The hydrophobic recovery of polydimethylsiloxane elastomers was studied after exposure to partial electrical discharge. Silicone elastomers that were thoroughly extracted of free oligomeric impurities as well as those deliberately contaminated with low molecular weight (LMW) silicone fluids were used for these studies. Contact angle and X-ray photoelectron spectroscopy revealed that the recovery rates of the oxidized extracted samples are strongly influenced by the applied voltage, humidity, and aging condition. The recovery rates increase considerably as the applied voltage and the humidity during discharge increase. Remarkably, the oxidized samples stored under high vacuum (10⁻⁷ Torr) exhibit lower recovery rates than those aged in air. Free silicone fluid, when added to the elastomer, affects the recovery rate as well; however, significant recovery is seen even without any added fluid. These results imply that the LMW species that are formed in situ during electrical discharge are sufficient to cause the hydrophobic recovery of oxidized PDMS elastomers.

Two different experimental approaches based on ellipsometry and zeta potential measurements have been employed to determine the dispersion and polar surface free energy components of glass. From ellipsometry the adsorption isotherms of n-octane and water have been determined, yielding values for the film pressures of n-octane and water and the dispersion and polar surface free energy components of glass. Similarly, zeta potentials in water of glass covered with various amounts of n-octane and n-hexanol have been determined. Next, the film pressures of these liquids and surface free energy components of glass were also calculated. Thus determined values are 32 and 80 mJ/m² (from ellipsometry) and 25 and 80 mJ/m² (from zeta potentials) for the dispersion and polar components, respectively. The correspondence between the surface free energies obtained by two completely independent methods gives confidence to the approaches employed.

A technique has been developed for rapid and extremely accurate measurements of contract angles formed by liquids on the surface of small-diameter filaments. The light beam reflection technique first de- scribed by Langmuir and Sehaeffer (1) and recently by Fort and Patterson (2) for liquid drops on flat plates has been refined for use with filaments and microscope equipment.

A new method for the measurement of apparent contact angles at the global energy minimum on real surfaces has been developed. The method consists of vibrating the surface, taking top-view pictures of the drop, monitoring the drop roundness, and calculating the contact angle from the drop diameter and weight. The use of the new method has been demonstrated for various rough surfaces, all having the same surface chemistry. In order to establish the optimal vibration conditions, the proper ranges for the system parameters (i.e., drop volume, vibration time, frequency of vibration, and amplitude of vibration) were determined. The reliability of the method has been demonstrated by the fact that the ideal contact angles of all surfaces, as calculated from the Wenzel equation using the measured apparent contact angles, came out to be practically identical. This ideal contact angle has been compared with three methods of calculation from values of advancing and receding contact angles.

Sessile-drop and captive-bubble techniques were used for contact angle measurements. The advancing and receding contact angles were measured for water and ethylene glycol at self-assembled monolayer surfaces of dodecanethiol, for water at methylated quartz surfaces, and for water at roughened polyethylene and polytetrafluoroethylene surfaces. It was found that for each technique used, sessile-drop and captive-bubble, different advancing contact angles and different receding contact angles were frequently obtained for nonideal systems with rough and heterogeneous solid surfaces. The disagreement between contact angles, as measured with the two different techniques, increased with increasing imperfection of the solid surface. Also, it was observed that solid surface roughness and heterogeneity affected a variation of the advancing and receding contact angles with drop (bubble) size. No contact angle change with respect to drop (bubble) size (in the range 1–7 mm base diameter) was observed when smooth and homogeneous solid surfaces were well prepared. It is possible that metastable states, which are responsible for the contact angle hysteresis, also affect the contact angle/drop (bubble) size relationship. These three-phase systems with sessile drop and captive bubble at heterogeneous and/or rough solid surfaces are complex because solid surface heterogeneity and roughness cause contortions in the shape of the three-phase contact line and the drop (bubble) surface in the vicinity of the three-phase contact line. These contortions may affect a variation of the internal free energy of the liquid drop (gas bubble). It is shown that a slight variation in the advancing contact angle value over a few millimeters change in drop (bubble) diameter does not guarantee a high-quality surface state. Measurements of the receding contact angles provide more information on the quality of the solid surface and they should always be included with the measurements of advancing contact angles.

