New approaches for electroless plating of nonconductive polymers or polymer-based materials are described. In this work, polyimide substrates were surface-functionalized (i) in nitrogenated (ammonia at reduced pressure) and oxygenated (air at atmospheric pressure) atmospheres under assistance of vacuum-ultraviolet (VUV) irradiation (use of a xenon silent discharge excimer source) or (ii) directly in air at atmospheric pressure using a dielectric-barrier discharge (DBD) device. After functionalization, the substrates were “activated” by dipping in a dilute acidic PdCl₂ solution or by spin-coating of a thin metal-organic film (from a solution of palladium acetate (PdAc) in chloroform). The catalytic activity of the so-deposited palladium species toward the electroless deposition of nickel was studied before and after a VUV post-irradiation (in air at atmospheric or reduced pressure) with a view to understanding better the role of the reducer (sodium hypophosphite) within the electroless bath.

This work confirms the specific interest of grafting nitrogenated functionalities onto polymer surfaces for attaching covalently the palladium-based catalyst (in particular in the case of the PdCl₂ route), forming thus strong Pd - N - C bonds at the metal/polymer interface. This results from the strong chemical affinity of palladium toward nitrogen. On the other hand, when oxygenated functionalities are surface-grafted, the conventional two-step procedure using SnCl₂ and PdCl₂ solutions can be proposed due to the strong chemical affinity of tin toward oxygen. The Ni deposits obtained under these different conditions pass the standard Scotch^®-tape test and, therefore, exhibit a good practical adhesion. For this same purpose, it is interesting to note that the DBD treatment operating in air at atmospheric pressure causes an increase of the surface roughness and, therefore, an improvement in adhesion of metallic films when their initiation is catalyzed through the PdAc route. In addition, this work demonstrates that extensive research still has to be performed to understand and improve the Ni/polymer adhesion when the PdAc route associated with a VUV irradiation is considered.

The surface of the bio-material polymethyl methacrylate (PMMA) was treated with CO₂, Nd:YAG, excimer and high power diode laser (HPDL) radiation. The laser radiation was found to effect varying degrees of change to the wettability characteristics of the material depending upon the laser used. It was observed that interaction with CO₂, Nd:YAG and HPDL effected very little change to wettability characteristics of the PMMA. In contrast, interaction of the PMMA with excimer laser radiation resulted an increase in a marked improvement in the wettability characteristics. After excimer laser treatment the surface O₂ content was found to have increased and the material was seen to be more polar in nature. The work has shown that the wettability characteristics of the PMMA could be controlled and/or modified with laser surface treatment. However, a wavelength dependence of the change of the wetting properties could not be deduced from the findings of this work.

Recently, much attention has been paid to gas discharges producing nonthermal plasma because of many potential benefits in industrial applications. Historically, past work focused on Dielectric Barrier (silent) Discharges (DBD) and pulse-periodical corona discharges. Recently, a number of new different discharge techniques succeeded in producing stable gas discharge at atmospheric pressure. Among these are repetitively pulsed glow discharge; continuous glow discharge in a gas flow; hollow-cathode atmospheric pressure discharge; RF and microwave (MW) discharges. Several new variants of the DBD have been demonstrated over a rather wide range of frequencies. All these forms of gas discharge are characterized by a strong nonequilibrium plasma state. We attempt to classify these discharges with respect to their properties, and an overview of possible applications is made. Conditions for the existence of homogenous and filamentary forms of each of the discharge types are discussed.

