The following is a list of the abstracts for papers which will be presented in the FIFTH INTERNATIONAL SYMPOSIUM ON POLYMER SURFACE MODIFICATION The listing is alphabetical by presenting author. This list is updated continually to add abstracts as they become available and make appropriate corrections. This list may be conveniently searched by using the editor provided with most popular browsers (e.g. Microsoft Explorer, Netscape, ... etc.)

Rashidul Alam1, M Ibrahim H Mondal1 & Mubarak A. Khan2

1) University of Rajshahi

2) Radiation and polymer Chemistry Laboratory, Institute of Nuclear Science and Technology, Bangladesh Atomic Energy Commission. P.O. Box 3787, Dhaka, Bangladesh

Roll of 3-(trimethoxysilyl) Methacrylate on the Improvement of Chitosan Film by Photocuring

Chitosan was prepared from chitin using a deacetylation process. The degree of deacetylation of chitosan were determined by infrared spectroscopy respectively. Chitosan film was cures under, ultraviolet radiation with 3-(trimethoxysilyl) propylmethaacrylate in order to improve the mechanical properties with reduced water absorption character. A series of solution of different silane concentrations in methanol, along with photoinitiator Darocur-1664, were prepared. The radiation doses, monomer concentration, soaking time were optimized with the extent of grafting of monomer and mechanical properties of the cured films. The maximum tensile strength and elongation at break was 28 MPa and 32% respectively. The silanized chitosan films were characterized by DSC, FTIR and SEM. All the results relevant that the silane might be reacted with chitosan or deposited on the surface of the film. Water uptake gel content were also studied The formulation contained 35% silane,61% MeOH and 4% photoinitiator Darocur 1664 showed the best performance at 24th UV pass for 4 min soaking time. The effect of simulating weather, soil and water on degradable properties of samples was also performed. The silane treated film produced the minimum loss of the properties as well as a lower water uptake than those of the untreated one.

Carl Lawrence Aronson1, Douglas Beloskur1, Bryce Burland1, Jared Perez1, Ali Zand1, John M. Kokosa1 and Lars Guenter Beholz2

1) Department of Science and Mathematics, Kettering University, Flint, Michigan 48504

2) Beholz Technology, L.L.C., Flint, Michigan 48502

New Pathways for Modifying the Surface of High Density Polyethylene: Chemically Benign Adhesion Promotion and Subsequent Functionalization

Despite the engineering versatility of high density polyethylene (HDPE), its pristine surface cannot be easily tailored chemically due to its non-polar and unreactive nature. The surface of HDPE was modified here using a two-step chemical process. HDPE panels were initially immersed in a heated, aqueous hypochlorite solution containing a carboxylic acid and quenched with deionized water at room temperature following a heterogeneous chemical reaction process patented by Beholz (U.S. Patents 6,077,913 and 6,100,343). 1 - 10 mole percent chlorine heteroatoms were identified on the resulting HDPE surface using ESCA techniques. The surface chlorine concentration was measured as a function of reaction time, stoichiometry and number of repeated treatments. The chlorinated HDPE surface was subsequently exposed to ultra-violet (UV) light and surface alkene moieties were noted using ATR FT-IR methods along with a concomitant reduction in surface chlorine. The free radical surface dehydrochlorination mechanism was observed to follow first-order kinetics. Reaction of small molecular weight molecules, including n-alkanes or aromatic compounds, with NaOCl/acetic anhydride in aqueous solution as characterized using GC/MS techniques has further elucidated the mechanistic pathway for HDPE chlorination. Reactivity of the surface alkene groups was demonstrated using a variety of electrophilic addition reagents including Br2. Poly(4-hydroxy styrene) architectures were covalently tethered to the unsaturated HDPE surface in an effort to ultimately tailor surface polarity and adhesiveness as well as create laminate poly(a-olefin) containing structures. This efficient, economical and benign surface chlorination/photochemical treatment process produces relatively small handling and disposal risks as well as no apparent polymer degradation.

Thomas Bahners, Klaus Opwis and Eckhard Schollmeyer; Deutsches Textilforschungszentrum Nord-West e. V., Adlerstr. 1, 47798 Krefeld, GERMANY

Shang-Lin Gao and Edith Mäder; Institut für Polymerforschung, Hohe Str. 6, D-01069 Dresden, GERMANY

Excimer UV Lamp Irradiation Induced Crosslinking on PET Surfaces

The irradiation of a polymer by UV light effects photochemical surface modifications, if the photons are sufficiently absorbed by the substrate. Due to their monochromatic nature, excimer lamps allows to optimize the light source for the absorption properties of the substrate, resulting in radical generation with a very high quantum yield.