The acid-base approach to the calculation of solid surface free energy and liquid-liquid interfacial tensions is a practical example of application of correlation analysis, and thus it is an approximate approach. In these limits, and provided that wide and well-obtained sets of contact angles or interfacial tension data are used for their computation, surface tension components can be considered as material properties. Although their numerical value depends on the characteristics of the chosen reference material, their chemical meaning is independent on the selected scale. Contact angles contain accessible information about intermolecular forces; using surface tension component (STC) acid-base theory, one can extract this information only making very careful use of the mathematical apparatus of correlation analysis. The specific mathematical methods used to obtain these results are illustrated by using as an example a base of data obtained by the supporters of the equation-of-state theory (EQS). The achievements are appreciably good and the agreement between STC and EQS is discussed.

This paper follows the “defense” of the Good-van Oss-Chaudhury (GvOC) acid-base approach made in Part I and carries out a detailed analysis of the Zisman critical surface energy and, mainly, of the Neumann equation-of-state (EQS) theory. The analysis is made on both a “practical” and a theoretical basis, trying to highlight the acceptable fitting results of axisymmetric drop shape analysis (ADSA) methods and their independence of the assumed thermodynamic foundations of EQS. Some new and original criticisms of the EQS approach are raised and it is shown that other purely semiempirical models, represented by different fitting equations with the same number of parameters, can represent the data measured by ADSA method with the same goodness as EQS. The equation of state appears as one of many semiempirical approaches for the evaluation of surface free energy of solids. Independent of the previous analysis, the criteria used in ADSA measurements are evaluated and some comments made on them.

Hypothesis: Both the surface free energy (γ) and solubility (δ) parameters of substances are related to their cohesive energies which are decided by intermolecular interactions, and there should be some intrinsic relationships between the two parameters. Understanding of the γ-δ correlations is of great fundamental and practical importance. Several empirical γ-δ equations have been proposed so far, but their application to solids is limited. This is because the molar volume (V~) as a parameter exists in these equations while the V~ of solids is commonly hard to be obtained. Hence, the development of γ-δ equations without the parameter V~ is essential for solids.

Method: The γ and δ data of 21 solids including polymers and layered solid materials were chosen, and possible γ-δ relationships were systematically explored using the parameter data of solids by a trial and error fitting method.

Finding: Six γ-δ equations without the parameter V~ are proposed. The γ parameters include total (γ_t), dispersive (γ_d), and polar (γ_p) ones, and the δ parameters include the Hildebrand parameter (δ_t) and the Hansen dispersive (δ_d), polar (δ_p), and hydrogen-bonding (δ_h) ones. Interestingly, the so-obtained V~-free γ-δ equations are also valid for most liquids including nonpolar and polar ones. These γ-δ equations can provide a way to estimate non-measurable parameters from measurable parameters for solid materials, which is beneficial to the application of the characteristic parameters (γ and δ) for solid material engineering.

The validity and the accuracy of both the Owens and Wendt and the Lifshitz–van der Waals/acid–base (LW/AB) methods for the determination of surface tensions of solids have been examined for a wide variety of situations. In each case, the allowed range of contact angles that result in positive values of all the square roots of the surface tension components of the solid has first been determined. Then the maximum relative errors in the surface tensions of solids that result from errors in contact angle measurements have been calculated within the allowed range. For both methods, it has been found that the maximum relative errors are minimal if one of the liquids is apolar. In the case of the LW/AB method, minimal errors are obtained if, in addition, the other two liquids are monopolar with different polarities. However, the more similar are the properties of the liquids, the narrower is the allowed range, and the larger are the maximum relative errors.

Contact angle data for sets of probe liquids allow the determination of components of solid surface energies which in turn can be used to calculate the work of adhesion of other materials to the solid surface. There is much debate currently about the correct choice of the acid–base components for the probe liquids. For many systems, the strength of adhesion measured independently correlates well with the calculated work of adhesion. Recent trends in this area include adhesion under water and the adhesion of bacterial and other cells to immersed solids.

