Plasma Polymerization and Its Applications in Textiles
Indian 10urnalof Fibre & Textile Research Vo1.31, March 2006, pp. 99-115
Plasma polymerization and its applications in textiles
Dirk Hegemann" EMPA - Materials Science & Technology, Functional Fibers and Textiles, Lerchenfeldstrasse 5, 9014 St.Gallen, Switzerland
Plasma polymerization enables the deposition of thin coatings on all kinds of substrates using electrical monomer discharges. This paper reviews plasma polymerization processes as surface modification (finishing) for textile applications. The dry and ecofriendly plasma technology aims at replacing wet-chemical process steps and adding new values to textile products. Characteristics of hydrocarbon, organosilicon, fluorocarbon, hydrophilic functional, monofunctional and ceramic coatings have been discussed to demonstrate their potential for textiles and fibers. Plasma technology requires adequate reactors for the continuous treatment of fabrics and fibers. To enable the optimization of plasma polymerization on batch reactors, questions of up-scaling are addressed to demonstrate the transfer to an industrial level. Both atmospheric and low pressure plasmas are considered regarding their effectiveness and efficiency. Examples for applications in textiles, such as hydrophobic, oleophobic and permanent hydrophilic treatments, have also been reported.
Keywords: Fluorocarbon coating, Hydrocarbon coating, Hydrophobic treatment, Hydrophilic treatment, Oleophobic treatment, Plasma polymerization 8 IPC Code: Int. CI. D06M 10100, H05H
1 Introduction the main part of the plasma-activated gas remains The challenges the European textile industry is close to room temperature. The electrons, however, facing today are enormous. Therefore, the need for a gain just the right energies to excite, dissociate and reorientation is strong. In order to survive, the ionize atoms and molecules. The degree of ionization European textile industry is taking the transition typically lies between lOA and 10-6. The earliest towards a knowledge-based economy focusing on plasma treatments on textiles and fibers date back to high-value added products. Plasma technology is the 1960s, focusing on the improvement of offering an attractive way to add new functionalities, wettability, shrinking resistance, tWIsting and such as water repellency, hydrophilicity, dyeability, desizing? Low pressure plasmas operating between conductivity and biocompatibility, due to the 0.1 Pa and 100 Pa were usually considered, which can nanoscaled modification of textiles and fibers. At the be activated by direct current (DC), alternate current same time, the bulk properties of textiles and fibers (Ae), radio frequency (RF) or microwave (MW). remain unaffected. Moreover, due to a low material Plasma polymerization is performed using different and energy input, while avoiding wet-chemical kinds of plasma-polymerizable gases (monomers).3 processes, the plasma technology provides the These gases might not undergo polymerization by realization of environmentally sound processes. I conventional activation (e.g. methane), showing a The plasma state consists of an equal part of nega main difference between plasma and conventional tively and positively charged particles (quasi polymerization. A plasma polymer typically results neutrality), excited states, radicals, metastables, and from a rivaling etching and deposition process vacuum ultraviolet (VUV) radiation. Surface treat depending on the plasma species present during film ments of materials can be performed by non growth yielding a more or less cross-linked structure. equilibrium plasmas which are excited by electric Atmospheric pressure plasmas, such as corona or fields. Since the energy coupling is conducted by dielectric barrier .discharges (DBD), however might electrons which achieve a mean temperature of seve be of special interest for the textile industry due to an ral electron volts (corresponding up to 100,000 K), easier processability.4 During the past decade, considerable efforts have been made to generate "E-mail: [email protected] stable atmospheric pressure plasmas.5 While they 100 INDIAN J. FIBRE TEXT. RES., MARCH 2006
show some use for activation and hydrophilization of reactivation of reaction products determine the plasma textiles6-8, it is rather difficult to obtain high quality polymerization. The reactive species are mainly plasma-polymerized coatings on textiles. Thus, low radicals, where cycle 1 consists of reactions of pressure plasma is a serious alternative for reactive species with a single reactive site, and cycle 2 multifunctional coatings for textile applications.9 First is based on divalent reactive species. Cross-cycle attempts to deposit plasma polymers on natural and reactions from 2 to 1 can occur. Furthermore, the synthetic fibers within a continuous low pressure surface takes part in plasma polymerization by third plasma reactor, where the fibers are processed air-to body reactions and etching processes that lead to air, were performed in the early 1980s.'0 Phosphorus ablation and re-deposition. containing monomers were used to impart flame The concept of chemical quasi-equilibria enables a retardancy to cellulosic fibers and acrylamide plasmas macroscopic approach to plasma polymerization. It is to improve the physico-mechanical properties. In assumed that the gas particles (e.g. monomer) first recent years, plasma polymerization on textiles and enter an active zone, where excitation and fibers was mainly investigated for hydrophobization, dissociation processes are taking place, and then permanent hydrophilization and adhesion I I travel through a passive zone yielding recombination improvement in fiber reinforced composites. and stable products, such as deposition on substrate, Although, within the textile industry up to now electrode or wall. Following this macroscopic merely special applications and niche products have 13 approach, the reaction parameter power input per gas been performed with the help of plasma flow (WIF), which represents the energy invested per polymerization, especially low pressure plasma particle within the active plasma zone, determines the polymerization is on the way to stimulate the textile mass deposition rate (Rill) using the following sector. relationship: 2 Plasma Polymerization When adverting of plasma polymerization, a ... ( 1 ) radical-dominated plasma chemical vapor deposition (plasma CYD) process is thought of, resulting in macromolecule formation, i.e. mainly amorphous, where is the reactor depending geometrical factor; G more or less cross-linked structures. The underlying W. the power input; F, the gas flow; and the Ea, growth mechanism is known as Rapid Step-Growth activation energy corresponding to the used '2 Polymerization (RSGP). As schematically shown in monomer. 14.15 Fig. 1, the recombination of reactive species and If Eq. (1) holds, a linear fit is obtained using an
I�.-.-.-.-.-.-.-.-.-.-.-.-.-.-.-.-.-.-.-.-.-.-., Arrhenius-type plot for the mass deposition rate per gas flow depending on the (inverse) energy input as shown by the straight line in Fig. 2 around the
I I I lon·induced : ,Deposition . I , I \, I I I I i Plasma I I I I ! boundary I I I I I I I I Oligomers taking part --,1-._._.1 I in deposition I - _ _ I I � - - I - - - I I - - I I - ! Activation energy : = : Slope of linear fit (Energy input)"' Fig. 1- Plasma polymerization via Rapid Step-Growth Polymerization (RSGP) involving an activation and a Fig. 2- Dependence of deposition rate per gas flow on energy recombination zone (concept of chemical quasi-equilibria) input HEGEMANN: PLASMA POL YMERIZAnON AND ITS APPLICATIONS IN TEXTILES 101