A photo-chemical process can be considered as irradiation of the substrate in some sort of reactive or inert atmosphere. Under the condition of a low or non-absorbing atmosphere and a strong absorbing substrate, the actual reaction takes place at the boundary, where radical processes are initialized. Four different types of reactions are possible: (I) Recombination of radicals, (II) cross-linking of polymer chains, (III) addition of radicals from the reactive atmosphere and (IV) addition of bi-functional molecules with ensuing cross-linking.

The scope of this work was to study the occurrence of cross-linking of the polymer itself (reaction type II) and deposition of cross-linked thin-layers (reaction type IV) following a photo-chemical surface treatment in the presence of bi-functional molecules.

Besides the study of the alkaline hydrolysis of PET fibers, which indicates barrier formation at the surface , microscopic/nanoscopic analyses were performed. Atomic Force Microscopy (AFM) was used as sensitive tool to investigate the outermost surface layer in nanoscale dimensions (up to 100 nm) both nanomechanically and thermally. In addition, the topography of modified surfaces and the adhesion forces (adhesive and attractive forces) were determined for differently modified surfaces together with ÁTMA measurements to characterise the local surface changes in comparison with the reference PET-surface.

Goknur Bayram, Guralp Ozkoc and Pinar Kurkcu; Department of Chemical Engineering, Middle East Technical University, 06531 Ankara, TURKEY

Improvement of Adhesion Between Poly(tetrafluoroethylene) and Poly(ethylene terephthalate) Films

Poly(tetrafluoroethylene) (PTFE) and biaxially oriented poly(ethylene terephthalate) (PET) films are two important classes of polymeric materials used in many industrial applications. PTFE, because of its chemical inertness, heat resistance, excellent barrier properties and low coefficient of friction, has a matchless position in the plastic markets. On the other hand, PET is an important polyester film having high tensile strength, excellent dimensional stability, good barrier properties, excellent optical properties, recycle-ability and reduced cost. Hence, combination of PET and PTFE in a multilayer film construction provides high performance/cost ratio compared to individual components. In the current study, it was aimed to improve the adhesion in multilayer films produced by hot-pressing of PTFE and recycled-PET films at the presence of a reactive tie layer of melt blended PTFE/Ethylene-methyl acrylate-glycidyl methacrylate terpolymer. The multilayer films with various compositions of tie layers (0% PTFE, 20% PTFE, 35% PTFE and 50% PTFE) were processed at 9 different bonding-time and bonding-temperature combinations. For the modification of PTFE to enhance adhesion, poly(acrylic acid) was grafted to the surface of PTFE film via wet chemistry. T-peel test, contact angle measurements, FTIR and SEM were performed to assess the adhesion between the film layers. The results indicated that adhesion between the layers increased with increasing bonding time and temperature. The wettability of PTFE was improved with surface modification of PTFE film.

Dierk Knittel, Hans-Jürgen Buschmann and Eckhard Schollmeyer; Deutsches Textilforschungszentrum Nord-West e.V. (DTNW), D-47798 Krefeld, GERMANY

Functionalization of Fiber Surfaces by Thin Layers of Chitosan and Related Carbohydrate Biopolymers and Antimicrobial Activity of Surfaces

An increasing demand develops for imparting active agents to textile materials by chemical ways in order to create additional properties ('functional textiles'). With synthetic fibers this may create a better hydrophilic behaviour (water retention, sweat transport ...). On natural fibers this could mean the anchoring of bacteriostatic or odour binding agents and similar. Such a strategy imparts more flexibility to the textile finishing industry.

Biopolymers or their derivatives as surface modifiers can offer special properties like water retention, hydrogel formation or complexing power. So an important task for research and development lies in the evaluation of methods how to anchor such biopolymers permanently onto fiber surfaces in a way that the biopolymers retain their bulk beneficial properties of action. Some properties of the biopolymers (in bulk) and properties to be achieved by a permanent textile finish are summarized in Tab. 1.

Tab. 1: Selected Properties of Biopolymers

Main interest is concerned with the use of chitosan which is said to have wound healing properties and being bacteriostatic and fungistatic. It can thus be shown that chitosan imparts antimicrobial activity to cotton fabrics even when tested under nearly neutral pH-conditions. The finish will be durable because of chemical bonding.