The dependence of cell or bacteria adhesion and growth on the polarity of a polymer substrate, as controlled by the composition of a HEMA-EMA copolymer, has been studied by contact angle measurements. These have been analyzed by the acid/base hydrogen bonding methodology of van Oss, et al. It was found that adhesion and growth of mouse 3T3 cells occurred on surfaces for which the acidic parameter, γ^⊕_S, was negligibly small. This was the case above 50% EMA, for which γ^p was zero, and both attachment and growth occurred. The γ^⊕ parameter was appreciable, but approximately constant, independent of composition of the copolymer. The acid/base theory thus supplants the simple polar-nonpolar (γ^pandγ^d) hypothesisin regard to cell adhesion. A new 3-dimensional representation of hydrophilic/hydrophobic behavior is suggested, to implement the acid/base description.

Plasma treatment of polymers encompasses a variety of plasma technologies and polymeric materials for a wide range of applications and dates back to at least the 1960s. In this article we provide a brief review of the United States patent literature on plasma surface modification technologies and a brief review of the scientific literature on investigations of the effects of plasma treatment, the nature of the plasma environment, and the mechanisms that drive the plasma–surface interaction. We then discuss low‐radio‐frequency capacitively coupled nitrogen plasmas and their characteristics, suggesting that they provide significant plasma densities and populations of reactive species for effective plasma treatments on a variety of materials, particularly when placing the sample surface in the cathode sheath region. We further discuss surface chemical characterization of treated polymers, including some results on polyesters treated in capacitively coupled nitrogen plasmas driven at 40 kHz. Finally, we connect plasma characterization with surface chemical analysis by applying a surface sites model to nitrogen uptake of poly(ethylene terephthalate) (PET) and poly(ethylene naphthalate) (PEN) treated in a 40 kHz nitrogen plasma. This example serves to suggest an interesting practical approach to comparisons of plasma treatments. In addition, it suggests an approach to defining the investigations required to conclusively identify the underlying treatment mechanisms.

By measuring contact angles with water, glycerol and formamide on a number of polar surfaces, an estimate could be made of the electron-acceptor (γ⁺ ) and the electron-donor (γ⁻ ) parameters of glycerol (G) and formamide (F), relative to the parameters of. water (W), for which a reference value of γ⁺ _W = γ⁻ _W = 25.5 mJ/m² has been assumed. The values thus found are: γ⁺ _G ≈ 3.92 mJ/m² (which yields γ⁻ _G ≈ 57.4 mJ/m²) and γ⁺ _F ≈2.28 mJ/m² (which yields γ⁻ _F ≈ 39.6 mJ/m²).

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 surface of polyimide (PI) films before/after plasma surface treatment using a remote-type modified dielectric barrier discharge was investigated to improve the adhesion between the PI substrate and the metal thin film. Among the plasma treatments of the PI substrate surface using various gas mixtures, the surface treated with the N-2/He/SF6/O-2 plasma showed the lowest contact angle value due to the high C=O bondings formed on the PI surface, while that treated with N-2/He/SF6 showed the highest contact angle value due to the high C-F-x chemical bondings on the PI surface. Specifically, when the O-2 gas flow was varied from 0 to 2.0 slm in the N-2(40 slm)/He(1 slm)/SF6(1.2 slm)/O-2 (x slm) gas composition, the lowest contact angle value of about 9.3 degrees was obtained at an O-2 gas flow of 0.9 slm. And it was due to the high content of oxygen radicals in the plasma, which leads to the formation of the highest C=O bondings on the PI surface. When the interfacial adhesion strength between the Ag film and PI substrate was measured after the treatment with N-2(40 slm)/He(1 slm)/SF6(1.2 slm)/O-2(0.9 slm) followed by the deposition of Ag, a peel strength of 111 gf/mm was observed, which is close to the adhesion strength between a metal and the PI treated by a low pressure plasma.