6 activation energy.1 The negative slope of the linear plasma these conditions are given for different fit represents the activation energy, which is found to monomers and gas mixtures within a broad parameter be the minimum energy required to initiate the plasma range, even when additional gases are added to obtain polymerization process and to obtain stable cross plasma co-polymerization.18 In the latter situation the linked plasma polymers.17 Deviations from this total gas flow is given by adding the different gases straight line might be found at low specific energies considering a flow factor that weights its contribution due to oligomerization and at high energies due to to the plasma polymerization process using the 8 etching, sputtering or temperature effects. 1 At rather following relationship: energetic plasma conditions or long durations, an . ( 3) increasing temperature during plasma polymerization .. has to be taken into account that might strongly where is the monomer gas; the non Fill Fe. influence the deposition rate depending on the type of polymerizable or carrier gas; and the reaction cross a, monomer used. section (flow factor) which is smaller than 1. Eqs (1) While the actual interaction of plasma particles and (3) enable the up-scaling of plasma polymerization plasma-induced radiation influence the absolute processes. The situation in atmospheric plasma deposition rates depending on the reactor geometry processes, which appears to be less defined, has not described by the geometrical factor in Eq. (1), the yet been examined using this macroscopic approach. activation energy merely depends on the plasma For plasma polymerization, in principle, all types chemistry of the considered monomer and is thus of materials might be treated. The plasma treatment of independent of the reactor design. To demonstrate the different types of textiles and fi bers has already been 1.8,1 1 20 2 general meani ng of the activation energy, the true reported. . , 1 Ho�ever, it has to be considered energy consumed within the active plasma zone that the film growth depends on all particles entering yielding the measured deposition rate (concept of the active plasma zone. Beside the selected gas flow, 8 chemical quasi-equilibria) has to be known.1 Beside which is applied externally, particles might also arrive the knowledge of the absorbed power and the gas from the inside of the plasma reactor, i.e. desorption flow, a geometrical consideration enables the finding from walls or from the substrates as well as etching or of the general activation energy corresponding to the sputtering products. Thus, the gas composition using a used monomer through the similarity parameter (S), as textile as substrate might substantially differ from the shown below: one without the substrate. Under certain ablation conditions, in particular with porous substrates, W S = duc,Vxus , (2) plasma polymer layers can be formed without external F dgu.,VcliS addition of polymerizable gases (redeposition). where is the length of active plasma zone; the Especially for textiles, their water content, additives dart ga" (mean) distance between gas inlet and depositiond and manufacturing residuals (such as sizes) have to be area; Vgas, the volume occupied by the gas; and taken into account that might strongly influence the di.\ the volume occupied by the gas discharge. 16.19 Eq.V (2), obtained film properties. Therefore, the textile helps to find out the specific energy consumed within samples have to be cleaned prior to the coating the active plasma zone which determines the process to obtain a suitable adhesion. Recently, it measured deposition rate. Replacing by S within could be demonstrated that RF-excited low pressure WIF Eq. (1), the general activation energy of a certain plasmas yield an excellent cleaning (desizing) and 3 t h us avO!'d e wet-ch' emlca process steps.22 .2. monomer gas can be derived. I At an energy input below the activation energy, Furthermore, the materials brought into the plasma oligomers can take part in the fi lm growth leading to disturb the quasi-neutral plasma state by implying an increased deposition rate compared to Eq. (1). electric fields which avoid the direct contact to High energy inputs, on the other hand, might also material surfaces. Therefore, active particles always yield a deviation from the straight line due to etching, travel through passive zones (concept of chemical sputtering or temperature-induced effects (Fig. 2). quasi-equilibria) which might be micrometer to However, the macroscopic approach helps to identify centimeter wide. The type of active particles the range of (basic) plasma polymerization and gives contributing to the deposition depends on the mean hints to optimize the film properties. In a low pressure free path (pressure), the lifetime (reaction probability) 1 02 INDIAN J. FIBRE TEXT. RES., MARCH 2006
and the width of the passive zone (plasma sheath). should be treated, to have the winding inside the Most of all, with low pressure RF plasmas a high chamber enabling a semi-continuous treatment. voltage drop might be observed across the plasma Obviously, this kind of process cannot be integrated sheath resulting in high energetic particle interactions. directly into a production line. However, when In case of textiles, this situation becomes complicated looking at achievable process velocities for plasma due to the structure of the considered textile which polymerization on plane substrates, a principle shows several dimensions, filament distance, incompatibility might occur, as discussed below. interfiber (yarn) distance as well as contacting areas Large reactors for low pressure plasma or protruding fi ber ends (as observed for staple yarn). polymerization on textiles are available in the Mainly by the variation in pressure, the plasma market.27.28 Plasma excitation in the kilohertz range process can be optimized for different textile (typically 40 kHz) is mainly used for industrial structures. At high pressures (atmospheric plasma), purposes due to lower costs. RF or MW sources are the plasma can be ignited within smaller volumes (due also applicable if required by the process. The to the Paschen law)?4 It is possible to have the plasma reactors are typically designed for the textile widths burning inside a textile structure (at least inside the up to 120 cm, larger widths of up to 4 m are also mesh openings), yielding plasma polymer growth. An possible. The reactors are loaded with textile atmospheric plasma generated outside the textile as packings, closed, evacuated and run in a semi usually done, on the other hand, hardly yields a continuous process. The textiles are led through the uniform coating since active particles are just able to plasma regions adapted to the required process, which reach the outside lying fiber sUIfaces. Uncoated areas comprises usually a cleaning and a plasma deposition are still taking part in external interactions. Moreover, step. a high pressure plasma is fi lamentary in nature, thus To avoid some limits of plasma polymerization on leading to moving hot spots. Therefore, it is difficult fabrics or other webs (huge reactor, semi-continuous to obtain controlled deposition conditions and the process, contacting fi bers), the direct treatment of effects that can be achieved by plasma polymerization fibers is also important. One advantage of fiber at atmospheric pressures on textiles are limited. processing is the possibility to perform winding off Moderate pressure plasmas (100-\ 000 Pa) were found and up in air by leading the fibers through suitable to give optimum cleaning and activation conditions openings into the low pressure region using a with non-polymerizable gases since a high number of differentially pumped sealing system. Flexible