The objective of this study was to determine the surface free energy components of aqueous-based cellulose ether films and compare these values with those of other cellulose polymers. The surface free energy parameters were calculated from the contact angles of sessile drops of apolar and polar liquids on cellulose ether films cast on glass slides using the Lifshitz–van der Waals/acid–base (LW/AB) approach according to the method of van Oss, Chaudhury and Good. The cellulose ethers studied were hydroxypropyl methylcellulose (HPMC), methylcellulose (MC), hydroxypropyl cellulose (HPC) and hydroxyethyl cellulose (HEC). The total surface free energy of these cellulose ethers ranged from 42 to 50 mJ m−². The contribution of the acid–base (AB) component of surface free energy to the total surface free energy of the polymers ranged from 4 to 12%, which was considerably lower than that of cellulose. The cellulose ethers demonstrated near monopolarity and had dominant electron donor (Lewis-base) character. The overall trend in the values of the thermodynamic terms derived from the surface free energy parameters as indicators of hydrophilicity and hydration were in good agreement with the relative bulk solubility and hydration behavior of the polymers. Independent estimates of the AB character of the polymers from work of adhesion terms calculated from the liquid wetting data agreed with those obtained from the surface free energy parameters. Calculation of the work of adhesion with substrates of varying surface free energy parameters indicated that acid–base interactions made a major contribution to the total work of adhesion between cellulose ethers and bipolar surfaces. Although no direct correlation could be established between the surface free energy parameters and the type of substitution on the cellulose backbone for the cellulose ethers, the values of the terms derived from the LW/AB approach were consistent with those of cellulose and ethylcellulose. The LW/AB approach provides a reasonably consistent method for estimating the surface properties of cellulose ethers and the resulting surface free energy parameters are shown to relate to the interfacial properties of the polymers.

A plasma treatment that renders asymmetric polysulfone membranes permanently hydrophilic is reported. Our modification strategy entails treating these membranes downstream from an inductively coupled rf plasma source. Contact angle measurements confirm that the membranes are completely wettable with water as a result of H₂O plasma treatment. More importantly, the hydrophilic modification is permanent as plasma-treated membranes remain wettable for more than 16 months after plasma treatment. This treatment achieves the desired change in wettability for microporous as well as ultrafiltration polysulfone membranes, illustrating the universality of this method. XPS analysis of treated membranes demonstrates this dramatic change in wettability is a result of chemical changes in the membrane induced by plasma treatment. Moreover, the membrane modification is complete as the plasma penetrates the thickness of the membrane, thereby modifying the entire membrane cross-section.

Scanning force microscopy has been used to characterize the surface structure and properties of poly(ethylene terephthalate) (PET) films. Two types of biaxially oriented film have been studied: one (Melinex O) is free of additives while the other (Mylar D) contains particulate additives at the surface. Contact mode characterization of both materials provide clear images of the polymer surface and (in the case of Mylar D) the additives. Phase images reveal substantial nanoscale morphological detail, including small features thought to be crystallites. To model the adhesive properties of polymer surfaces, mixed self-assembled monolayers containing polar and methyl terminated adsorbates were studied using chemical force microscopy. It was found that the strength of the tip-sample adhesion increased with the fraction of polar terminated adsorbates at the surface when a carboxylic acid terminated tip was employed, while the trend was reversed when a methyl terminated tip was used. Adhesion forces measured for plasma treated PET increased with treatment time, and linearly with the cosine of the water contact angle, illustrating the chemical selectivity of chemical force microscopy. However, friction forces were found to vary in a non-linear fashion, indicating that changes to the polymer surface mechanical properties following treatment were important.

Hydrophilicity of polyethylene modified by electric discharge in the course of aging was investigated. The experiments were carried out with the foils of low-density polyethylene (PE) containing additives as well as with additive-free foils. Antiblocking or sliding agents, antioxidants and antistatic agents were used as additives. The results showed that the absence of additives in PE was responsible for the higher degree of modification of PE foils by corona discharge when compared with the polymer containing additives. The value of surface free energy (SFE) found after 30 days of aging of the modified PE foils was lower than the value recommended for inking the printing foils.