In a number of automotive applications of polypropylene (PP) good paint adhesion is essential. For industrial applications, the initially poor adhesion properties of PP compounds are often improved by flame treatment, resulting in good paint adhesion on the PP parts. For control purposes, intensive and time consuming paint tests are required. To relate adhesion behaviour with the parameters used in the flame treatment modification, several methods are applied such as simple surface tension tests with inks (wetting tests), contact angle measurements and standard XPS(ESCA) measurements. Unfortunately a good correlation is rarely obtained between these tests and the desired adhesion behaviour under rigid test conditions. Good wetting, for example, is necessary, but is no guarantee for good adhesion. In this paper results are presented on the characterisation of flame treated PP compounds by XPS, as well as the predictive information obtained from the XPS study concerning the paint adhesion behaviour of the modified PP surfaces.

Electret charging methods on the basis of gas discharge in air offer many advantages, including a very simple arrangement, no direct contact to the electret surface, and no restrictions on charging temperature. For discharge in air two arrangements are in use: (1)discharge in a parallel air gap and (2) corona discharge. A comparison of both methods, showing significant similarities, is given.

Starting with investigations of charging in a parallel air gap, the practical knowledge is applied to the more complex corona charging. The characteristics of equilibrum electret voltage and its dependence on applied voltage are measured and interpreted theoretically. The influence of deviations in gap spacing on electret voltage is discussed. Electrical breakdowns of the electret foil affect the results. Therefore the role of breakdown is investigated in more detail.

In this paper, the corona charge stability in electret polytetrafluoroethylene Teflon film is investigated after the film is treated by radio-frequency plasma. It is found that the charge stability depends strongly on the plasma composition and the film exposure to plasma, especially for negative charge. When a non-metalized film is held horizontally on the ground holder, i.e. with one side facing the plasma, oxygen plasma treatment achieves a superior negative charge retention on the front side, while its rear side retention decreases significantly. Under the same conditions in oxygen/helium and helium plasmas, the charge stability also increases but the potentials are lower compared with pure oxygen plasma after annealing. In a hydrogen plasma, the stability only slightly enhances. If the film is held vertically on the holder, so that both sides contact the plasma, the surface potential on both sides decreases dramatically and arrives at a few volts within 2 min, after annealing at 170°C. By Fourier transform infrared (FTIR) and X-ray photoelectron spectroscopy (XPS), we conclude that oxidation formed on the front side is responsible for increasing the stability of negative charge. The positive carriers, generated in the film during plasma treatment, recombine with charge from corona charging and causes the surface potential in the rear side of the horizontal non-metalized film, or in both sides of the vertical non-metalized film, to discharge after heating.

Currents during corona charging and surface potential decay after corona charging have been studied on polymeric films. As has been reported before, surface potential is a useful tool for investigating the electrical properties of an insulating material, making it possible to discriminate charge injection from polarization processes, when data are correctly analysed, and it has also been shown that, on thin polymeric films, slow polarization processes leading to heterocharge formation dominate at low fields, while charge injection occurs above a given field threshold. We present here a combined study of the surface potential after charge deposit and current flowing on the back electrode during the corona charge; we show that current measurements during the charge confirm the interpretation of potential measurements after corona charge. The outbreak of “hollows” in the potential distribution on the surface is clearly linked to the predominance of injected charge on the polarization charge. However, even at high fields, polarization phenomena will dominate again a given time after corona discharge stopping.

We examined the influence of the geometric parameters of the system on the modification power as determined by the contact angle on the surface of the treated low-density polyethylene (LDPE). We have found that (1) with a constant electric energy to generate a corona discharge, the modification power decreases as the distance from the center of surface (the point on the film immediately below the point electrode) increases and that the corona discharge in a point-to-grid system can modify the film surface over a wider area than in a point-to-LDPE system without grid; (2) with a constant discharge current, the modification power on the center of surface decreases when the point-to-grid gap in negative corona treatment increases, but increases in positive corona treatment; (3) the modification power compared to the electric energy used to generate a corona discharge (the yield) is inversely proportional to the point-to-grid gap. However, in a positive corona discharge, the yield did not reach zero when the point-to-grid gap was extrapolated to infinity, possibly because the streamer reduces the effective point-to-grid gap and produces neutral activated species along the streamer; and (4) in a negative corona, the modification power as measured by the temperature increases at the plain electrode (anode) and varies with the energy dissipated by neutral activated species.