textile acti ve particles contribute to chemical etching.22.25 fi bers, yarns, etc. can be run several times through the Plasma polymerization fi nally can best be controlled plasma zones enhancing the plasma length and thus using low pressure plasmas (1-100 Pa) due to well the process velocity. Furthermore, different treatment defined plasma zones. In this pressure range, the mean times that might be required for different process free path lengths are high enough to allow the steps such as cleaning, deposition, and post-treatment penetration of the textile structure by energetic can thus be adapted for a one-step processing. In-line particles and long-living radicals. Good conditions for production is achievable by process velocities as high plasma polymerization are thus enabled on textile as several hundred meters per minute. fibers up to several fiber layers in depth so that the Therefore, both a semi-continuous web coater (up external media interact with the treated fibers. to 63 cm in width) and a continuous fiber coater are Therefore, at EMPA, mainly the low pressure plasmas present at EMPA (Fig. 3) beside several batch are considered to obtain plasma-polymerized coatings reactors. 19 While the flexible batch reactors, where on textiles. different geometries are realized to allow for To build up a reactor for plasma polymerization on symmetric and asymmetric radio frequency excitation, textiles, a vacuum chamber is required. First note that microwave and magnetron sputtering as well as no ultra high vacuum conditions must be fulfilled combinations thereof, are used for the optimization of regarding the outgassing of textiles26, and secondly plasma processes, the continuous pilot-plant reactors the atmospheric plasma chambers also require a serve to demonstrate industrial scale-up. surrounding box to allow for defined gases. In 3 Plasma-polymerized Coatings vacuum it is easier, at least when different types of 3.1 Hydrocarbons textile fabrics, nonwovens, membranes and papers Unlike conventional polymerization, plasma poly- HEGEMANN: PLASMA POLYMERIZATION AND ITS APPLICATIONS IN TEXTILES 103
0.1
E <.) u f/) '"'E u co 0.01 'E " a, n "' <:> ::. u... E a:: Q 0 o 0 0.001 0 0 0.002 0.004 0.006 0.008 0.01 0.012 (W/Fr' [(J/cmJr'l Fig. 4-Mass deposition rates per monomer tl ow for pure methane, ethylene and acetylene discharges, depending on the reaction parameter WI F within our web coater. The slope of the linear fits represents the corresponding activation energy
l00 r----,�r_------, I I 1 -MW - C2H2 1 I o RF - CH4 � � '" 10 D q "0 1 o I NE o ",- :00I E 0 0 _ _ .£ : a:: - t- 1-- O : C- .. 1 Fig. 3-Web coater (a) and fiber coater (b) developed and used at :1 E� 0.1 EMPA I 0 234E.l merization can be performed with any kind of C; [in units of hydrocarbon monomer (gaseous). For the ease of Fig. 5- Oxygen transmission rates (OTR) for plasma processing, mainly methane (CH4), ethylene (C2H4) or polymerized hydrocarbon layers acetylene (C2H2) is used. While the achievable film properties of the amorphous hydrocarbon layers shows that the activation energy indicates the mainly depend on the degree of cross-linking, which transition from weakly cross-linked to dense plasma is rather independent of the used monomer, saturated polymers. While at an energy input below the and unsaturated monomers show a difference in activation energy no barrier properties can be deposition rate and amount of unsaturated bonds left obtained, the permeation can be reduced at higher within the film structure. Most of all, the acetylene specific energies both for RF and MW activated 29 derived plasma polymers appear to be yellowish by discharges. These coatings are of interest for the light adsorption at unsaturated bonds. Methane, on the controlled drug release from textile substrates and for other hand, shows noticeably reduced deposition rates their hydrophobic properties. (Fig. 4). At increasing energy input, the internal stress The deposition of plasma-polymerized increases within the hydrocarbon network yielding hydrocarbon layers with defined permeation diamond-like coatings (OLe). It could be shown that properties can be controlled by the energy input into the fi lm properties nOw depend on the voltage drop the active plasma zone using the reaction parameter across the plasma sheath (given mainly by the bias and deriving the activation energy (Fig. 5). These potential) and thus on the interaction of energetic WIF parameters control the polymeric character of the particles during fi lm growth, which favor the coatings by the residual hydrogen content. The figure formation of a Sp3 hybridized network. OLC coatings 104 INDIAN FIBRE TEXT. RES., MARCH 2006 1. on textiles and fibers are investigated for their retained within the plasma-polymerized coatings can mechanical, tribological and biological properties.30 be successively reduced to attain more inorganic Adhesion on flexible substrates can be enhanced by quartz-like coatings (SiOx)' Thus, a wide range of interfacial gradient layers. different film properties can be adjusted by mainly The deposition of hydrocarbon plasma polymers varying the gas ratio using moderate energy inputs to was investigated as adhesion improvement in fiber keep the deposition temperature below about 60 °C. reinforced composites. Plasma polymerization of The organic/inorganic character that varies from ethylene was found to increase the adhesion strength polydimethylsiloxane (PDMS)-like to quartz-like between PET fibers and a PE matrix from I N/mm to (Fig. 6) directly affects the surface energy (adjustable 2.5 N/mm7, while pYlTole or acetylene as monomer between 20 mN/m and 68 mN/m), the permeability gases increased the pull-out force of aramid cords (down to oxygen transmission rates of 0. 1 cm3/m2 d 3 embedded in rubber by up to 90% with negligible bar), the density (between 1.0 g/cm and g/cm 2.0 \ decrease in single fiber tensile strength.3!.32 Ooij the mechanical properties (up to a hardness of about 6 et al.32 used a semi-continuous DC plasma reactor to GPa), the friction and the flame retardance.39-45 treat the aramid cords. Ultrathin «SO nm) plasma Films with desired properties can be designed polymerized acetylene layers were also found to depending on the energy input and the gas ratio increase the tensile strength of carbon fibers due to (e.g. 02/HMDSO) using the activation energy for their cross-linked network of molecular chain the plasma polymerization process derived from Eqs structure.3 (1) - (3).
3.2 Organosilicones Plasma-polymerized SiOx coatings usually show Organosilicones are the materials consisting of Si excellent adhesion on flexible substrates due to an atoms bonded to organic hydrocarbon groups. interface formation within the first steps of fi lm 46 Additionally, they might contain oxygen or nitrogen growth. Increased internal stresses which imply bonds. In general, Si-containing fi lms can be plasma higher forces acting on the interface within thicker or polymerized using gaseous mixtures of silane (SiH ) more inorganic coatings, however, can be adapted by 4 42 or silicontetrachloride (SiCI4), mainly used to deposit depositing a gradient layer on the interface. In this amorphous silicone (a-Si:H) layers for semi case, the film character is changed from more organic conductor fabrication, and is also of interest for to inorganic by variation of the gas ratio. The flexible solar cells on textiles.34 However, for textile structure of the gradient layer can be optimized using the mass deposition rate [Eq. (1) and Eq. with application, the organosilicon monomers show some (3)] a = advantages due to the possibility of low deposition 0.6 for oxygen added to HMDSO. Therefore, SiOx temperatures: PIasma po ymenzatlon coatings can be deposited on all textile and fiber 35 I" 0 f' organosilicon compounds is used to impart good materials. Gradient layers can also be deposited dielectric properties, thermal stability, scratch within continuous processes by flowing the gases in resistance, lowered friction, flame retardance and 120 r------baITier properties as well as to adjust the wettability of �------JPr. 100 PDMS textiles. Moreover, these films have been employed as • • gas filtering membranes36 or for UV protection of C • �g> 80 polymers.37 ro • SiO,Cy: H films Hexamethyldisiloxane [HMDSO; (CH3hSi-O 60 t5 • ro • Si(CH3hJ is the most common monomer, since the C o 40 liquid precursor has a high vapor pressure, is non u ;> • toxic and enables the deposition of siloxane coatings '0 20 �.------quartz at low temperatures. While at low energy inputs
