The article throws light on the physical methods to modify natural fibers to be used in composites. Physical methods in natural fiber processing are used to separate natural fiber bundles into individual filaments and to modify the surface structure of the fibers so as to improve the use of natural fibers in composites. Steam explosion and thermomechanical processes fall in the first category while plasma, dielectric barrier techniques and corona fall in the second. The physical treatments have also been used to modify the thermoplastic polymeric films like polyethylene and polypropylene in a bid to impart reactivity. Reviewing such developments, the areas for further research are suggested.

Long-term durability of a structural adhesive joint is an important requirement, because it has to be able to support the required design loads, under service conditions, for the planed lifetime of the structure. One way of improving bond durability is through the use of surface treatments prior to bonding, which will activate the adherends’ surface, making it more receptive to the adhesive. In this study, the effects of two surface pre-treatments (corona discharge and flame ionization) on three timbers (maritime pine, iroko, and European oak) were evaluated quantitatively through contact angle measurements. These measurements allowed the determination of the changes in the timber surface thermodynamic characteristics, thus indicating which pre-treatment performed better. The results showed that both techniques increased each timber's surface free energy, which could translate into a durability enhancement of bonded joints. Overall, the corona-discharge treatment looks more promising, since this treatment leads to a bigger increase in the timber's surface energy, especially in its polar component, whilst also tended to be less species specific, less susceptible to variation, and the treatment effects lasted longer for this type of treatment.

In order to functionalize the surface of blown low-density polyethylene (LDPE) and cast polypropylene (CPP) films, and ultimately to maximize the attachment of active molecules onto them, the optimum treatment parameters of capacitively-coupled radio-frequency (13.56 MHz) oxygen plasma were investigated by using contact angle, toluidine blue dye assay, X-ray Photoelectron Spectroscopy (XPS) and Attenuated Total Reflectance Fourier Transform Infrared Spectroscopy (ATR-FTIR). Contact angle values of LDPE and CPP samples decreased significantly after oxygen plasma treatment. They further decreased as the plasma power level increased. The treatment time had no substantial effect on contact angle value. The optimum treatment conditions for LDPE and CPP films for maximizing carboxyl functionality without causing observable surface changes were found to be 200 W/200 mTorr and 250 W/50 mTorr, respectively, when treated for 3 min. The maximum carboxyl group concentration obtained with LDPE and CPP films were 0.46 and 0.56 nmol/cm², respectively. The percent of oxygen atoms on the surface of plasma-treated LDPE and CPP films was determined by XPS analysis to be 22.6 and 28.7%, respectively. The ATR-FTIR absorption bands at 1725–1700 cm⁻¹ confirmed the presence of carboxylic acids on LDPE and CPP films. By exposing the plasma-treated sample to air rather than water and treating films repeatedly with oxygen plasma, a higher carboxyl group concentration could be obtained. Copyright © 2008 John Wiley & Sons, Ltd. https://onlinelibrary.wiley.com/doi/abs/10.1002/pts.829

Plasma treatment of polyimide surfaces not only causes structural modification during the plasma exposure, but also leaves active sites on the surfaces that are subject to post-reaction. In this work, the effects of atmospheric fluorine plasma treatment on the surface properties and dielectric properties of polyimide thin film were investigated by using X-ray photoelectron spectroscopy (XPS), Fourier transform-IR (FT-IR) spectroscopy, and contact angle measurement. The results indicated that plasma treatment successfully introduced fluorine functional groups on the polyimide surfaces. The polyimides also exhibited good thermal stability and a lower dielectric constant. It appears that the replacement of fluorine led to the decrease of the local electronic polarizability of polyimide. Consequently, it was found that the atmospheric fluorine plasma-treated polyimides possessed lower dielectric characteristics than the untreated polyimides.

Without any preprocessing, polyester fabric has a lower ability to hold on water and inks due to the smooth morphology and chemistry property of polyester fibers. Therefore, patterns directly printed with pigment inks have poor color yields and bleed easily. Plasma surface treatment of polyester fabrics was carried out in composite atmosphere with air and 10% Ar under different experimental conditions. After plasma treatment the samples were printed with pigment inks. The results show that surface-modified polyester fabrics exhibited enhanced color yields and excellent pattern sharpness. SEM and XPS analyses indicated that this improved color performance was mainly contributed by not only the etching effect but also oxygen-containing polar groups induced onto fiber surfaces through plasma treatment. Thereby the surface modification of polyester fabrics using air/Ar plasma offers a potential way to fabric pretreatment for pigment inkjet printing with the advantages of environmental friendly and energy saving over traditional pretreatment methods.