Textile goods, fabrics or non-wovens, treated according to the strategies outlined above - having a permanent finish of biopolymers - may be useful as odour masking materials in fashion, in home textiles or for the automotive sector. Even more important will be the aspects of biopolymer-modified textiles for the protective clothes and for medical or hygienical applications.

Hans-Jürgen Buschmann and Eckhard Schollmeyer; Deutsches Textilforschungszentrum Nord-West e.V., Adlerstrasse 1, D-47798 Krefeld, GERMANY

Dendrons for the Surface Modification of Polymeric Materials

Dendrimers are fascinating molecules from the point of chemists. Due to their molecular similarity with trees they received the general trival name dendrimers. These molecules have a well defined structure combined with a high molecular weight. In contrast to polymers dendrimers have a well defined molecular weight. Due to the branched structure these molecules possess large molecular cavities and pseudocavities. During the last decade several synthetic strategies have been developed to synthesize spherical branched molecules (dendrimers) or parts of them (dendrons). Even single polymer chains with dendrons on their surface are known. A new developed strategy for the surface modification of polymeric materials is the fixation of dendrons on their surface, see Figure 1.

Figure 1: Polymer surface with fixed dendrons

Due to the presence of the dendrons the surface properties of the polymeric materials change, e.g. the fixation of dendrons with hydrophobic end groups on cottons results in an increasing hydrophobicity of the surface depending on the size of the dendrons. Fixing dendrons with a hydrophilic shell alters a hydrophobic surface into a hydrophilic one. The cavities and the shell of the dendrons may have the same polarity. On the other hand the dendrons may possess hydrophilic cavities and a hydrophobic surface or vice versa. The fixation of dendrons on results in polymeric materials with new surface characteristics. The cavities and paseudocavities of the dendrons can be used for the storage of water or hydrophobic substances. In the case of textile surfaces these substances can be released in contact with the human skin.

Saswati Datta; Procter & Gamble , Miami Valley Innovation Center, 11810 East Miami River Road , Cincinnati OH 45252

Recent Advances and Industrial Applications of Plasma Polymerization for Surface Modification

Plasma processing has traditionally been used for high value products such as microelectronics components and various machine parts. However, applications of this surface modification technique for lower value consumer goods has been extremely limited at best. Several factors have contributed to this, including the limitation of batch processing due to vacuum needs, lack of control in the chemistry of the plasma coating, and general absence of extensive studies and knowledge of coating chemistry systems that are compatible with plasma processing for polymeric substrates. Yet, the potential of this processing method for application to polymeric materials used in consumer goods has been recognized for some time - both for processing advantages and for environmental reasons. Recent advances in pulsed plasma polymerization have revived interest in plasma processing as a method for applying polymeric coatings to thermally sensitive substrates. Further, the development of atmospheric pressure plasma processing equipment and systems have opened up the possibility of applying plasma surface modification to continuous web processing without the need for expensive vacuum equipment. This paper will focus on some specific examples of applications of vacuum plasma polymerization for surface modification of polymeric materials that are commonly used in consumer goods such as paper goods and diapers, showing advantages of this process over conventional wet chemical processes. The paper will then discuss new developments in atmospheric pressure plasma tools at Procter & Gamble, and their applications for surface modification of fabrics and polymeric substrates.

A. del Campo, C. Greiner, H. Pfaff and E. Arzt; Max-Planck-Institut für Metallforschung, Heisenbergstraße 3, 70569 Stuttgart, GERMANY

Mimicking Bioadhesion Mechanisms with Polymeric Structured Surfaces

Structured surfaces are responsible for several unique effects occurring in nature (self-cleaning, anti-reflection, drag reduction etc.). Among them, "hairy" surfaces possessing densely packed elongated elements of micro to nanometer dimensions have been demonstrated to play an important role in animal attachment systems. Our quantitative studies of attachment pads of insects, spiders and lizards have revealed a powerful design principle: higher adhesion forces are achieved in nature by splitting up a larger contact into successively finer contacts, which in the case of the gecko reach sub-micron dimensions. This "contact splitting mechanism" has been shown to be a theoretical consequence of contact mechanics [1-5]: according to the JKR theory, the balance between elastic strain energy expended and the surface energy gained becomes more favourable in smaller dimensions. Such a working principle has inspired us as materials scientists to create dry-adhesive systems based on artificial micro and nanostructured surfaces.

