This chapter provides a general summary of the current state of knowledge of plasma modification of various natural cellulosic fibres. Much of the information reported here is taken from the references cited at the end of the chapter, which should be consulted for a more in-depth treatment. Several aspects of plasma modification of various natural cellulose fibres are thoroughly treated in a number of excellent works. [1, 2]

Growing demands on the functionality of technical textiles as well as on the environmental friendliness of finishing processes increase the interest in physically induced techniques for surface modification and coating of textiles. In general, after the application of water-based finishing systems, the textile needs to be dried. The removing of water is energy intensive and therefore expensive. In contrast to conventional wet finishing processes, a plasma treatment is a dry process. The textile stays dry and, accordingly, drying processes can be avoided and no waste water occurs. Plasma treatments represent, therefore, energy efficient and economic alternatives to classical textile finishing processes. Within plasma processes, a high reactive gaseous phase interacts with the surface of a substrate. In principle, all polymeric and natural fibres can be plasma treated. For many years, mainly low-pressure plasma processes have been developed for textile plasma treatment. However, the integration of these processes, which typically run at pressures between 0.1 and 1 mbar, into continuously and often fast-running textile production and finishing lines is complex or even impossible. In addition, due to the need for vacuum technology, low-pressure processes are expensive. The reasons why plasma processes at atmospheric pressure are advantageous for the textile industry are in detail: • The typical working width of textile machines is between 1.5 and 10 meters. Textile-suited plasma modules need to be scalable up to these dimensions, which is easier for atmospheric-pressure techniques.• Textiles have large specific surfaces compared to foils, piece goods or bulk solids. Even with strong pumps, the reduced pressure which is necessary for low pressure plasma will only be reached slowly due to the desorption of adsorbed gases.

Although the power of plasma surface engineering across vast areas of industrial manufacturing, from microelectronics to medical and from optics to packaging, is demonstrated daily, plasma in the textile industry has been cynically described as the technology where anything can happen... but never does. Research into the application of plasmas to textiles goes back to the 1960s but, despite the reporting of novel and potentially commercial effects, it is only in recent years that plasma processing systems have begun to emerge into textile manufacturing in the production of specialty/high value fabrics. It is instructive to look at major criteria for the introduction of new technology into the textile market and to assess plasma processing against such criteria. They can be separated into qualifiers (must be satisfied by the new technology as a minimum) and winners (motivate take-up of the new technology by the industry). Here are ‘qualifier’criteria for new textile technologies:

Plasma diagnostic tools are an essential element towards the proper understanding and development of technological plasmas. Knowledge of the particle densities and energies in the bulk and at boundaries, the electrical potentials and the spatial and temporal evolution of these parameters allow technologists to operate plasmas in the most efficient way and allow the intrinsic plasma processes to be tailored to suit a particular application. There are many different diagnostic tools that can be used, depending on the type of plasma under investigation and the specific information that is required. Here, we have chosen to highlight four techniques frequently used in both academia and industrial settings. The first of these is the interpretation of the driving current and voltage waveforms. These measurements do not affect the plasma and can yield useful information on the major processes in the discharge. The second is electrical probing which, by their nature, are intrusive, since their presence affects the plasma under investigation. Their use is usually confined to low-pressure and low-temperature plasmas in which the heat flux will not destroy the integrity of the probe. The third area is mass spectrometry, which is most often performed at the substrate or plasma boundaries and may in many cases not affect the plasma unduly. The fourth diagnostic method discussed, optical emission spectroscopy, is non-perturbing; however, interpretation of spectral response is often difficult in low-pressure plasmas where the species are not in local thermodynamic equilibrium.

Contact angle behavior of four relatively high surface tension ionic liquids (1,3-dimethylimidazolium methyl sulfate, 1-ethyl-3-methylimidazolium ethyl sulfate, 1-ethyl-3-methylimidazolium fluoroborate, and bis(hydroxyethyl)dimethylammonium methane sulfonate) was studied on seven hydrophobic surfaces and compared with water contact angle behavior. Smooth surfaces of various chemical compositions exhibit contact angles with ionic liquids that are lower than values obtained with water and that scale with liquid surface tension values. Contact angles of ionic liquids on rough perfluoroalkyl surfaces exhibit the highest contact angles reported for liquids other than water and are indistinguishable from those of water and not dependent on liquid surface tension. Superhydrophobic methylsilicone surfaces that exhibit high water contact angles and low hysteresis exhibit very low receding contact angles with ionic liquid probe fluids and high hysteresis. The potential for ionic liquids as probe fluids is argued because of their variable and controllable surface tension, interface charge density, interface dipole density, as well as their variable and controllable cation/anion structure and molecular volume.

Surface properties of a Melinex 800 PET polymer material modified by an atmospheric-pressure air dielectric barrier discharge (DBD) have been studied using X-ray photoelectron microscopy (XPS) and contact angle measurement. The results show that the material surface treated by the DBD was modified significantly in chemical composition, with the highly oxidised carbon species increasing as the surface processing proceeds. The surface hydrophilicity was dramatically improved after the treatment, with the surface contact angle reduced from 81.8° for the as-supplied sample to lower than 50° after treatment. Post-treatment recovery effect is found after the treated samples were stored in air for a long period of time, with the ultimate contact angles, as measured, being stabilised in the range 58–69° after the storage, varying with the DBD-treatment power density. A great amount of the C–O type bonding formed during the DBD treatment was found to be converted into the CO type during post-treatment storage. A possible mechanism for this bond conversion has been suggested.