During the past decade polylactide acid (PLA) polymer has been the subject of numerous researches aimed at comparing it with traditional petroleum based polymers for many packaging applications. PLA is biodegradable and derived from agricultural by-products such as corn starch or other starch-rich substances like maize, sugar or wheat.While PLA is currently being used in many packaging applications with well documented performance, little work has been done comparing printing processes and performance. This study presents PLA printing performance and sustainability findings using the common flexography printing process. Various analytical methods were used to evaluate performance and provide recommendations for optimized printing on PLA as compared to PET, oriented PP and oriented PS. Results of this study found that PLA films were comparable in printability and runnability to standard petroleum based flexible packaging films.

Two engineering thermoplastic polymers (polycarbonate, PC, and acrylonitrile butadiene styrene copolymer, ABS) were treated with atmospheric plasma torch using different treatment rates (1, 5 and 10 m/min). The modifications produced by the treatment were analysed by contact angle measurements, XPS, SEM and ATR-IR spectroscopy. Particular emphasiswas placed on the ageing (up to 30 days) after atmospheric plasma treatment on both polymers. The slower the atmospheric plasma treatment, the greater the wettability of the treated polymers. The decrease in water contact angle was mainly ascribed to a significant increase in oxygen content due to the formation of carboxylic and hydroxyl groups and a decrease in the carbon content on the polymer surfaces. After natural ageing, there was an increase in the water contact angle, although the values of the untreated polymer surface were never reached.

In this paper, a dielectric barrier discharge (DBD) operated at (sub)atmospheric pressure in a 95/5% He/CF₄ mixture is employed to increase the hydrophobicity of a poly(ethylene terephthalate) (PET) film. This paper studies the influence of different operating parameters on the hydrophobic properties of the PET film using contact angle measurements. Results clearly show that the hydrophobicity of the PET film is only enhanced when using large gas flows. Moreover, this work demonstrates that operating pressure and discharge power have a significant influence on the rate of plasma modification as well as on the uniformity of the plasma treatment. Also important to mention is that no ageing effect is observed. As a result, one can conclude that the utilized DBD is an efficient tool to create stable, hydrophobic PET surfaces.

Influence of the unit energy (E_u) of corona discharge used for modification of pure polylactide (PLA) and polylactide nanocomposite (PLAC) containing 5 wt% of an aluminosilicate nanofiller (Cloisite 30B) on water (Θ_W) and diiodomethane (Θ_D) contact angles as well as on surface free energy (γ_s) of these polymers was studied. Θ_W and Θ_D as advancing contact angles were measured with use of a goniometer while γ_s was calculated by the Owens–Wendt method. It was found that Θ_W increased with the rising E_u while Θ_D remained approximately constant. Assuming E_u = const, it could be stated that the increase in γ_s was much more evident for PLA than for PLAC. This increase resulted practically from the change in the polar component of γ_s because the dispersive component for the two materials only slightly decreased with increase in E_u.

Adhesion of epoxy resins on copper foils for printed circuit board (PCB) applications is improved by nearly a factor of 5, using surface cleaning and deposition of a 15-nm-thick film in a low-pressure remote plasma-enhanced chemical vapor deposition process. The cleaning pretreatment, using an N₂–O₂ oxidizing gas mixture with moderate heating (343 K), gives the best results. This pretreatment removes the carbonaceous contaminants present on the topmost surface of the sample and slightly oxidizes the copper into CuO. This oxide is then reduced during the deposition treatment, presumably by reaction with the aminopropyltrimethoxysilane (APTMS) precursor. The surface roughness is unchanged after treatment, thereby showing that the improvement of the copper/epoxy adhesion is only due to the chemistry of the plasma coating. Applying these results to dielectric barrier discharges allows us to achieve the same level of adhesion, which, therefore, does not depend on the process.

Low-pressure plasma generated in a typical parallel plate reactor and atmospheric pressure plasma produced by a plasma needle were utilized to modify the surface of poly(styrene–butadiene–styrene) (SBS) elastomers. An RF discharge (13.56 MHz) in helium was used in the both cases. The SBS surfaces were investigated by T-peel tests, contact-angle measurements, and IRS–FTIR spectroscopy. It has been found that such plasma treatments drastically improve the strength of adhesive-bonded joints between the SBS surfaces and polyurethane adhesives, however, the plasma needle operation has turned out to be more effective. The molecular processes proceeding on the SBS surfaces have been briefly discussed.

An environmentally friendly plasma amination process for the activation of polymers prior to electroless metallization using dielectric barrier discharges (DBD) at atmospheric pressure was investigated. One focus of the work was on the correlation between plasma parameters and palladium coverage on the polymer on the one hand and the palladium coverage and adhesion of a galvanic copper metallization on the other hand. Using XPS spectroscopy it was found that a DBD treatment of polyimide (PI) films with mixtures of N₂ and H₂ leads to considerably higher Pd surface concentrations than on untreated reference samples or foils treated in air-DBD. The Pd coverages achieved result in peel strengths of a copper metallization of up to 1.4 N · mm⁻¹.