Young's modulus, the surface energy and the viscoelastic response of the structural material strongly influence the pull-off force involved in the attaching/releasing process. Design maps for material selection criteria have been recently created and predict a Young's modulus of around 1GPa for an optimum adhesion performance [6]. Therefore polymeric systems, with characteristic Young's moduli between 10MPa and 10 GPa, depending on their chemical structure and physical morphology, offer the best choice for artificial adhesives.

Based on our observations in natural systems and our thorough theoretical analysis, we have tested several different fabrication techniques to obtain arrays of pillars possessing high aspect ratio on a soft substrate. The influence of the array geometry (diameter, aspect-ratio and packing density of the elements), the contact geometry (punch, sphere, torus) and the material properties on the final adhesion performance of the structured surface have been analyzed. From this, possible paths to optimum bio-inspired adhesive systems are beginning to emerge.

1. E. Arzt, S. Gorb, R. Spolenak (2003) From micro to nano contacts in biological attachment devices. PNAS 100 (19), 10603-10606

2. E. Arzt, S. Gorb, H. Gao, R. Spolenak (2003) Verfahren zur Herstellung mikrostruktirierter Oberflächen mit gesteigerrter Adhäsion und adhäsionssteigernd modifizierte Oberflächen. Patent DE 102 23 234 B4

3. K. Autumm, M. Sitti, Y. A. Liang, A. M. Peattie, W. R. Hansen, S. Sponberg, T. W. Kenny, R. Fearing, J. N. Israelachvili, R. J. Full (2002) Evidence for van der Waals adhesion in gecko setae. PNAS 99 (19), 12252-12256

4. H. Gao, H. Yao (2004) Shape insensitive optimal adhesion of nanoscale fibrillar structures. PNAS 101 (21), 7851-7856

5. R. Spolenak, S. Gorb, H. Gao, E. Arzt (2005) Effects of contact shape on the scaling of biological attachments. Proceedings of the Royal Society of London A 461 (2054), 305-319

6. R. Spolenak, S. Gorb, E. Arzt (2005) Adhesion design maps for bio-inspired attachment systems. Acta Biomaterialia 1(1), 5-13

Ezequiel Delgado1; Graham G. Allan2; Angel Andrade1, Héctor Contreras1, Higinio Regla1 and Guillermo Toriz1.

1) Department of Wood, Cellulose and Paper, University of Guadalajara, P.O. Box 52-93 45020 Zapopan, Jalisco, MÉXICO.

2) College of Forest Resources and Chemical Engineering, University of Washington, USA

On the Chemical Modification of Cellulose Fibres Using Triazine Chemistry: from Fiber-reactive Dyes to Molecular Encapsulation

Reviewed is the chemistry of triazines as a means to modify cellulose fibres. This paper reviews the fixation of functionalities to fiber surface, starting from the classic fiber-reactive dyes, hydrogen-bonding compounds, ionic compounds and zwitterions. The different approaches are discusses in terms of the reaction kinetics, topochemistry of the reaction and effects on the morphology of the fibers. The attachment of ionic moieties to cellulose is addressed particularly on their effect on wet and wet-web strength of paper. A new system of fibre-fibre bonding is presented based on zwitterions and its contributions to a greater enthalpy and balance of charges is analyzed. Finally, the usefulness of the triazine coupling to fix cyclodextrins to cellulosic surfaces is described and the molecular encapsulation of fluorescent dyes by means of complexation is discussed.

Casey Finstad, John Madocks, Patrick Marcus, and Patrick Morse; Applied Process Technologies, Inc., 546 E 25th Street, Tucson, AZ 85713

Surface Treatment for Improved Adhesion of Thin Films on Plastic Substrates Through Ion Bombardment by an Anode Layer Ion Source

(Abastract not yet available)

M. Ghoranneviss, D. Dorranian, S. Shahidi , B. Moazzenchi, A. Rashidi, H. Hosseini and Amir H. Sari; Plasma Physics Research Center, Science and Research Campus, Islamic Azad University, Tehran, IRAN

Investigation of Antibacterial Activing on Cotton Fabrics with Cold Plasma in the Presents of Magnet

It has been recognized that micro-organisms, can thrive on textile substrates. Natural fibers such as cotton are more susceptible than synthetics because their porous hydrophilic structure retains water, oxygen and nutrients, providing a perfect environment for bacterial growth. Most textile materials currently used in hotels and hospitals are conductive to cross infection or transmission of diseases caused by microorganisms. A variety of antimicrobial finishes have now been developed for application to textiles. Earlier efforts were based on insolubilization of inorganic compounds, like copper and other organometallic salts. Copper's sterilization capabilities prevent the growth of bacteria, fungi, and germs. Low temperature plasma is a useful technique for surface modification of polymers and textile fibers in dry systems. In this study, we used plasma technique for antibacterial the cotton fabrics and plasma produced by D.C discharge in a cylindrical glass tube. The copper anode and cathode were used. The cathode particles were scattered by attacking active ions, radicals, electrons. The antibacterial has been developed, through incorporation of copper particles on fiber surfaces. The antibacterial properties of the fibers are connected with the presence of copper on their surface. The details will be discussed in full paper.