Surface potential decay after negative corona charge deposition has been studied for polypropylene films 50μm thick, over a wide range of decay times and charging voltage (500–2800V). At low initial potential (500–800V), the surface potentials were stable and did not decay. At high initial potential (1200–2800V), the surface potential decay has been clearly observed with differences in the decay rate. The observed decay behavior has been computer simulated to elucidate the transport mechanism in polypropylene films. A good agreement between measured and calculated decay curves was obtained with a model in which charges are transported by hopping of injected carriers between localized trapping centers. The model is characterized by parameters such as the free carrier mobility, the mean free time of carrier between traps and the mean capture time in trap. The transport parameters have been determined by a fitting procedure.

A viscous-liquid drop spreads on a smooth horizontal surface, which is uniformly heated or cooled. Lubrication theory is used to study thin drops subject to capillary, thermocapillary and gravity forces, and a variety of contact-angle-versus-speed conditions. It is found for isothermal drops that gravity is very important at large times and determines the power law for unlimited spreading. Predictions compare well with the experimental data on isothermal spreading for both two-dimensional and axisymmetric configurations. It is found that heating (cooling) retards (augments) the spreading process by creating flows that counteract (reinforce) those associated with isothermal spreading. For zero advancing contact angle, heating will prevent the drop from spreading to infinity. Thus, the heat transfer serves as a sensitive control on the spreading.

Macroscopic wetting behavior is investigated theoretically from a thermodynamic viewpoint. The axisymmetric liquid meniscus formed under a conical solid surface is chosen as the subject of the theoretical analysis. Using the meniscus configuration obtained by the Laplace equation, the total free energy of the system is calculated. In the case of the half vertical angle of the cone φ = 90 deg (horizontal plate), the system shows thermodynamic instability when the meniscus attaches to the solid surface at the contact angle. This result, unlike the conventional view, agrees well with the practical wetting behavior observed in this study. On the other hand, when 0 deg < φ < 90 deg, the system shows thermodynamic stability at the contact angle. However, when the solid cone is held at a position higher than the critical height from a stationary liquid surface, the system becomes unstable. It is possible to measure the contact angle easily using this unstable phenomenon.

By fluorinating the surface of a polymer, the hydrogen bonding energy of a polar surface has been defined. The contact angles for three solvent classes; nonpolar, polar and hydrogen bonding, on a polar surface results in the separation of dispersion, polar, and hydrogen bonding energies. Both critical surface tension plots and theoretical calculations were used to define the surface energy for fluorinated polyethylene.

In adhesion applications, the rapid ageing of corona discharge pretreated surfaces is a well-known problem. Very often the corona treatment has to be renewed just before the application. Oxyfluorination process presents an interesting alternative to the corona discharge treatment. In this work, the outstanding ageing properties of the oxyfluorinated polyolefin surfaces are described on the basis of acid–base surface characteristics.

Polypropylene (PP) was exposed to various fluorine-gas mixtures and the fluorinated PP surfaces were characterised by means of X-ray photoelectron spectroscopy, Rutherford backscattering, attenuated total reflectance infrared spectroscopy, solid–liquid contact angles and thermogravimetric analysis. The surface wettability and surface tensions of PP, as functions of fluorination and oxyfluorination times, were also determined and discussed.

Surface fluorination is an interesting method of rendering surfaces more acceptable to adhesion. The adhesive properties of fluorinated and oxyfluorinated propylene surfaces, using epoxy, polyester and epoxy vinyl ester adhesives, are described. Lap shear tests were carried out to determine the strength of the adhesive joints.

In this work a DC plasma reactor was used for deposition of plasma polymerized coating from hexamethyldisiloxane-Ar (35/65%) mixture on polypropylene films. Surface energy parameter have been calculated using Owens-Wendt approaches with the sessile drop method are used to obtain the dispersive γ^D and polar γ^P component of surface free energy. The surface morphology of samples were investigated using scanning electron microscope. Also the chemical properties and wetability of prepared samples were tested using Fourier transform infrared spectroscopy and contact angle measurement, respectively.