We present our unified Lewis acid–base approach to adhesion and solvation at the liquid-polymer interface. This approach is to complement the original methodologies proposed by Fowkes and by van Oss, Chaudhury and Good (VCG). Intermolecular interactions are primarily dominated by dispersion, d, hydrogen bonding, h, and secondarily affected by orientation, o, and induction, i. Generally, the polarization component, p, represents both i and o interactions. Fowkes suggested that the acid–base component, γ^ab, of the surface tension should consist of both h and p interactions. However, VCG proposed that the acid–base components, γ^ab, result solely from hydrogen bonding, γ^h, that is equivalent to 2(γ⁺ γ⁻)^1/2, where γ⁺ and γ⁻ are the two hydrogen bonding parameters. VCG defined γ^LW as the Lifshitz-van der Waals component consisting of d, o and i contributions, thus, surface tension, γ, equals γ^ab(VCG)+γ^LW. Both Fowkes and VCG assumed that the polar interactions for a liquid on a low energy surface are negligible.

Now, we assume otherwise, and we treat the specific acid-base interaction to be hydrogen bonding. In addition, we also take into account the nonspecific polarization, p, interaction in terms of the equilibrium spreading pressure, π_e, resulting from the adsorption of a liquid vapor on the polymer surface. Thus, our unified approach uses the dispersion component, γ^d, of Fowkes, the hydrogen bonding, h, of VCG and the polarization, p, in terms of π_e. The difference between the initial (theoretical) and equilibrium (experimental) surface tensions is π_e, and others have observed that π_e on some polymers is substantial. The determination of several initial surface tensions of polymers by considering the effect of polarization is discussed.

In the Appendix, we shall illustrate that this polar component, π_e, is equivalent to the LESR polarity-dipolarity parameter, π^e, (represented by the same symbol but in different context) for the solvatochromic treatment. Furthermore, the surface tension components, π^d, γ⁺, γ⁻ and π_e, are now somewhat comparable with the four parameters in the original Taft-Kamlet relationship, δ, α, B, and π^e. Thus, our proposed unified approach may finally help elucidate the long-debated Lewis acid–base theories pertaining to adhesion and solvation of polymers.

Poly(methylmethacrylate) (PMMA), poly(2-hydroxyethyl methacrylate (PHEMA), and poly(2-hydroxypropyl methacrylate) (PHPMA) were modified to improve the wettability by two techniques: plasma and plasma source ion implantation. The modified surfaces were characterized to investigate the dependence of the modification and hydrophobic recovery on the polymer structure. The differences obtained under optimal experiment conditions among the polymers were interpreted in terms of their polymer structures including the glass transition temperature. The surface free energy, calculated from the contact angle measurements, revealed that its polar component was a dominant factor in improving the wettability. The PSII treatment created more functional groups on the surface and extensively modified the polymer layer than the plasma treatment.

Large area atmospheric-pressure plasma jet. A plasma discharge that can be operated at atmospheric pressure and near room temperature using 13.56 MHz rf power is described. Unlike plasma torches, the discharge produces a gas-phase effluent no hotter than 250° C. at an applied power of about 300 W, and shows distinct non-thermal characteristics. In the simplest design, two planar, parallel electrodes are employed to generate a plasma in the volume therebetween. A “jet” of long-lived metastable and reactive species that are capable of rapidly cleaning or etching metals and other materials is generated which extends up to 8 in. beyond the open end of the electrodes. Films and coatings may also be removed by these species. Arcing is prevented in the apparatus by using gas mixtures containing He, which limits ionization, by using high flow velocities, and by properly spacing the rf-powered electrode. Because of the atmospheric pressure operation, there is a negligible density of ions surviving for a sufficiently long distance beyond the active plasma discharge to bombard a workpiece, unlike the situation for low-pressure plasma sources and conventional plasma processing methods.