M. Ghoranneviss*, B. Moazzenchi, S. Shahidi, R. Rashidi, H. Hosseini and Amir H. Sari; Plasma Physics Research Center, Science and Research Campus, Islamic Azad University, Tehran, IRAN

Decolorization of Denim Fabrics with Cold Plasma in The Presence of a Magnet Field at Various Times

Denim jeans have consistently been fashionable in the world culture, it inspires strong opinions from historians, designers, teenagers, movie stars, etc. But style have changed significantly throughout the years. Most jeans today are stonewashed, this technique first became popular. Now in addition to pumice stones, enzymes are used at the cotton fibers and create a stonewashed look. Now days the plasma treatment is a cost-effective and ecological process able to modify properties of the fabrics surface. Plasma surface treatment causes changes to a limited depth (several molecular layers), bulk properties of even the most delicate materials remain unchanged. In this study low temperature plasma of Argon for pick up the denim surface dyestuffs were used. The denim fabrics were placed on the copper cathode and treated for 2.5, 5, 10, 15 minutes. By this work good varnish appeared on the fabrics like stonewash. Scanning electron microscopy (SEM), X-Ray difractometry techniques were used to analyze the properties of untreated and plasma treated samples. The details will be discussed in full paper.

* Corresponding Author

Jeremy Grace, H. Kent Zhuang and Louis Gerenser, Eastman Kodak Company, Rochester, New York

Importance of Process Conditions in Polymer Surface Modification: a Critical Assessment

Plasma web treatment is a common practice for promoting adhesion, wettability, and other surface or interfacial properties in the conversion industry. While the objective of creating new surface functional groups is conceptually simple, it can be difficult to choose the most appropriate kind and configuration of plasma source, the most appropriate feed gas composition, and the most appropriate operating pressure for a given application. Such difficulties arise from the variety of species that can be formed in the plasma and the variety of possible plasma-surface interactions that can occur. A brief review of the importance of various plasma parameters (e.g., specific energy, species concentrations and energy distributions) and an example relating nitrogen uptake in poly(ethylene-2, 6-naphthalate) to plasma diagnostic data in a low-radio frequency capacitively coupled nitrogen plasma are presented. The importance of driving frequency and treatment configuration are then discussed in detail. Uptake kinetics for samples treated at floating potential at low radio frequency are compared with those treated in the cathode sheath. Analysis of the treatment kinetics is based on a simple model of surface saturation. This approach can be used not only to compare practical treatment results as a function of process conditions, but also to compare different treatment technologies in a practical manner.

Yu. Gudimenko1, R. Ng, Z. Iskanderova1, J. Kleiman1, A. Grigorevsky2, L. Kiseleva2, M. Finckenor3 and D. Edwards3

1) ITL Inc, Markham, Ont., CANADA

2) Komposit Institute, Korolev, Moscow region, RUSSIA

3) Marshall Space Flight Center, NASA, USA

Protection of Conductive and Non-conductive Advanced Polymer-based Paints from Highly Aggressive Oxidative Environments

Research has been continued to further improve the space durability of conductive and non-conductive polymer-based paints and of conductive thermal control paints for space applications. Efforts have been made to enhance the space durability and stability of functional characteristics in ground-based space environment imitating conditions, using specially developed surface modification treatment. The results of surface modification of new conductive paints, including the ground-based testing in aggressive oxidative environments, such as atomic oxygen/UV and oxygen plasma, and performance evaluation are presented. Functional properties and performance characteristics, such as thermal optical properties (differential solar absorptance and thermal emittance representing the thermal optical performance of thermal control paints) and surface resistivity characteristics of pristine, surface modified, and tested materials were verified. Extensive surface analysis studies have been performed using complementary surface analyses including SEM/EDS and XPS. Test results revealed that the successfully treated materials exhibit reduced mass loss and no surface morphology change, thus indicating good protection from the severe oxidative environment. It was demonstrated that the developed surface modification treatment could be applied successfully to charge dissipative and conductive paints.