Surface tension is probably one of the most difficult phenomena to measure. Although a great deal of ingenuity has been spent for almost a century in devising accurate techniques, the figures obtained deviate more from each other for the same substance, according to different authors, than any other constant characterizing the substance. It is well ,known that the two classes of methods of measurement, the static and the dynamic give entirely different results when applied to the same liquid.

The effects of corona discharge treatment (CDT) on ink drop impact and spreading on a coated polypropylene film substrate were investigated. Substrate surface energies were determined from static contact angles with water and ethylene glycol. The polar component increased with increasing CDT. Drops 39 um in diameter of an acrylate-based UV-curable ink were printed on to the substrate, and the spreading process studied by high-speed photography. No changes occurred during the initial stages, but the wetting phase was shorter for higher doses of CDT. Drops spread further on substrates with low doses of CDT than with higher doses. White light interferometry was used to determine the final heights of drops after UV-curing. The height was significantly affected by CDT, with minimum height at low doses. The relationship was investigated between the static contact angle for large sessile drops and the equilibrium contact angle for printed drops after spreading. Contact angle measurements with millimeter-sized sessile drops of ink provide a reliable method to determine the effects of corona treatment on wetting by ink jet printed drops.

Atmospheric low-temperature plasma was produced using dielectric barrier discharge (DBD) plate-type plasma reactor and high frequency of 13.56 Hz. The surfaces of polyimide films for insulating and packaging materials were treated by the atmospheric low-temperature plasma. The contact angle of 67 was observed before the plasma treatment. The contact angle was decreased with deceasing the velocity of plasma treatment. In case of oxygen content of 0.2 %, electrode gap of 2 mm, the velocity of plasma treatment of 20 mm/sec, and input power of 400 W, the minimum contact angle of 13 was observed. The chemical characteristics of polyimide film after the plama treatment were investigated using X-ray photoelectron spectroscopy (XPS), and new carboxyl group bond was observed. The surfaces of polyimide films were changed into hydrophilic by the atmospheric low-temperature plasma. The polyimide films having hydrophilic surface will be very useful as a packaging and insulating materials in electronic devices.

The modification of polymer surfaces by gas plasma treatment is reviewed. The two regimes of major interest are radio-frequency at low pressure (about 1 torr) and corona discharge at atmospheric pressure. The reactions produced by plasmas at polymer surfaces are due to both radiation and chemically active species created by electron bombardment. The major changes produced are in wettability, molecular weight, chemical composition, and surface morphology. The mechanisms of plasma polymerization and the properties of polymers produced by this technique are described. Finally, a brief outline is given of the industrial applications of plasma techniques.

The surface structures of low-density polyethylene (LDPE) film exposed to plasma or γ-ray in air were characterized by ESCA, IR, and EMS. The formation of trans C[dbnd]C bond on the LDPE film surface was observed by the exposure to ac air plasma (2 × 10⁻² torr, 19 W plasma power). Large amounts of O and N atoms as an amide structure were incorporated into the polymer surface by the plasma treatment. These plasma reactions occurred mainly in the amorphous region, and the polymer surface became rough enough to have a microdomain structure upon increasing the plasma treatment time up to 3 h. γ-Irradiation of LDPE in air only brought about O-atom incorporation as ketone and ether linkages. The polymer surface did not undergo etching under γ-irradiation as it did in plasma treatment.

The chemical species created in a low-pressure electrical discharge in oxygen attack the polymer at the surface, converting it to gaseous products. This process is interesting because: 1) the chemical changes on the resulting surface facilitate the formation of strong adhesive bonds and provide sites for the chemical attachment of other molecules, 2) significant morphological features lying below the surface may be revealed, 3) polymer can be cleanly removed from surfaces which are resistant to oxidation, and 4) dielectric breakdown frequently is preceded by the attack on the polymer of chemical species created in a corona discharge. Atomic oxygen is an important chemical species created in such a discharge. It reacts with organic substances rapidly at room temperature, but lives long enough in the low-pressure gas that it can be separated from many other reactive species created in the discharge. “Titration” with NO₂ provides a straightforward chemiluminescent means for determining the concentration of atomic oxygen to which the sample is exposed. This paper characterizes the attack of atomic oxygen, perhaps in the presence of long lived but less reactive species such as excited O₂molecules, on polymer surfaces, using electron microscopic observations of known morphological features of polyethylene to observe the changes produced by atomic oxygen. Lamellar polyethylene crystals were attacked both at the edges and the fold surfaces. Layers many microns thick were removed from spherulitic samples and replicas obtained from the surfaces thus exposed. Thick samples were thinned to the point at which they were transparent to an electron beam and interior morphological features were directly observed.