However, due to long-living radical sites left within 3.4 Hydrophilic functional coatings the fluorocarbon film, these surfaces tend to get the Hydrophilic treatments of textiles and fibers are of aging effects by oxidation and reorientation, which great importance for many applications in printing, limits the oleophobic properties of plasma dyeing, lamination, fiber reinforced composites, polymerized FC coatings. Moreover, using textiles as capillary transport, etc. To avoid wet-chemical substrates an increased amount of unwanted treatments, plasma activation with non-polymerizable additional gases (water vapor and additives) might gases shows some positive effects such as cleaning, strongly influence the fluorocarbon film growth with etching, cross-linking, formation of radical sites and respect to adhesion and repellency. functional groups, which are able to enhance the Fluorocarbon plasmas were also investigated by binding in subsequent process steps. However, this 59 Vinogradov and Lunk under atmospheric pressure. type of plasma activation is prone to aging due to They obtained no deposition rate with the saturated internal re-orientation effects as well as external monomer C3FS unless hydrogen is added. Due to the influences. Aging can be strongly minimized by formation of toxic byproducts, low process velocities deposition of functional plasma polymers since and incorporation of oxygen, there are no real internal re-orientation processes are hindered by the advantages compared to low pressure plasmas. cross-linked film network. Moreover, a higher density Hence, though the plasma polymerization is of functional groups can be obtained by the film considered as an ecofriendly technique, the still volume as long as they are accessible within a improving wet-chemical treatments dominate the polymer matrix. market for stain repellent textiles, which show a good Thus, hydrocarbons can be effectively mixed with permanence by cross-linking through annealing (120- non-polymerizable gases such as Nz, NH3, O2, H20, 160 °C) and envelopment of the single fibers. A CO2 or others to obtain functional groups within a plasma activation, however, might be used to enhance cross-linked amorphous hydrocarbon network.3 the capillary transport of wet chemicals within the Rivaling processes of etching and polymerization can textile structure to improve the envelopment and thus be used to yield highly functionalized and permanent reduce the amount of chemicals needed.60 Oil plasma polymers. We used RF plasmas at Pa of to repellency of the maximum grade of 8 (according to gaseous mixtures of acetyle!1e with water vapor, AATCC 118-1972) can be attained. carbon dioxide and ammonia to obtain oxygen or Nevertheless, fluorocarbon treatments within low nitrogen containing functional groups on fabrics (PP, pressure plasmas are industrially performed on PET, CA, cotton and others) within our web coater. selected textiles when a low film thickness « 100 Evaluation of the mass deposition rates compared to HEGEMANN: PLASMA POLYMERIZATION AND ITS APPLICATIONS IN TEXTILES 107
pure C2H2 discharges shows that the admixture of A mixture of acetylene and oxygen (2: 1) was used 3 H20 has no influence on the deposition rate for by Feih and Schwartz6 to deposit plasma polymers on moderate specific energies W/Fm related to the PAN-based carbon fibers to increase the fiber-epoxy monomer flow (Fm) of C2H2 (Fig. 8). The reduced resin adhesion in composites. A 90% improvement in deposition rates compared to pure C2H2 indicates interfacial shear strength (IFSS) is found to be deviations in the growth mechanism. At higher energy accompanied by no significant change in the tensile inputs, however, a drop in the deposition rate strength of the carbon fibers, which is attributed to indicates inhibition of plasma polymerization. carbonyl and hydroxyl groups on the surface as well Admixture of CO2, on the other hand, reveals a as long-living free radicals entrapped within the reduced deposition rate by chemical etching effects, plasma polymer. Dilsiz al.64 used dioxane and et while ion-induced and chemical etching effects can be xylene/air plasmas to treat carbon fibers. The plasma observed with NH3. polymerized layers are fo und to heal flaws on the l2 According to Yasuda , the excessive H20 added to fiber surfaces and increase their tensile strengths. Low a monomer acts as an efficient modifier of the growth pressure plasma co-polymerization of hydrocarbon mechanism, which shifts the major growth path from monomers and oxygen or nitrogen containing reactive cycle 2 to cycle 1 (Fig. I), thus inhibiting plasma gases are carried out on an industrial level to obtain a polymerization. Water vapor admixture is found to permanent hydrophilic treatment of synthetic fabrics os strongly reduce the concentration of dangling bonds such as polyester and polyamide used for filtration. in the plasma polymers. Nitrogen and carbon oxide, Using dichloromethane within a RF plasma (10 on the other hand, have similar electron structures as Pa), the dyeability with reactive dyes can be enhanced acetylene and evidently participate in the chemical at short treatment times (10-45 s) on cotton and 06 reactions of cycle 2 (divalent reactive species). polyester fabrics. Functional C-O groups and free However, both 0 and N are etching gases, and radicals are formed within a plasma-polymerized thin energetic N2+ ions formed at higher energy inputs surface layer, whereas at longer treatment times yield strong etching effects. 18 etching processes are found to dominate. An increase Compared to Corona treatments, low pressure in the diffusion coefficient of acid dyes into wool is 67 plasma activation and plasma-polymerized SiOx reported by Wakida al. using an atmospheric coatings, these coatings show less aging effects under pressure plasma. Acetone/et Ar plasma polymerization storage at ambient air (Fig. 9). It is found that the produces a hydrophilic polymer which modifies the static contact angles increase less for mixtures of surface of the endocuticle or the cell membrane acetylene with oxygen or nitrogen containing gases. complex contributing to accelerated dye diffusion. Permanent hydrophilic treatments are of interest to Plasma-polymerized hydrophilic coatings of H20 or improve the sweat management of clothing. N2 mixed with acetylene, benzene and heteroaromatic amines are found to improve the characteristics of 0. 1 reverse osmosis membranes.68 oC2H2 C2H21NH3 o 80 E .c2H21H20 u u . C2H2IC02 70 NVl 0.01 E . u . ��.8. ___. - .-. _- c60 A - '-CL '. �------3 - - c .... 'i" ...... S1 'E .' .... Corona treatment 50 • 0 g> 0, , ...... ""G- -O--�--- '" Arl02 plasma , '" 0.001 0 � " • /0 0 � 4 .....SiOx coating .- /6 0 c: v a-C:H (O.N) coating 8 30 E / -0- u.. / . o E ' I' ex: -£ 20 .., 0.0001 10 02 'P-"v-:-: o Ql Q3 Q4 0.5 o CN/Fmrl [(W/sccmr11 o 5 10 15 20 25 Fig. 8- Mass deposition rates per monomer flow for pure Aging [days] acetylene discharges as well as C2H2!NH3, C2HiH20 and Fig. 9- Aging observed for polyester fabrics treated with C2H21C02 mixtures depending on the reaction parameter WIF", different kinds of plasma activation and plasma polymerization 108 INDIAN 1. FIDRE TEXT. RES., MARCH 2006