P. Haque1, A.I. Mustafa1, and Mubarak A. Khan2

1) Applied Chemistry and Chemical Technology Department, University of Dhaka, Dhaka 1000, BANGLADESH

2) Radiation and Polymer Chemistry Laboratory, Institute of Nuclear Science and Technology, Bangladesh Atomic Energy Commission, P.O. Box 3787, Dhaka 1000, BANGLADESH.

Photografting of Chitosan Film with Ethylene Glycol and Ethylene Glycol Dimethacrylate Using Ultraviolet Radiation

Natural polymer chitosan was obtained from dried prawn shell waste through the preparation of chitin, and was characterized. Thin films of chitosan solution were prepared by casting method. Mechanical properties like tensile strength (TS), elongations at break (Eb) of chitosan film were studied. Five formulations were developed with ethylene glycol (EG) in presence of photoinitiator Irgacure-651 (2%). The films were soaked in those monomer formulations in dissimilar soaking times and irradiated under UV-radiation at different radiation intensities for the improvement of the properties of chitosan film. The cured films were then subjected to various characterizations like TS, Eb, polymer loading (PL), water uptake, gel content etc. The best result was obtained at 5% EG concentration for 20 min soaking time and after 15 UV passes. 5% ethylene glycol dimethacrylate (EGDMA) was also used as soaking formulation for chitosan film at different UV radiation and soaking time. The film were characterized by DSC, FTIR and UV spectrophotometer.

Liang Hong; Department of Chemical & Biomolecular Engineering, National University of Singapore, 4 Engineering Dr 4, Singapore 117576, SINGAPORE

Creating Regularly Arrayed Pores on Polystyrene Thin Film as a Micro-Reactor

(Abstract not yet available)

Michel Ignat, Bruno A. Latella, Gerry Triani, Ken T. Short, John R. Bartlett; Laboratoire de Thermodynamique et de Physico-Chimie Métallurgique, associé au CNRS, E.N.S.E.E.G., BP 75, F-38402 Saint Martin d'Hères, FRANCE

The Adhesion of TiO2 and Al2O3 Thin Layers Deposited by Atomic Layer Deposition (ALD) on a Polycarbonate Substrate

The mechanical stability and adhesion behaviour of single and two-layered coatings fabricated by atomic layer deposition was investigated by using tensile experiments. The systems consisted of titania and alumina layers ,deposited on polycarbonate substrates. The tensile tests were conducted in a micromechanical tester positioned under an optical microscope allowing in-situ viewing of cracking damage. The strain to initiate first cracking and the crack density as a function of strain were obtained. Moreover: the rupture strength, the fracture toughness and the interfacial adhesion of the films on the substrate, were deduced from analytical models, in which the experimentally determined parameters were included.

A special interest was devoted to analyse the effect induced by a prior water plasma treatement of the polycarbonate substrate surface, on the mechanical stability of the investigated systems. As a matter of fact, it is shown that this treatment will improve their mechanical response, delaying the initiation of the cracking and the debonding, when it occurs

N. Inagaki, Laboratory of Polymer Chemistry, Shizuoka University, 3-5-1 Johoku, Hamamatsu, 432-8561 JAPAN

Surface Modification of Liquid Crystal Polyester, Vecstar, Films for Copper Metallization

(Abstract not yet available)

Z. Iskanderova1, J.Kleiman1, Yu. Gudimenko1, R. Ng1 and D. Kaute2

1) ITL Inc, Markham, Ont., CANADA

2) PlasmaTreat, Mississauga, Ont., CANADA

Surface Treatment of Advanced Organosilicones by OpenAir Plasma to Enhance Oxidative Resistance in Severe Environments

Several space related organosilicone materials have been treated by ground-based OpenAirTM plasma for in-space atomic oxygen resistance enhancement and for contamination prevention. Necessity of a drastic reduction of the outgassing of volatiles and the following contamination has become a challenging problem. Oxygen plasma asher testing and complementary surface analysis techniques have been used to assess the surface composition, bounding states and atomic oxygen resistance of the treated materials. Effective surface conversion of space related organosilicones to oxide-based protective sub-surface layers under selected preferential regimes has been achieved and confirmed by oxygen plasma asher testing and complementary surface analysis techniques such as SEM/EDS and XPS. As OpenAirTM plasma treatment is performed at the atmospheric pressure, this surface modification technology may be applied to three-dimensional complex shapes. It is easy and cost-effective to apply, these preliminary results indicate potential opportunities of an advanced ground-based pre-treatment technology of silicone materials for space applications. It was shown that the application of this approach may essentially simplify the technological development to reduce or prevent contamination caused by silicone-coated space materials and structures.