Interfacial and surface tensions of polymers are important in the technology of plastics, coatings, textiles, films, and adhesives through their roles in the processes of wetting, adsorption, and adhesion. Because of experimental difficulty due to high viscosity, however, reliable measurements of these quantities were not reported until 1965 for surface tensions [l, 2] and 1969 for interfacial tensions [3, 4]. A body of scattered data has been accumulated in the literature. This review will evaluate, compile, and interpret these results.

The effect of nonpolymer-forming plasma (e.g., plasma of hydrogen, helium, argon, nitrogen) can be viewed as the following two reactions: 1) reaction of active species with polymer, and 2) formation of free radicals in polymer which is mainly due to the UV emitted by the plasma. The incorporation of nitrogen into the polymer surface by N₂ plasma and the surface oxidation by O₂ plasma are typical examples of the first effect. The latter effect generally leads to incorporation of oxygen in the form of carbonyl and hydroxyl and to some degree of cross-linking depending on the type of substrate; however, the degradation of polymer at the surface manifested by weight loss occurs in nearly all cases when polymers are exposed to plasma for a prolonged period of time. The effects of polymer-forming plasma is predominated by the deposition of polymer (plasma polymer); however, with some plasma-susceptible polymer substrates the effect of UV emission from polymer-forming plasma cannot be neglected. The mechanism of polymer formation can be explained by the stepwise reaction of active species and/or of an active specie with a molecule, and the chain addition polymerization of some organic compounds (e.g., vinyl monomers) is not the main route of polymer formation.

Plasma polymers contain appreciable amount of trapped free radicals; however, the concentration is highly dependent on the chemical structure of the monomer. In plasma polymerization, 1) triple bond and/or aromatic structure, 2) double bond and/or cyclic structure, and 3) saturated structure are three major functions which determine the rate of polymer formation and the properties of plasma polymers. The changes of some properties of plasma polymers with time are directly related to the concentration of trapped free radicals in plasma polymers. The amount of trapped free radicals in a plasma polymer is also influenced by the conditions of discharge; however, the UV irradiation from the polymer-forming plasma is not the main cause of these free radicals. Excess amount of free radicals are trapped during the process of polymer formation (rather than forming free radicals in the deposited polymer by UV irradiation). The properties of a plasma polymer is generally different from what one might expect from the chemical structure of the monomer, due to the fragmentation of atoms and/or functions during the polymerization process. This is another important factor to be considered for the modification of polymer surfaces by plasma polymerization.

A technique is described for performing temperature scanning measurements of the surface tension of polymer solutions. Measurements on solutions of a high molecular weight and a low molecular weight monodisperse polystyrene in tetralin, decalin, and n-hexadecane are reported. Whereas previous investigations of other physical properties of polystyrene solutions had revealed only one anomaly, at about 50°C in some cases and at about 70–80°C in others, the curves presented here show two anomalies, near 45°C and 70°C, respectively. These anomalies are tentatively attributed to conformational changes of the polymer chains.

Surface tension data can be used for estimating the solubility of polymers in liquids. By determining the apolar and the polar components of the surface tension of polymers and of solvents, the attractive free energy, δG₁₂₁, of a polymer (1) in a given solvent (2) can be established. By also taking into account the contactable surface area of two polymer molecules, immersed in a liquid, δG₁₂₁ can be expressed in units of kT. Solubility then is favored when -1.5 kT < δG₁₂₁ < 0 for apolar systems, and when -1.5 kT < δG₁₂₁ for polar systems. In polar solvents, hydrogen bonding can often increase δG₁₂₁ from <-1.5 kT to > + 1.5 kT. Positive values are frequently attained and this strongly shifts the behavior from insolubility to solubility. A number of proteins exemplify this behavior.