Silicontetrachloride (SiCI4) can also be used to enzyme immobilization on polysulphone deposit hydrophilic plasma coatings. While energetic membranes.82 plasma conditions lead to the formation of amorphous Allylamine plasma polymerization was silicon layers, milder plasmas retain some SiClx (x investigated for the improvement of fiber-matrix < 3) molecular fragments that easily convert to Si-OH adhesion in PE fiber reinforced epoxy resins83 or ' groups in the presence of atmospheric moisture (post aramid fiber reinforced composites.84 Monofunctional 9 plasma reactions).6 Additionally, the roughened plasma coatings are industrially used for the surface enhances the hydrophilicity of the treated PET regioselective treatment of separation membranes fabric surface. These layers were also reported to required for blood dialysis.85 Therefore, the blood is improve the PET fabric dyeing properties.7o led through a bundle of hollow fibers to separate blood cells from the blood plasma by suitable pore 3.5 Monofunctional Coatings sizes.86 The membrane wall should be functionalized Plasma polymers with functional groups can also with primary amino groups to immobilize scavengers be obtained using suitable monomers which already that are able to bind toxic components (endotoxines) contain the required functional group. Depending on sometimes found in the patient's blood. However, the energy input into the active plasma zone, these NH2 groups are not allowed at the inner surface of the functional groups can be retained during plasma hollow fibers to avoid direct contact with the blood. polymerization. Thus, monofunctional coatings can be Hence, wet-chemical treatments are excluded. tailored containing a varyirig amount of distinct Therefore, the fibers are continuously led through a functional groups, such as carboxyl (-COOH), amino sealing system from atmosphere to the low pressure (-NH2), hydroxyl (-OH) or ethylene-oxide (EO) units region, where an allylamine discharge is generated 71 (-CH2-CHrO-). -J7 which is not able to burn inside the hollow fi bers.87 Plasma polymerization of acrylic-like coatings on The reactive plasma species penetrates the fiber wall fabrics such as polyester or polyamide was from the outside to about two third of the wall investigated using low pressure plasmas with acrylic thickness forming amino groups within the porous acid as monomer.78 Keeping the fabrics inside the wall but not at the inner surfaces. plasma zone (at floating potential), good penetration Even polyaniline-like plasma polymers can be of the fabrics is achieved by a both side treatment. deposited from aniline within low pressure discharges Acrylic-like coatings are found to enhance wettability, (40-50 Pa) by retention of quinoid and benzenoid dyeability (using basic dyes) and soil resistance, while rings, showing a conductivity of 10-1 1 cm-I , which rrl they show less aging compared to plasma treatments is noticeably higher than other plasma pOlymers.88 78 with non-polymerizable gases (02, H20, Ar, air). However, the quality of conductive plasma polymers The color depth of dyed fabrics (polyester/cotton is limited due to cross-linking reactions, Conductive 8 blend) increases with the acrylic-like film thickness. polypyrrole-coated polyester fabrics are produced by Stable plasma-deposited acrylic acid surfaces also plasma polymerization of 1-(3-hydroxypropyl)pyrrole enable improved cell adhesion for tissue resulting in pyrrole moieties covalently bonded to the . . 9 engmeenng. 7 fabrics.89 It is observed that the coated fabrics neither Sarmadi et al. 80 reported the surface modification cause hemolysis nor they alter the blood coagulation of PP fabri'cs by acrylonitrile cold plasma to deposit properties. Hence, they are considered as polyacrylonitrile-like (PAN) layers. The presence of biocompatible coatings in cardiovascular applications. nitrogen- and carbon-based unsaturated linkages and The retention of ethylene-oxide moieties within the formation of second generation =C=O groups led plasma polymer films is known to impart non-fouling to improved water absorption and dyeing properties. properties to surfaces by deposition of polyethylene According to the authors, short treatment times should oxide (PEO)-like coatings.9o Using di-ethylene glycol make industrial application possible. dimethyl ether (DEGDME or diglyme) as monomer, Plasma deposition of acrylamide (AAm) on silk the PEO character of the plasma-polymerized films fabrics (RF plasma, 650 Pa) was found to improve the (RF plasma, 50 Pa) can be varied depending on the elastic recovery of the fabrics. 8 I The retention of power input and gas flow.77 The PEO character is hydroxyl groups (-OH) can be performed using commonly defined as the relative per cent of ether plasma polymerization of allyl alcohol, e.g. for carbon functionalities (at 286.5 e V) of the CIs high- HEGEMANN: PLASMA POL YMERIZA TION AND ITS APPLICATIONS IN TEXTILES 109
resolution scan usmg X-ray Photoelectron 80 Spectroscopy (XPS). Figure 10 shows the evolution 70 of PEO character, depending on the energy input (WIFm) with respect to the monomer flow. Higher 60 * amounts indicate a higher retention and less -;:: 50 CD fragmentation during the plasma process. U� 40 Good non-fouling properties can be obtained for a .s:: @0 PEO character exceeding 75%. Therefore, low 30 specific energies, noticeably below the corresponding a. 20 activation energy, are required to obtain swellable (hydrogel) coatings that effectively screen the surface 10 by water adsorption to avoid biomaterial adhesion. 0 0 1000 2000 3000 .aoo 5000 6000 7000 The energy input can be further decreased using [J/Cm31 pulsed plasma polymerization. Wu et al.91.92 used WlFm Fig. 10- Retention of ethylene-oxide units during plasma diethylene glycol vinyl ether (E02V) well cyclic as as polymerization of DEGDME, given by the PEO character ethers at 4-10 Pa pressure and varying RF plasma depending on energy input77 cycles (on and off times) for power modulation. A high PEO character was reported for low specific energies, which can be further examined by evaluation of the mass deposition rates as shown in 10 Fig. 11. Non-fouling properties can be observed for • E02V E energy inputs below the activation energy. 8 o 12-crown-4 ether 5 0.------__ -, metal cathodic arc ignited in the presence of acetylene l14 As-deposited to form a dual plasma or by combining plasma -<>- _ 40 ..... IterA annealing (Ar. 1200 .c) polymerization of CHJAr with DC magnetron o :i? .....-Afterannea ling lAir. 12oo'C) sputtering of several target materials.1 15 Thus, metal c �o 30 nanoclusters or nanocrystalline metallic carbides can C be embedded in the carbon network. � 116 11 20 Barranco et al. . 7 examined the possibility of the 8c incorporation of macromolecules such as dyestuff in c Ql 0> porous columnar inorganic SiOx coatings using 0>- 10 plasma co-polymerization. The films were deposited in a remote microwave reactor using tetramethylsilane __�� __ O������������ 100 200 300 400� �600 (TMS) and tetraethylorthosilicate (TEOS) as a SiBCN SOO organosilicone precursors and dye sublimation, filmdepth [nm) yielding a durable dyeing procedure. Fig. 12- Oxygen concentration at SiBCN film surfaces measured by XPS under Ar sputtering 4 Up-scaling The transfer of plasma polymerization processes transparent conductive oxide or piezoceramic lead into the textile industry is a major concern of today's 105.106 zirconate titanate (PZT) coatings. plasma research activities. As long as the effects that can be achieved by atmospheric plasmas are weak, 3.7 Plasma Co-polymerization low pressure plasma processes are still state-of-the-art By using proper experimental configurations, it is technology. Generally, these processes are optimized possible to couple a sputtering or an evaporation using batch reactors and then transferred to (semi process with plasma co-polymerization in a way that continuously operating pilot-scale reactors to clusters of material (metal, ceramic, polymer) can be demonstrate the feasibility for an industrial up-scale. 