Satoru Iwamori and Yoshinori Yamada; Division of Human & Mechanical Science and Engineering, Graduate School of Natural Science and Technology, Kanazawa University: 2-40-20 Kodatsuno, Kanazawa, 920-8667, Japan

Poly(tetrafluoroethylene) Thin Film Deposited by PVD

Polytetrafluoroethylene (PTFE) thin films were deposited by a conventional vacuum evaporation apparatus and characterized by measuring contact angles of water and n-hexadecane on the PTFE thin films. Contact angles of water and n-hexadecane on the PTFE thin films shows higher value than that of the bulk PTFE. Although contact angles of water on the PTFE thin films deposited at the pressure between 0.01 and 10 Torr were almost the same value, those of n-hexadecane increased with increase of pressure. Surface tension of these PTFE thin films were calculated with the contact angles of water, n-hexadecane. Surface tension of these PTFE thin films was almost twice higher and the polar component in the surface tension was ten times higher than those of the bulk PTFE.

PTFE thin films were also deposited with a conventional RF sputtering apparatus at various conditions. Atomic compositions of these PTFE thin films were analyzed with X-ray photoelectron spectroscopy (XPS). The surface tension of these PTFE thin films were calculated with the contact angles of water, n-hexadecane and methylene iodide droplets. The surface tension decreased with increase of fluorine content of the PTFE thin films. Although dispersion force component of the surface tension slightly decreased, dipole force component dramatically decreased with increase of temperature of the substrate.

P. Jovancic1, R.Molina2, E.Bertran3, D.Jocic1, M.R.Julia2, P.Erra2

1) Textile Engineering Department, Faculty of Technology and Metallurgy,

University of Belgrade, YUGOSLAVIA

2) Department of Surfactant Technology, IIQAB-CSIC, Barcelona, SPAIN

3) Applied Physics Department, Faculty of Physics, University of Barcelona, SPAIN

Wool Surface Modification and Its Influence on Related Functional Properties

Since the surface related functional properties are important for the final use of textile material, the modern treatments for surface modification are nowadays of growing interest. Low-temperature plasma is nowadays an intensively investigated superficial treatment of wool. Owing to the selective modification of wool surface, low-temperature plasma treatment leads to the formation of new surface groups and also to the "step-by-step" removal of the F-layer. Consequently, the better wettability, shrink resistance, enhanced dyeing properties and better polymer adhesion can be easily achieved.

In this study, we investigated the possibility of using low temperature plasma treatment as a pre-treatment step to the subsequent enzymatic treatment in order to achieve the best technique complying with the purpose to obtain shrink-resistant wool (Woolmark TM31) without conventional post-application of polymer. This technique is compared to the modern chemical treatment of wool combining liquid systems (peroxide, peroxide/enzyme), with a liquid biopolymer system (chitosan) as well as with the low-temperature plasma/chitosan system. These techniques are already known to control well surface characteristics of wool fiber.

To provide evidence of the extent of wool surface modification, we measured wettability, swelling and contact angle. Fourier Transform Infrared Analysis (FTIR-ATR) and XPS analysis have been used to provide evidence about the chemical changes on the surface of the wool fiber. SEM observation and AFM analysis have been used for routine examination and gaining information about wool fiber topography.

Mubarak A. Khan, Rashidul Alam and S.K Bhattacharia; Radiation and Polymer Chemistry Laboratory,Institute of Nuclear Science and Technology,

Bangladesh Atomic Energy Commission. P.O. Box 3787, Dhaka, BANGLADESH

Modification of Bio-blend of Chitosan and Water Soluble Polymers by Photocuring with Acrylic and Silane Monomer

(abstract not yet available)

S. K.Bhattcacharia and Mubarak A. Khan; Radiation and Polymer Chemistry laboratory, Nuclear Radiation Chemistry division, Institute of Nuclear Science and technology, Bangladesh Atomic Energy Commission, P.O Box 3787, Dhaka 1000, BANGLADESH

Roll of Silane, Silicate and Sand on the Modification of the Wood Surface Properties by Photocuring