World-class, fully automated manufacturing processes rely more and more on advanced, environmentally friendly surface treatment technologies. An innovative atmospheric pressure plasma technique allows inline rubber and plastic manufacturing processes to become fully automated with total process control. A thorough pretreatment must produce surfaces with reliable and repeatable characteristics to achieve optimal adhesive bonding, coating and printing results. In addition, pretreatment must be delivered in a cost-effective and safe manner. The new process uses the high effectiveness of plasma for microfine cleaning, high-surface activation and nanocoating. In most cases the plasma application takes the place of environmentally unfriendly and costly solvent cleaning or chemical adhesion promoters and primers.

A low-temperature, atmospheric pressure oxygen and helium plasma was used to treat the surfaces of polyetheretherketone, polyphenylsulfone, polyethersulfone, and polysulfone. These aromatic polymers were exposed to the afterglow of the plasma, which contained oxygen atoms, and to a lesser extent metastable oxygen (^1δ_g O₂) and ozone. After less than 2.5 seconds treatment, the polymers were converted from a hydrophobic state with a water contact angle of 85±5 to a hydrophilic state with a water contact angle of 13±5 . It was found that plasma activation increased the bond strength to adhesives by as much as 4 times. X-ray photoelectron spectroscopy revealed that between 7% and 27% of the aromatic carbon atoms on the polymer surfaces was oxidized and converted into aldehyde and carboxylic acid groups. Analysis of polyethersulfone by internal reflection infrared spectroscopy showed that a fraction of the aromatic carbon atoms were transformed into C=C double bonds, ketones, and carboxylic acids after plasma exposure. It was concluded that the oxygen atoms generated by the atmospheric pressure plasma insert into the double bonds on the aromatic rings, forming a 3-member epoxy ring, which subsequently undergoes ring opening and oxidation to yield an aldehyde and a carboxylic acid group.

The role of roughening and functionalization processes involved in modifying the wettability of poly(ε-caprolactone) (PCL) after treatment by an atmospheric pressure glow discharge plasma is discussed. The change in the ratio of CO/C–O bonds is a significant factor influencing the wettability of PCL. As the contact angle decreases, the level of CO bonds tends to rise. Surface roughness alterations are the driving force for lasting increases in wettability, while the surface functional species are shorter lived. We can approximate from ageing that the increase in wettability for PCL after plasma treatment is 55–60% due to roughening and 40–45% due to surface functionalization for the plasma device investigated.

A new version of axisymmetric drop shape analysis (ADSA) called ADSA-NA (ADSA-no apex) was developed for measuring interfacial properties for drop configurations without an apex. ADSA-NA facilitates contact angle measurements on drops with a capillary protruding into the drop. Thus a much simpler experimental setup, not involving formation of a complete drop from below through a hole in the test surface, may be used. The contact angles of long-chained alkanes on a commercial fluoropolymer, Teflon AF 1600, were measured using the new method. A new numerical scheme was incorporated into the image processing to improve the location of the contact points of the liquid meniscus with the solid substrate to subpixel resolution. The images acquired in the experiments were also analyzed by a different drop shape technique called theoretical image fitting analysis-axisymmetric interfaces (TIFA-AI). The results were compared with literature values obtained by means of the standard ADSA for sessile drops with the apex. Comparison of the results from ADSA-NA with those from TIFA-AI and ADSA reveals that, with different numerical strategies and experimental setups, contact angles can be measured with an accuracy of less than 0.2°. Contact angles and surface tensions measured from drops with no apex, i.e., by means of ADSA-NA and TIFA-AI, were considerably less scattered than those from complete drops with apex. ADSA-NA was also used to explore sources of improvement in contact angle resolution. It was found that using an accurate value of surface tension as an input enhances the accuracy of contact angle measurements.

The effect of different nebulized liquids directly introduced into the dielectric barrier discharge (DBD) was compared with simple air DBD treatment of polyethylene foils. Water, alcohols and aqueous solutions of different organic substances (environmentally compatible) and water soluble polymers were applied as aerosols and injected into the DBD zone. The DBD residence time (number of treatment cycles) and the power were varied. The durability of the surface modification effect was studied after removing of Low-Molecular Weight Oxidized Material (LMWOM) by washing the samples with water and ethanol. The modified foils were characterized by XPS and contact angle measurements as a function of the applied plasma conditions. The concentration of functional groups at modified surfaces was estimated by derivatization and subsequent XPS measurement.