107 included in a plasma-deposited organic matrix. For an efficient up-scaling similarity parameters can Examples are Au-containing teflon-like and quartz be identified enabling the transfer of plasma 108.109 like coatings. Released Au nanoparticles are polymerization processes to different reactor found to specifically bind to cancer cells pushing the geometn. es. llo 16 field of nanobiotechnology. Of special interest for The deposition from highly fragmented monomers textile application are silver-containing PEO-like under the interaction of high energetic particles is coatings, which couple the non-fouling properties of mainly controlled by the bias potential applied to the polyethylene-oxide (PEO) polymers with the anti deposition electrode. The transfer to different reactor 111 bacterial effects of silver. Combining sputter geometries can then simply be performed by conditions with plasma polymerization through a high maintammg bias potential and pressure. The excess of Ar added to the OEGOME monomer, Ag deposition of DLC and ceramic coatings are 77 nanoparticles are incorporated in the growing film. examples. Nevertheless, the deposition rates should be The remaining PEO character (27.5 %) and the anti adapted since the forces applied by the internal bacterial effects through the release of Ag ions in wet stresses of the hard coatings linearly scale with the + conditions are found to completely prevent the film thickness. For thicker films, gradient layers adhesion of P. aeruginosa, which might be used for might be required to attain good adhesion on flexible medical textiles such as wound bandages. Monovalent substrates, which must also be controlled. In most silver ions specifically bind to bacteria via sulphydryl cases, the deposition of plasma polymers obtained (-SH) groups at their cell membrane surface and under moderate or weak interaction of energetic 112 h· d er t h elr' energy trans fer system. particles has to be transferred to different (larger) III Certain toxic elements such as Cu, Ag and V can reactors. Thus, the identification of a similarity also be embedded in OLC coatings, which are parameter strongly facilitates up-scaling. released and cause toxic reactions when exposed to As discussed earlier, the measurement of the mass biological media.113 This allows the preparation of deposition rates of plasma polymers depending on the surfaces with a tunable antibacterial effect. Metal energy input, which can easily be carried out by containing OLC coatings can be prepared using a weighing the samples (e.g. thin glass slides), is a HEGEMANN: PLASMA POLYMERIZATION AND ITS APPLICATIONS IN TEXTILES III convenient method to corresponding lIS · derive the · activation energy according to Eq. (1). This activation · 110 energy can be used to optimize the hydrophobic o properties of plasma-polymerized siloxane coatings -; 105 � using HMDSO as monomer while obtaining highly 100 • cIO � 15 til durable surfaces. If the geometrical factors used in ti _ Receding til �d- ��• E y . Eq. (2) are not known for the considered plasma 95 -." 0-_ 8 -�-����====��--o reactors, the measurement of the deposition rates is · Q; · --Web --- Adv.lre<:.. i· iii 90 coater repeated for the new reactor to identify the · -<>-Sym. -<>-Adv.frec. � · · small · _Sym. large --Adv.frec. corresponding reactor, depending on the activation 85 : -O--Asym. large Adv .frec. energy that can then be used to scale the plasma Ea -0-- process. Knowledge or an estimation of the 80 50 100 1 50 250 350 o 200 300 [J/cm1 geometrical factors help to speed up the transfer by S reducing the required experiments due to a good Fig. 13- Water contact angles of HMDSO-derived plasma starting range for the reaction parameter power input polymers using different batch reactors (asymmetric and per gas flow (W/F). Figure 13 shows the water contact symmetric set-ups of different sizes) angles of plasma-polymerized siloxane coatings (ref. 66), whereas fluorocarbon layers can be 2 obtained using different plasma reactors with respect deposited within 30s and 4 rnlmin respectively.6 to the activation energy (E{/). Deposition rates for hard coatings (ceramics, DLC), The highest contact angles are obtained at energy on the other hand, might be around 10 nrnlmin. If inputs close to Ea. A slight difference can be observed rather thick coatings of around 200 nm are required, using either asymmetric or symmetric reactors. While the process velocity might be reduced down to 0. 1 the interaction of energetic particles during plasma rnlmin. These considerations demonstrate that it is polymerization is weak within the symmetric reactor, generally difficult to integrate a plasma the asymmetric set-up causes a stronger ion polymerization process directly into a textile bombardment due to a higher sheath voltage, yielding production line, even if atmospheric pressure plasma a shift in the retention of methyl groups at the processes would be available. For SiOx deposition on growing film surface. Nevertheless, the hydrophobic PET fabrics within a dielectric barrier discharge a plasma treatments can be transferred using the deposition rate of around 15 nrnlmin (for HMOS and demonstrated macroscopic approach. Recently, it has TIMSVS) was reported51, which is noticeably lower been demonstrated that in addition to pure monomer than low pressure plasma polymerization from discharges, the mixture of different gasses can also be organosilicones. Therefore, there is no real difference IS transferred [Eq. (3)]. between low and atmospheric pressure plasmas with For industrial-scale processes also the efficiency of respect to the processability being a semi-continuous plasma polymerization processes is of great interest. process. For the treatment of textile fabrics, knits and Hence, it strongly depends on the application and nonwovens, a plasma length and width of around 2 m the corresponding market situation, whether a plasma can be assumed; a larger width might also be polymerization is economically suitable or not. The 6 possible. 