This paper deals with the plasma surface treatment of polymers in a low frequency bell jar reactor with non-symmetrical configuration of electrodes. The highly energetic character of this discharge due to its low excitation frequency and electrode configuration, as well as its small discharge volume makes it a very efficient and fast functionalization process. Amongst the different plasma gases used for the adhesion improvement of polypropylene to aluminum, ammonia has shown to be the most suitable one for this application. Since the NH and NH ₂ radicals play an important role in the kinetics of nitrogen incorporation in polymers, mixtures of N ₂ and H ₂ were also used as possible substitutes for ammonia. The former are more environmentally friendly and easier to handle in industry than ammonia. The efficiency of nitrogen rich mixtures in the case of the second application, i.e. adhesion improvement of copper to fluoropolymers has been compared to that of ammonia which still shows faster nitrogen incorporation. The last part of this paper is devoted to the study of the energetic character of plasmas of mixtures of He+NH ₃ by OES and electrical measurements in the whole range of composition of the two gases. The results show that an ammonia percentage ranging from 5 to 10% in plasmas of mixtures of He/NH ₃ represents a transition between two different discharge regimes. Plasmas of mixtures of He+2% NH ₃ , characterized by highly energetic electrons, ions and probably metastables of helium give rise to enhanced adhesion of PP to aluminum which remains stable with time.

We present a new approach for the surface treatment of polymer films at atmospheric pressure. The DC glow discharge is generated by applying a high voltage between two electrodes which are placed in a channel with a high flux of air. The air flow removes charge carriers from the plasma zone which prevents the formation of sparks. In the almost homogeneous plasma a comparably high electrical power is converted forming a high concentration of active species. The flowing air transports them to the polymer surface. We report the results of the first experiments with this set-up. The influence of various process parameters on the discharge properties is shown. The resulting alterations in the surface structure of the polymers are characterised by XPS and contact angle geometry.

The surface energy and adhesion dynamics of pressure sensitive adhesives-like networks (PSA-LNs) as mimics for PSAs were studied using JKR-based contact mechanics and peel tests. Acrylic acid (AA) was co-polymerized with 2-ethyl hexyl acrylate (2-EHA) and 1,6-hexane diol diacrylate (HDDA) to create PSA-LNs. The measured surface energy (27 to 31 mJ/m²) was sensible as surmised from their structure. Acrylic acid content increases the surface energy, threshold adhesion energy and adhesion hysteresis of PSA-LNs. Measurements of adhesion dynamics showed a dependence of adhesion energy to the 0.6–0.8 power of crack speed, depending upon the model chosen for analysis of the data. When compared with actual pressure-sensitive adhesive tape peel tests, the adhesion dynamics data predicted the peel strength. This study shows a direct relationship between threshold adhesion energy, crack propagation mechanics and peel strength measurements.

An atmospheric pressure non-equilibrium plasma (APNEP) developed in the UK by EA Technology Ltd is currently being investigated in collaboration with the University of Surrey. Of the many applications of surface modification that can be induced using plasmas, adhesion enhancement is one of the most commercially important. In this paper, we illustrate the use of an atmospheric plasma to enhance the adhesion characteristics of low-density polyethylene (LDPE) and poly(ethylene terephthalate) (PET). The polymers were treated in the remote afterglow region of an atmospheric pressure plasma to avoid the thermal effects that can cause degradation for thermally sensitive materials when placed in direct contact with the plasma. Reactive (oxygen containing) and inert (oxygen free) atmospheric plasmas rapidly impart adhesion enhancement by a factor of two to ten as measured by 180° peel tests. However, extended exposure to the atmospheric plasma does not impart additional adhesion enhancement as the surface is ablated revealing the underlying polymer with poor adhesive characteristics. In contrast, vacuum plasma treated LDPE and PET show increased adhesion with extended plasma treatment. An adhesion enhancement in excess of two to three orders of magnitude was found to be achievable for vacuum plasma treatment times greater than 10 min.