Combined surface treatments using plasma fluorination and surface roughening were applied to investigate whether they could increase the peel property of PET beyond the value needed for use as a release coating of pressure-sensitive adhesive tapes. The peel strength of PET treated with CF₄/He APG plasmas decreased to approximately 100 N · m⁻¹, but not quite to the ideal value of PTFE, 20 N · m⁻¹. We also prepared PET with a rough surface (matte PET) to examine the effect of surface roughening. The matte PET peel strengths were decreased by plasma fluorination; the roughest matte PET showed even lower peel strength than PTFE. We conclude that the combined treatments could be effective in the formation of a surface with high peel property on PET.

This study describes experiments to quantify polymer surface energy changes after exposure to atmospheric plasma. Atmospheric plasma treatment permits surface functionalization at near-ambient temperatures. Polyethylene and polystyrene are treated with an atmospheric plasma unit. The increased surface energy and improved wetting characteristics lead to a significant adhesion improvement with adhesives that cannot be used without surface treatment.

The effect of ultraviolet (UV) radiation in the presence of ozone as a surface treatment for polycarbonate is examined in regards to changes in the wettability, adhesion, and surface mechanical properties. Standalone, 175-µm-thick films of a commercially available polycarbonate were exposed to UV radiation from sources of different power with various treatment times in the presence of supplemental ozone. Significant decreases in the water contact angle were observed after exposure to UV radiation in the presence of ozone. After several variations in the experimental setup, it was determined that the change in water contact angle is a function of the UV irradiance and the work of adhesion follows a master curve versus UV irradiance. Nanoindentation experiments revealed that the modulus of the top 500 nm of the surface is increased following UV exposure, attributable to surface cross-linking. Adhesion tests to the surface (conducted by a pneumatic adhesion tensile test instrument) showed little change as a function of UV exposure. Analysis of adhesion test failure surfaces with X-ray Photoelectron Spectroscopy (XPS) showed the locus of bond failure lay within the bulk polycarbonate and the measured bond strength is limited by the bulk properties of the polycarbonate and/or the creation of a weak boundary layer within the polymer.

The surface free energy is an essential paper property affecting liquid/ink interaction with the ink-jet paper surface. Different ways of calculating surface energy components for ink-jet papers is introduced. The results given by the very useful van Oss–Chaudhury–Good (vOCG) bi-bidentate model are compared with simpler mono-bidentate and mono-monodentate models. The unbalance in the acid–base (AB) values of the vOCG-model is compensated for, and occasional negative roots obtained are removed when applying the simpler mono-bidentate- and mono-monodentate models. The simple and elegant mono-monodentate model produces comparable values with the other models, and is thus recommended. The calculated percent work of adhesion between the probe liquids and substrates correlates well with surface energy component values. Also the percent work of adhesion between the inks and substrates correlates with surface energy values.

Recently, there has been increased interest in using atmospheric pressure plasmas for materials processing, since these plasmas do not require expensive vacuum systems. However, APGDs face instabilities. Therefore, special plasma sources have been developed to overcome this obstacle, which make use of DC, pulsed DC and AC ranging from mains frequency to RF. Recently, the APPJ was introduced, which features an α-mode of an RF discharge between two bare metallic electrodes. Basically, three different geometric configurations have been developed. A characterization of the APPJs and their applications is presented.

The use of gas and/or liquid-phase carbon dioxide (CO2) with atmospheric plasma discharge surface pretreatment technology can remove micron and submicron particulates and hydrocarbon-based contaminations on plastics and metals. The cleaning process is based upon the expansion of either liquid or gaseous carbon dioxide through an orifice. The paper provides an understanding of the basic removal mechanism and provides experimental evidence of remarkable adhesion improvements relative to a broad range of applications in electrical, medical, and automotive manufacturing communities.

A study on oxygen-plasma treatment of ink-jet paper is presented. Paper was exposed to a weakly ionized, highly dissociated oxygen plasma with an electron temperature of 5 eV, a positive-ion density of 8 × 10¹⁵ m⁻³ and a density of neutral oxygen atoms of 5 × 10²¹ m⁻³. Optical emission spectroscopy (OES) was applied as a method for detection of the reaction products during the plasma treatment of the paper. OES spectra between 250 and 1000 nm were measured continuously during the plasma treatment. The wettability of the samples before and after the plasma treatment was determined by measuring the contact angle of a water drop. The appearance of the surface-functional groups was determined by using high-resolution x-ray photoelectron spectroscopy (XPS), while changes in the surface morphology were monitored with scanning electron microscopy (SEM). Already after 1 s of the plasma treatment the surface, which was originally hydrophobic, changed to hydrophilic, as indicated by a high absorption rate of a water drop into the paper. The OES showed a rapid increase of the CO and OH bands for the first few seconds of the plasma treatment, followed by a slow decrease during the next 40 s. The intensity of the O atom line showed reversed behaviour. The XPS analyses showed a gradual increase of oxygen-rich functional groups on the surface, while SEM analyses did not show significant modification of the morphology during the first 10 s of the plasma treatment. The results were explained by degradation of the alkyl ketene dimer sizing agent during the first few seconds of the oxygen-plasma treatment.