1 High deposition rates can be achieved, e.g. decisive add-on value, that allows the cost of product with organosilicones to influence wettability, friction, to be well above the cost of unprocessed product permeability and mechanical properties of textiles. and/or that cannot be attained by other means, is the Considering that, for a typical treatment a film key factor in selecting plasma polymerization. I IS thickness of at least 10 nm is required to account for Further advantages of plasma, which should be taken the textile structure and roughness, which can be into account, are an environment-friendly dry process deposited at a rate of 10 nrnls and the process without requiring any additional manipulation such as velocities exceeding 100 rnlmin are thus achievable. wetting or drying, deposition of nanoscaled coatings, However, many plasma polymerization processes take that do not significantly affect the original more than one second. The improvement of the characteristics of fabrics, such as breathability, feel, dyeability of cotton is reported to be optimum within softness, and mechanical strength, and the higher 12s, yielding a possible process velocity of 10 rnlmin durability of the plasma-polymerized coatings 112 INDIAN FIBRE TEXT. RES., MARCH 2006 1. compared to many wet-chemical processes. Yasuda11S covalently bonded to the textile surfaces, being an has recently proven the efficiency of plasma ecofriendly technique. The key factor for plasma polymerization processes for different commercial polymerization, however, is given by the add-on applications, even when the investment of a large value . outperforming other available techniques. vacuum system has to be taken into account. Web Examples are tailored plasma polymers containing coaters suitable for plasma polymerization processes functional groups to achieve permanent hydrophilic on textiles can be purchased from different treatments for improved wicking and adhesion or companies. specific binding of linker molecules, enabling Process velocities can be enhanced if the treatment regioselective treatments on hollow fibers used for is performed on yarns or monofilament fibers that can blood dialy,sis. be processed in air and led several times through the The industrial scale-up is facilitated by the (low pressure) plasma zone, thus improving the identification of similarity parameters, which enable plasma length. Process velocities of several 100 the optimization of plasma polymerization conditions mlmin can be achieved with a true continuous on (lab-scale) batch reactors. Both industrial-scale process, meeting the velocity of other textile web and fiber coaters are already implem(�nted by processes and thus enabling the integration into a different companies to produce high-value added production line (e.g. for aramid fibers). Industrial textiles and related materials. However, a direct implementation is currently under way. incorporation into an in-line production is difficult to attain due to the achievable process velocities. Conclusions 5 Moreover, high investment costs or the requirement The textile industry nowadays strongly requires of vacuum technology hold back many interested . innovations and transformations to account for the companies, although the new technology might be challenging market situation and thus demands the more efficient for the considered process. Hence, inclusion of new technologies. Especially, plasma plasma polymerization is still a process merely used technology is offering an attractive way to add new for textile niche products. Comparing the functionalities such as water repellence, development with other web-based products such as hydrophilicity, dyeability, conductivity and packagings, however, a high potential can be expected biocompatibility due to the nanoscaled and tailored for the future. Therefore, research both on low and modification of textiles and fibers. Plasma atmospheric pressure plasmas is assumed to be polymerization, which leads to the deposition of thin forward-looking and should be strongly supported to coatings via gas phase activation and plasma-substrate stimulate the textiie sector. interactions, enables the design of more or less cross Plasma-modified textiles enable new and linked plasma polymers containing more or less interesting application in different fields such as functional groups covering the entire range from clothing, filtration, automotive industry, architecture, swell able hydrogel-like (PEO-like) up to diamond medical engineering and biotechnology. like (DLC) coatings. Generally, these plasma polymers are more durable compared to other surface Acknowledgement modification techniques (wet-chemistry, radiation or The author is thankful to all the co-workers at plasma activation), being surface sensitive and EMPA for their contributions. Thanks are also due to ecofriendly. the Commission of Technology and Innovation (CTI) , Different (low pressure) plasma polymerization Switzerland, for granting funds for parts of the study. processes are already transferred to an industrial level. Siloxane coatings derived from organosilicone References discharges are used as fluorine-free hydrophobic 1 Kang Y & Sarmadi M, AATCC Rev. lO (2004) 28. 1- coatings, whereas fluorocarbons are plasma 2 Li R, Ye L & Mai Y-W, Composites Part A, 28 (1997) 73. polymerized as stain repellent coatings showing better 3 Yasuda H, Plasma Polymerization (Academic Press, New York), 1985. durability compared to common wet-chemical 4 Wakida T & Tokino S, Indian J Fibre Text Res, 21 (1996) treatments. Moreover, textile properties, such as feel 69. (touch), optics and mechanical strength, remain 5 Massines F, Rabehi A, Decomps P & Gadri R B, J Appl unaffected by the nanoscaled plasma polymers Phys, 83 (1998) 2950. HEGEMANN: PLASMA POLYMERIZATION AND ITS APPLICATIONS IN TEXTILES 113 6 Pichal J, Koller J, Aubrecht L. Vatuna T & Spatenka P, in d' Agostino (Academic Press, San Diego, USA), 1990, Plasma Polymers lind Related Materials, edited by M 163. Mutlu (Hacettepe University Press, Ankara, Turkey), 36 Roualdes S, Van der Lee A, Berjoan R, Sanchez J & 2005, 201. Durand J, A1ChE J, 7 (1999) 1575. 7 Hocker H, Pure Appl Chem, 74 (2002) 423. 37 Zajickova L, Bursickova V, Perina V, Mackova A, Subedi 8 Kang J-Y & Sarmadi M, AATCC Rev, 11 (2004) 29. D, Janca J & Smirnov S, Surf Coat Tee/lIlol, 142-144 9 Kaplan S L, Praceedings, 41th Ann Tech Canf SVC (2001) 449. (Boston, MA), 1998, 345. 38 Jiao C Q, DeJosph C A (Jr) & Garscadden A, J Vac Sci 10 Simionescu C I, Denes F, Macoveanu M M & Negulescu Technol A, 23 (2005) 1295. I, Makromal Chem , 8 (1984) 17. 39 Hegemann D, Brunner H & Oehr C, Proceedings, 45th 11 Luo S & van Ooij W J, J Adhesian Sci Techl/al, 16 (2002) Ann Te ch COllf SVC (Lake Buena Vista, FL), 2002, 174. 1715. 40 Chatham H, Stll! Coat Te clulOl, 78 (1996) 1. 12 Yasuda H, Luminaus Chemical Vapar Depasition and 41 Li K & Meichsner J, SUI! Coat Tee/mol, 116- 119 (1999) Interfa ce Engineering (Marcel Dekker, New York), 2005. 84 1. 13 Rutscher A & Wagner H-E, Plasma Saurces Sci Te chllol, 42 Hegemann D, Oehr C & Fischer A, J Vae Sci Techl/ol A, 2 (1993) 279. 23 (2005) 5. 14 Yeh Y S, Shyy I N & Yasuda H, J Appl PalYIll Sci, Appl 43 Benitez F, Martinez E & Esteve J, Th ill Solid Films, 377- Palym Symp, 42 (1988) 1. 378 (2000) 109. 15 Hegemann D, Brunner H & Oehr C, Plasmas PolYIll, 6 44 Hegemann D, Brunner H & Oehr C, Nucl lllstr Metll Ph),s (2001) 221. Res B, 208 (2003) 281. 45 Schartel B, KUhn G, Mix R & Friedrich J, Maeromal 16 Hegemann D, Balazs D J, Amberg M & Fischer A, Mater Ellg, Praceedings. 17th Intematianal SympasiulIl an Plasllla 287 (2002) 579. 46 Hegemann D, Oehr C & Fischer A, in Plasma Processes Chemistry (Toronto, Canada), 2005. and Polymers, edited by R d' Agostino, P Favia, C Oehr & 17 Hegemann D, SchUtz U & Fischer A, Surf Caat Te e/mal, M R Wertheimer (Wiley-VCH, Weinheim, Germany), 200 (2005) 458. 2005, 23. 18 Hegemann D & Hossain M M, Plasma Process PalYIll, 2 47 Zanini S, Riccardi C, Orlandi M, Esena P, Tontini M, (2005) 554. Milani M & Cassio V, SlIrfCoat Te chnal, 200 (2005) 953. 19 Hegemann D, in Plasma Polymers & Related Materials, 48 Sarmadi M, Ying T H & Denes F, Eur PalYIll J, 31 (1995) edited by M Mutlu (University Press, Ankara, Turkey), 847. 2005, 191. 49 Kettle A Jones F R, Alexander M R, Short R D, 20 Radu C-D, Kiekens P & Verschuren J, in Surfa ce Stollenwerkp, M, Zabold J, Michaeli W, Wu W, Jacobs E & Characteristics of Fibers and Textiles, edited by C M Verpoest I, Camposites-Part A, 29 (1998) 241. Pastore & P Kierens (Marcel Dekker, New York), 2001, 50 Bankovic P, Demarquette M R & Da Silva M L P, Mater 203. Sci Eng B, 112 (2004) 165. 21 Vohrer U, MUller M & Oehr C, SUI! Coat Technal, 98 51 Lee H-R, Kim D & Lee K-H, SUI! Caat Te chnol, 142- 144 (1998) 1128. (2001) 468. 