The corona discharge technique was explored as a means of forming chemically active sites on a low-density polyethylene (LDPE) film surface. The active species thus prepared at atmospheric pressure in air was exploited to subsequently induce copolymerization of 2-hydroxyethyl methacrylate (HEMA) onto LDPE film in aqueous solution. The results showed that with the corona discharge voltage, reaction temperature, and inhibitor concentration in the reaction solution the grafting degree increased to a maximum and then decreased. As the corona discharge time, reaction time, and HEMA concentration in the reaction solution increased, the grafting degree increased. With reaction conditions of a 5 vol % HEMA concentration, 50°C copolymerization temperature, and a 2.0-h reaction time, the degree of grafting of the LDPE film reached a high value of 158.0 μg/cm² after treatment for 72 s with a 15-kV voltage at 50 Hz. Some characteristic peaks of the grafted LDPE came into view at 1719 cm⁻¹ on attenuated total reflectance IR spectra (CO in ester groups) and at 531 eV on electron spectroscopy for chemical analysis (ESCA) spectra (O_1s). The C_1s core level ESCA spectrum of HEMA-grafted LDPE showed two strong peaks at ∼286.6 eV (CO from hydroxyl groups and ester groups) and ∼289.1 eV (OCO from ester groups), and the C atom ratio in the CO groups and OCO groups was 2:1. The hydrophilicity of the grafted LDPE film was remarkably improved compared to that of the ungrafted LDPE film. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2881–2887, 2001
https://onlinelibrary.wiley.com/doi/abs/10.1002/app.1738

An atmospheric pressure non-equilibrium plasma (APNEP) has been developed in the UK by EA Technology Ltd and is currently being investigated in collaboration with the University of Surrey. The main focus is the use of atmospheric pressure plasmas to modify the surfaces of commercially important polymers including polyolefins, poly(ethylene terephthalate) and poly(methyl methacrylate). These surface modifications include surface cleaning and degreasing, oxidation, reduction, grafting, cross-linking (carbonization), etching and deposition. When trying to achieve targeted surface engineering, it is vital to gain an understanding of the mechanisms that cause these effects, for example, surface functionalization, adhesion promotion or multi-layer deposition. Hence comparisons between vacuum plasma treated surfaces have also been sought with a view to using the extensive vacuum plasma literature to gain further insight. In this paper, we will introduce the APNEP and compare the key characteristics of the plasma with those of traditional vacuum plasma systems before highlighting some of the surface modifications that can be achieved by using atmospheric plasma. Data from the analysis of treated polymers (by spectroscopy, microscopy and surface energy studies) and from direct measurements of the plasma and afterglow will be presented. Finally, our current understanding of the processes involved will be given, particularly those that are important in downstream surface treatments which take place remote from the plasma source.

The effects of the unit corona-treatment energy on the contact angle of various liquids, on the surface free energy, on the extent of oxidation of a surface layer, and on the adhesion of acrylic adhesive were studied using a biaxially-oriented polypropylene (BOPP) film. The surface free energy was determined with the van Oss-Chaudhury-Good (VCG) approach as well as with the wettability method. The extent of oxidation of the surface layer of the corona-treated BOPP film was evaluated with X-ray photoelectron spectroscopy. The adhesion strength of joints between the BOPP film and the acrylic adhesive was measured using the 180°

In the range of the unit corona-treatment energy up to 1.2 kJ/m², a rapid increase in the surface free energy with the treatment energy is observed. In the range above that value, the surface free energy rises relatively slowly. The extent of oxidation of the surface layer and the adhesion strength of joints between the BOPP film and the acrylic adhesive are approximately in direct proportion to the unit energy of the corona treatment. A five-fold growth of the adhesion strength of the studied joints within the examined range of the treatment energy was found.In the range of the unit corona-treatment energy up to 1.2 kJ/m², a rapid increase in the surface free energy with the treatment energy is observed. In the range above that value, the surface free energy rises relatively slowly. The extent of oxidation of the surface layer and the adhesion strength of joints between the BOPP film and the acrylic adhesive are approximately in direct proportion to the unit energy of the corona treatment. A five-fold growth of the adhesion strength of the studied joints within the examined range of the treatment energy was found.In the range of the unit corona-treatment energy up to 1.2 kJ/m², a rapid increase in the surface free energy with the treatment energy is observed. In the range above that value, the surface free energy rises relatively slowly. The extent of oxidation of the surface layer and the adhesion strength of joints between the BOPP film and the acrylic adhesive are approximately in direct proportion to the unit energy of the corona treatment. A five-fold growth of the adhesion strength of the studied joints within the examined range of the treatment energy was found.

