to a variety of industries a universally accepted method or set of methods for determination of solid surface free energies has not been agreed upon. In this review article various methods that have been used for the calculation of surface free energies are discussed. The limitations and concerns for employment of each of these methods are furthermore highlighted. Of principal concern is the use of contact angles that meet the requirements to be Young’s contact angles and the mixing of quantities obtained by contact angle measurements with those obtained by IGC, as surface free energies obtained by IGC tend to be larger than those obtained from contact angle measurements. Calculated values from IGC data are presumably larger than those from contact angle data as IGC data are often collected at very low surface coverages.

This chapter highlights a variety of techniques that are commonly used to measure contact angles, including the conventional telescope-goniometer method, the Wilhelmy balance method, and the more recently developed drop-shape analysis methods. The various applications and limitations of these techniques are described. Notably, studies of ultrasmall droplets on solid surfaces allow wetting theories to be tested down to the nanometer scale, bringing new insight to contact angle phenomena and wetting behavior.

The sessile drop contact angle measurement is a useful and reliable method for surface energy determination and cleanliness verification. A review of the available methods, commercial instruments, patents, and literature describing the state of the art in contact angle measurement is followed by a description of contact angle measurement techniques that have been modified for use on large surfaces. The negative effects of these changes on accuracy and precision are discussed, and remedies are proposed including the use of standard reference objects that mimic the size and shape of sessile drops. The combination of these validation tools and the modified contact angle measuring techniques fills a need for robust, production-line capable cleanliness verification methods.

Contact angle measurement has wide application in studying the wettability of a surface. This paper presents a contact angle measurement system developed using simple apparatus. The system consists of a bespoke measurement software, USB microscope, motorized linear position slider and a sample holder with back lighting system. The advantages of this system include user friendly, compact size, allow manual and automatic measurements and cost effective. This system is established with the contact angle and surface tension measurement experiment which is based on Fox-Zisman theory. Different probe liquids were suggested and the critical surface tension of polydimethylsiloxane (PDMS) and polyimide were determined using both the software and the hardware system developed.

Nylon 6 electrospun nanofibers were deposited on plasma-pretreated woven fabric substrates with the objective of improving adhesion between them. The prepared samples were evaluated for adhesion strength and durability of nanofiber mats by carrying out peel strength, flex resistance, and abrasion resistance tests. The test results showed significant improvement in the adhesion of nanofiber mats on woven fabric substrates due to atmospheric plasma pretreatment. The samples also exhibited good flex and abrasion resistance characteristics. X-ray photoelectron spectroscopy and water contact angle analyses indicate that plasma pretreatment introduces radicals, increases the oxygen content on the substrate surface, and leads to formation of active chemical sites that may be responsible for enhanced cross-linking between the substrate fabric and the electrospun nanofibers, which in turn increases the adhesion properties. The work demonstrates that the plasma treatment of the substrate fabric prior to deposition of electrospun nanofiber mats is a promising method to prepare durable functional materials.

This paper describes our investigation of the effects of forced air plasma treatment on polypropylene and polyethylene. The morphology of the treated surfaces has been carefully examined using a variety of tools including optical profiling. The complex surface morphology was observed to change with increasing treatment and varying intensity of the treatment over the surface. Optimum treatment conditions have been deduced using surface energy determinations and can be compared with the morphological changes. Determinations of surface energy, both the polar and non-polar components, have been made after exposure to varying moisture conditions for varying times. Different results are obtained for different environments and from different materials. These results demonstrate that forced air plasma treatment is a highly effective means of increasing the surface energy of polymers, which can be long-lasting, provided the treated surfaces are kept in dry conditions.

Surface charge decay on thick flat samples of high temperature vulcanized silicone rubber is studied prior and after ac and dc corona pre-treatments. It is found that the charge decay rate on the material exposed to ac corona becomes much higher and sensitive to moisture content in the surrounding air. These features are associated with an increased surface conductivity and formation of a silica-like layer on the polymeric surface, both resulting from ac corona treatment. In contrast, characteristics of the charge decay on the material exposed to dc corona are found to be similar to that measured on untreated samples.

This paper investigates the surface modification of Parylene-C thin films under various oxygen plasma treatment conditions, such as power intensity (50:400 W) and exposure time (1:20 min). The extent of hydrophilicity was investigated through contact angle measurements, and correlations between treatment parameters, film thickness, restoration of hydrophobicity and etching rates were experimentally established. We also demonstrate the selective modification of Parylene-C films, facilitating distinct hydrophilic and hydrophobic areas with μm-resolution that can be exploited in self-alignment applications.

In this work, the acrylic acid (AAc)-corona discharge was carried out on biaxially oriented polypropylene (BOPP) films by introducing AAc vapor into the corona region of a normal corona treater. Three different corona energies of 15.3, 38.2 and 76.4 kJ/m² were studied. Surface properties of treated films were compared with those of air-corona treated films prepared with the same corona energies. The change in chemical composition on the film surface was characterized by curve-fitting of the ATR-FTIR spectra. The wettability of treated films, before and after aging in different environments, was observed by water contact angle and surface free energy. The surface morphology of air- and AAc-corona treated films was investigated using SEM and AFM techniques. Adhesion of the treated films to some other substrate was determined with the T-peeling test. It was found that the hydrophilicity of all treated films increased with increasing corona energy. AAc-corona treated films showed greater wettability than did the air-corona treated films and could retain the surface hydrophilicity for more than 90 days of aging under ambient conditions. The surface morphology of BOPP films changed after corona treatment into a globular structure. The AAc-corona treated films showed rougher surfaces due to surface oxidation and polymer formation, whereas, air-corona treated films displayed a similar structure but of smaller size due to the formation of low molecular weight oxidized materials (LMWOM) arising from the degradation of BOPP films. AAc-corona treated films showed greater peel strength than did the air-corona treated films.