22 Keller M, Ritter A, Reimann P, Thommen V, Fischer A & 52 Fisher E R, Exploring radical-slll!ace illferactiolls during Hegemann D, Surf Coat Te chnol, 200 (2005) 1045. plasma etching and deposition, paper presented at the 17th 23 Pane S, Tedesco R & Greger R, J Industrial Text, 31 International Symposium on Plasma Chemistry, Toronto, (2001) 135. Canada, 07- 12 August 2005. 24 Lindner M, Bauer-Gogonea S, Bauer S, Paajanen M & 53 Iriyama Y, Yasuda T, Cho D L & Yasuda H, J Appl Polym Raukola J, J Appl Phys, 91 (2002) 5283. Sci, 39 (1990) 249. 25 Poll H U, Schladitz U & Schreiter S, SUI! Coat Technal, 54 d' Agostino R, Cramarossa F, Fracassi F & IIluzzi F, in 142-144 (2001) 489. Plasma Depasition, Treatment, and Etching of Polymers, 26 Bami R, Riccardi C & Fontanesi M, J Vac Sci Te e/1I101 A, edited by R d' Agostino (Academic Press, San Diego, 21 (2003) 683. USA), 1990, 95. 27 Europlasma Technical Paper, 2004. www.europlasma.be. 55 CoburnJ W & Winters H F, J Vac Sci Technol, 16 (1979) 28 Sigma Technologies International. www.sigmalabs.com. 391. 29 Harmati Z & Hegemann D, Materia/wiss We rkstofftechnik, 56 Cheng T-S, Lin H-T & Chuang M-J, Mater LeU, 58 (2004) 36 (2005) 198. 650. 30 Hauert R & MUller U, Diam Rei Mater, 12 (2003) 171. 57 Barz J, Haupt M, Vohrer U, Hilgers H & Oehr C, Sill! 31 Luo S, van Ooij W J, Mader E & Mai K, Rubber Chelll Coat Te chnol, 200 (2005) 453. Technol, 73 (2000) 121. 58 Chaivan P, Pasaja N, Boonyawan D, Suanpoot P & 32 Ooij W J, Luo S & Datta S, Plasma PolYIll, 4 (1999) 33. Vilaithong T, Sw! Coat Te chnol, 193 (2005) 356. 33 Weisweiler W & Schlitter K, Th in Solid Films, 207 (1992) 59 Yinogradov I P & Lunk A, Surf Coat Te chllol, 200 (2005) 158. 660. 34 Wilson J & Mather R, Technical Text Int, 12 (2002) 5. 60 Hegemann D, Adv Eng Mater, 7 (2005) 40 I. 35 Wrobel A M & Wertheimer M R, in Plasma Depositian, 61 Lippens P, Low pressure vacuum plasma treatment of Treatment, and Etching £If Palymers, edited by R technical textiles and lion wavens: An overview, paper 114 INDIAN 1. FIBRE TEXT. RES., MARCH 2006 presented at Nano Textiles, SLGallen, Switzerland, 15 88 Gong X, Dai L, Mau A W H & Griesser H J, J Polym Sci September 2005. [AJ Polym Chem, 36 (1998) 633. 62 Zhang 1, France P, Radomyselskiy A, Datta S, Zhao J & 89 Zhang Z, Roy R, Dugre F J, Tessier 0 & Dao L H, J van Ooij W, J App! Polym Sci, 88 (2003) 1473. Biomed Mate·r Res, 57 (2001) 63. 63 Feih S & Schwartz P, J Adhesion Sci Technol, 12 (1998) 90 Lopez G P, Ratner B 0, Tidwell C 0, Haycox C L, 523. R J & Horbett T A, J Biomed Mater Res, 26 64 Dilsiz N, Ebert E, Weisweiler W & Akovali G, J Colloid Rapoza(1992) 415 . 111le�lSci, 170 (1995) 24 1. 91 Wu Y J, Timmons R B, Jen J S & Molock FE, Coll Surf 65 Chabrecek P, New surfa ce fu nctionalities fo r technical [BJ Bioilllelfaces, 18 (2000) 235. Sefa r fa brics, paper presented at the conference on Nano 92 Wu Y J, Griggs A J, Jen J S, Manolache S. Denes F S & Textiles, SLGaUen, Switzerland, 15 September 2005. Timmons R B, PLasmas Polym, 6 (200 I) 123. 66 Jahagirdar C 1 & Tiwari L B. J Appl Polym Sci, 94 (2004) 93 Daoud W A & Xin J JAm Ceram Soc, 87 953. H, (2004) 2014. 94 Fujishima A, Rao T N & Tryk 0 A, J Photochelll 67 Wakida T, Tokino Niu S, Kawamura H, SatoY, Lee M, S, Phmobio C: Photochem Rev. 1 (2000) 1. Uchiyama H & Inagaki H, Text Res J. 63 (1993) 433. 95 Guillard C, DebayJe D. Gagnaire A, Jaffrezic H & 68 Yasuda H, MaTsh H C & Tsai J, J AppL Polym Sci, 19 Herrmann1-M, Mater Res Bull, 39 1445. (1975) 2157. (2004) % Szymanowski Sobczyk A, Gazicki-Lipman M, 69 Negulescu Despa S. Chen J Collier B, Res J, 70 lL l, & TeK.! Jakubowski W & Klimek L, Swj" Coat TechnoL, 200 (2000) I. (2005) 1036. 70 Sarmadi M, Denes A R & Denes F, Text Chem Color, 28 97 M & Hirthe B, Chem Fibers Int, 49 (1999) 528. (19%) 17. WedIer 98 Aragi L M, Mater Te chno!, 10 (1995) 192. 71 Oehr C, MUller M, Elkin B, Hegemann D & U, Vohrer 99 D, Pwsma-assisted processes fo r the Surj"Coat Te chnol, 116- 119 (1999) 25. Hegemann deposition of /lew hard cOalings, PhD thesis, Technical 72 Sciarratta Vohrer U, Hegemann 0, MUller M & Oehr V, University, Darmstadt. Germany, 1999. C, Surj"Coar Techno!. 174-175 (2003)805. 100 Robertson J, Diam ReL Marer, 3 (1994) 361. 73 Friedrich 1, KUhn G & Mix R, in Plasma Processes and' Polymers, edited by R d'Agostino, P Favia, C Oehr & M 101 Hegemann 0, Oehr C & Riedel R, Proceedings, 14th R Wertheimer (Wiley-VCH, Weinheim, Germany), 2005, IlIternatiollaL Symposium on Plasma Chemistry (Prague, 3. Czech Republic), 1999, 1573. 74 Besch W, Schroder K & Ohl A, Plasma Process PolYl11, 2 102 Hegemann 0, Riedel R & Oehr C, Chem Yap Deposition, (2005) 97. 5 (1999) 61. 75 Oran U, Swaraj S, Friedrich 1 F & Unger W E S, Plasma 103 Hegemann 0, Plasma deposition of hard and thermal Process Polym, 2 (2005) 563. resistant coatings ill the system Si-B-C-N, paper presented 76 Swaraj S, Oran U, Lippitz A, Friedrich 1 F & Unger W E at the 47th A VS International Symposium, Boston, MA, S, Plasma Process Polym, 2 (2005) 572. 02-06 October 2000. 77 Balazs 0 J, Triandafillu K, Sardella E, Iacoviello G, Favia 104 Rooke M A & Sherwood P M A, Chem Mater, 9 (1997), P, d'Agostino R, Harms H & Mathieu H J, in Plasma 285. Processes alld Polymers, edited by R d' Agostino, P Favia, 105 Fischer A. Schwarz R, GHintz K, Haug F J, Amberg M & C Oehr & M R Wertheimer (Wiley-VCR Weinheim, Seyfang G, ITO thill .film depositioll by reactive DC Germany), 2005, 351. magnetron sputtering 011 poLymer substrates, paper 78 Oktem T, Seventekin N, Ayhan H & Piskin E, Turk J presented at the 9th International Conference on Plasma Chelll, 24 (2000) 275. Surface Engineering, Garmisch-Partenkirchen, Germany, 79 Detomaso L, Gristina R, Senesi G S, d'Agostino R & 13-17 September 2004. Favia P, Biomater, 26 (2005) 3831. 106 Thapliyal R, Schwaller P, Amberg M, Haug F J, Fortunato 80 Sarmadi M, Ying T H & Denes F, Text Res J, 63 (1993) G, Hegemann 0, Hug H J & Fischer A, Surf Coat Techno/, 697. 200 (2005) 1051. 81 Zhang J, J Appl Polym Sci, 64 (1997) 1713. 107 Biederman H & Martinu L, in Plasma Deposition. 82 Gancarz I, Bryjak J, Bryjak M, Pozniak G & Tylus W, Eur Treatment, and Etching of PoLymers, edited by R Polym J, 39 (2003) 1615. d' Agostino (Academic Press, San Diego, USA), 1990, 83 Li Z-F & Netravali AN. J Appl Polym Sci, 44 (1992) 333. 269. 84 Shaker M, Kamel I, Ko F & Song J W, J Composite 108 d' Agostino R, Martinu L & Pische V, PLasma Chelll Te chnol Res, 18 (1996) 249. Plasma Proc, 11 (1991) I. 85 Oehr C, in Plasma Processes and PoLymers, edited by R 109 Fracassi F, d' Agostino R, Palumbo F, Bellucci F & d' Agostino, P Favia, C Oehr & M R Wertheimer (Wiley Monetta, T, Th in Solid FiLms, 272 (1996) 60. VCH, Weinheim, Germany), 2005, 309. 110 EI-Sayed I H, Huang X & EI-Sayed M A, Nal/o Lett, 5 86 Goehl H, Deppisch R, Storr M & Buck R, Blood Purif, 15 (2005) 829. (1997) 36. III Favia P, Pinto Mota R, Vulpio M, Marino R, d' Agostino R 87 MUller M & Oehr C, Surf Coat Te chnol, 116-1 19 (1999) & Catalano M, PLasmas Polym, 5 (2000) 1. 802. 112 Davies R L & Etris SF, Cawl Today, 36 (1997) 107. HEGEMANN: PLASMA POLYMERIZATION AND ITS APPUCATIONS IN TEXTILES Il5 113 Hauert R, Diam Rel Mater, 12 (2003) 583. Barranco A, Bielmann Groening Wildmer R & 117 M, 0, 114 Fu R K Y, Mei Y F, Fu M Liu X Y & Chu P K, Diam Groening P, dye-contailling thill y, Plasma polymerization of Rel Mater, 14 (2005) 1489. films, paper presented at the International Conference 9th 115 Corbella C, Pascual E, Canillas A, Bertran E & Andujar J on Plasma Surface Engineering, Gannisch-Partenkirchen, L, Th in Solid Films, 455-456 (2004) 370. Germany, 13-17 September2004. 116 Barranco A, Cotrino 1, Yubero F & Gonzalez-Elipe A R, 118 Yasuda H & Matsuzawa Y, Plasma 2 Process Po/ym, J Vae Sci Te clmol A, 21 (2003) 1655. (2005) 507.