We present new spreading-drop data obtained over four orders of time and apply our new analysis tool G-Dyna to demonstrate the specific range over which the various models of dynamic wetting would seem to apply for our experimental system. We follow the contact angle and radius dynamics of four liquids on the smooth silica surface of silicon wafers or PET from the first milliseconds to several seconds. Analysis of the images allows us to make several hundred contact angle and droplet radius measurements with great accuracy. The G-Dyna software is then used to fit the data to the relevant theory (hydrodynamic, molecular-kinetic theory, Petrov and De Ruijter combined models, and Shikhmurzaev’s formula). The distributions, correlations, and average values of the free parameters are analyzed and it is shown that for the systems studied even with very good data and a robust fitting procedure, it may be difficult to make reliable claims as to the model which best describes results for a given system. This conclusions also suggests that claims based on smaller data sets and less stringent fitting procedures should be treated with caution.

The surface of high-performance poly(ethylene terephthalate) (PET) fibers is difficult to wet and impossible to chemically bond to different matrices. Sizing applied on the fiber surface usually improves fiber wetting, but prevents good adhesion between a matrix and the fiber surface. The present study demonstrates that the plasma treatment performed by Surface dielectric barrier discharge (Surface DBD) can lead to improved adhesion between sized PET fabric and polyurethane (PU) or poly(vinyl chloride) (PVC) coatings. Moreover, it points out that this plasma treatment can outperform current state-of-the-art adhesion-promoting treatment. Plasma treatment of sized fabric was carried out in various gaseous atmospheres, namely N₂, N₂ + H₂O, N₂ + AAc (acrylic acid) and CO₂. The adhesion was assessed by a peel test, while wettability was evaluated using strike-through time and wicking rate tests. Changes in fiber surface morphology and chemical composition were determined using scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS), respectively. Only the CO₂ plasma treatment resulted in improved adhesion. As indicated by the analyses, increased surface roughness and the incorporation of specific oxygen-containing groups were responsible for enhanced adhesion. The results presented were obtained using a plasma reactor suitable only for batch-wise treatment. As continuous treatment is expected to provide higher homogeneity and, therefore, even better adhesion, a scaled-up Surface DBD plasma system allowing continuous treatment is presented as well.

Polymer and paper structures have been successfully utilized in several fields, especially in the packaging industry. Together with barrier properties, printability is an important property in packaging applications. From the point of view of printing, the dense and impervious structure of extrusion coatings is challenging. Flame, corona and atmospheric plasma treatments were used to modify the surface of low density polyethylene (LDPE) and polypropylene (PP) and the influence of these surface modifications on print quality, i.e., toner adhesion and visual quality was studied. The traditional surface treatment methods, i.e., flame and corona treatments, increased the surface energy by introducing oxygen containing functional groups on the surfaces of LDPE and PP more than helium and argon plasma treatments. Only in the case of flame treatment, the higher surface energy and oxidation level led to better print quality, i.e., toner adhesion and visual quality, than the plasma treatments. The morphological changes observed on LDPE surface after flame treatment are partly responsible for the improved print quality. Atmospheric plasma treatments improved the print quality of LDPE and PP surfaces more than corona treatment. The electret phenomenon observed on LDPE and PP surfaces only after corona treatment is the most likely reason for the high print mottling and low visual quality of corona treated surface.

Using dielectric barrier discharges (DBDs) in suitable gas atmospheres, appreciable densities of amino groups can be generated on polymer surfaces. After the introduction and a few remarks on analytical methods for the determination of functional groups densities, this paper presents a short summary of recent studies on the mechanism of the polymer surface amination from nitrogen and nitrogen/hydrogen mixtures, and possible relevant precursor species. Combination of chemical derivatization with quantitative FT-IR spectroscopy was employed for the determination of primary amino groups densities introduced on polyolefin surfaces in DBD afterglows in N₂ and N₂ + H₂ mixtures. Owing to the possibility to generate atmospheric-pressure plasmas in sub-mm³ volumes, DBD plasmas can be used to modify polymer surfaces area selectively: a new process termed 'plasma printing' can be applied for the achievement of micropatterned surface modifications, such as hydrophilization/hydrophobization or chemical functionalization. Direct-patterning polymer surface modification processes are of interest for biochemical/biomedical applications as well as for polymer electronics. Two examples are presented in more detail: • the area-selective plasma amination of carbon-filled polypropylene minidiscs to manufacture microarrays with peptide libraries utilizing parallel combinatorial chemical synthesis, and •the continuous treatment of polymer foils by means of reel-to-reel patterned plasma amination for the subsequent electroless copper metallization, leading to a fast and highly efficient process for the manufacture of structured metallizations for flexible printed circuits or RFID antennas.