The interfacial adhesive behavior between acrylic pressure sensitive adhesive-like networks (PSA-LNs) and poly(vinyl N-alkyl carbamate) release coatings was studied using a contact mechanical method and peel tests. Surface energy and interfacial energy were directly measured in JKR tests using a novel sample construction. The surface energy of the poly(vinyl N-alkyl carbamates) was found to be around 20 mJ/m². Interfacial energies between PSA-LNs and the release coatings were found to be quite high – between 7 and 24 mJ/m². Changes in adhesion dynamics were governed by acid-base interactions between the carbamate in the release coating and the acid groups in the PSA-LN. The length of the alkyl chain in the release coating moderated this effect. We also found a correlation between fundamental adhesion energy and peel strength. Examination of this phenomenon provides a basis for understanding the poor storage stability of PSA tapes made using alkyl carbamates and acid-containing PSAs.

The increased use of polyphenylene sulphide (PPS) and polyetheretherketone based composites for aircraft structures has highlighted the need for reliable methods of bonding these materials to metallic components such as titanium. Both composite and titanium adhesive bonds exhibit poor long-term durability when exposed to hot/wet conditions, aerospace fluids and solvents. As a result, surface treatments are employed to enhance surface energy, surface roughness and alter surface chemistry to provide better long-term durability. In this initial study the adhesive bonding of glass fibre reinforced GFR-PPS and commercially pure titanium was investigated. Prior to bonding, both materials were plasma treated using argon and oxygen gases in a RF discharge. Surface characterisation was carried out to optimise these treatments. Surface energy and wettability were examined using contact angle analysis, surface roughness was examined using scanning electron microscopy and atomic force microscopy, while X-ray photo-electron spectroscopy (XPS) was employed to study the surface chemistry. Bond strengths were determined using lap shear tests. Initial results reveal that these optimum plasma treatments produce a significant increase in bond strength.

The present invention relates to a corona station for the preliminary processing of a strip material. The corona station includes at least one electrode (18) connected to a high-voltage power supply through connection means, a housing containing at least partially the electrode (18) and the connection means, and at least one cylindrical counter-electrode (17), wherein the strip of material (16) does not rest on the whole surface of said counter-electrode (17).

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.

Nitrogen-containing plasmas are widely used to improve wettability, printability, bondability, and biocompatibility of polymer surfaces. Plasma-treatments fed with NH₃ give rise to N-functionalities, such as amino ( NH₂), imino ( CH NH), cyano ( C N) and others on polymers, plus oxygen-containing groups due to post-plasma atmospheric oxidation. This work deals with NH₃ plasma treatment of PA 6 foils and the evaluation of surface modification as a function of treatment time. The introduced functionalities were observed by streaming potential measurements (surface charge), X-ray photoelectron spectroscopy analysis (nature of introduced functionalities), atomic force microscopy (surface topography), and contact angle measurement (assessment of treatment effect). The results show that the introduction of N-containing groups is increasing with longer treatment time only to a certain extent where the negative effect of surface destruction prevails over the positive effect of introduction of functional groups. The treatment causes a shift of the isoelectric point (IEP) toward pH of 6.2 as compared to 4.2 found for the untreated foil. If the treatment time is longer than 1 min the IEP is shifted to lower pH, the number of amino groups on the surface is reduced and the contact angle is increased.