Photocuring technique emerged as a promising technology to improve the properties of wood surface. Low graded wood showed significant improved surfaced properties after treated with Ultraviolet radiation using photo curable formulation. Oligomer, monomer and different types of additives are the key ingredients of a photo curable formulation. Some of additives play a great role to get the desired properties along reduction of the cost of the formulation. The frequently used oligomers for photocuring are Urethane, Epoxy, and Polyester etc. Silane proves to be good component as part of a photocurable formulation to improve the surface properties. Sand is proved as the cheapest available additives for the photo curable formulations. Thin films are prepared on glass plate with different photo curable formulations using UV radiation to select which formulation could be used as top coat or a base coat. Various characteristics properties such as Pendulum Hardness, Abrasion, Gloss (60o &20o), and Micro scratch hardness, weathering effect, adhesion strength are studied. Then the formulations are applied on the desired wood surface and same properties were investigated. Base coat containing magnesium tri silicate and silica shows to be an ideal one and 3% silane in the formulation produces optimized surface properties on a particular wood surface.

E.T. Kang and K.G. Neoh, Dept. of Chemical and Biomolecular Engineering,

National University of Singapore, Kent Ridge, SINGAPORE 119260

Plasma Graft Copolymerization of 4-Vinylpyridine on Dense and Porous SiLK® for Electroless Plating of Copper and for Retardation of Copper Diffusion

Argon plasma-pretreated dense and porous SiLK® films coated on Si(100) wafers (Si-SiLK® wafers) were subjected to plasma graft polymerization of 4-vinylpyridine (4VP). X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FTIR) spectroscopy results revealed that the pyridine functional groups of the plasma graft-polymerized 4VP (pp4VP) could be retained to a large extent under certain grow discharge conditions. The topography of the pp4VP grafted Si-SiLK® (Si-SiLK-g-pp4VP) surface was studied by atomic force microscopy (AFM). The preserved pyridine groups were used as the chemisorption sites for the palladium complexes (without prior sensitization by SnCl2) to catalyze the electroless deposition of copper. Rutherford backscattering spectrometry (RBS) and transmission electron microscopy (TEM) were employed to investigate the extent of copper diffusion into the pristine and graft-modified Si-SiLK substrates after thermal annealing. The grafted pp4VP layer on the dense and porous Si-SiLK surface served effectively as (i) a sensitization layer for the electroless plating of copper, (ii) an adhesion promotion layer for the electrolessly deposited copper, and (iii) a diffusion barrier for the electrolessly deposited copper. These functionalities arose from strong interactions of the metal ions and atoms with the pyridine moieties of the grafted pp4VP layer.

Daniel A. Kaute1 and Christian Buske2

1) PlasmaTreat North America Inc., 1-2283 Argentia Road, Mississauga, ON L5N 5Z2 CANADA

2) PlasmaTreat GmbH, Bisamweg 10, 38003 Steinhagen, GERMANY

Advances in the Understanding of Open Air Plasma Technology and Latest Applications

FLUMEtm plasma systems create atmospheric pressure plasma based on Openairtm plasma technology. They are unique in that they clean surfaces to molecular levels, and strongly activate polymer based surfaces by creating a high amount of polar groups, mainly ketonic and hydroxile, when using air as carrier gas. As a result, pristine and strongly activated surfaces fully wet out with water, even low surface energy materials, like polypropylene (PP), thermoplastic olefins (TPO), thermoplastic elastomers (TPE), and ethylene/propylene/diene rubber (EPDM). This makes possible the use of simple, water based, environmentally friendly, and cost effective adhesives, coatings and inks without compromising the performance of the bond. Latest advances in the understanding of the Openairtm Plasma, and case studies with latest industrial applications are discussed.

Z. Iskanderova1, J. Kleiman1, V. Issupov1, A. Chambers2, G. Roberts2, C. White2,

1) ITL Inc, Markham, Ont., CANADA

2) School of Engineering Science, University of Southampton, UK

Oxidation Protective Surface Modification of Graphite and Polymer-based Carbon Filled Conductive Coatings

ITL has developed in the past a number of surface modification technologies for advanced space-related thin polymer films and polymer-based paints, including specially defined ion implantation technology named ImplantoxTM to enhance the resistance to highly aggressive oxidative environments. The same approach has been successfully applied to HOPG graphite. In this presentation, an extensive study of the oxidative resistance and electro-physical characteristics has been performed for pristine and surface modified graphite-polymer compositions known as conductive inks and used mostly in screen-printing for micro-electronic applications. These "thick films" materials are attractive for development of advanced atomic oxygen sensors for real time in-situ flux measurements in long-term space missions, based on resistivity change. Pristine and ImplantoxTM-treated 4200-Series Polymeric Resistor Compositions have been analyzed using various surface analysis and characterization techniques, including surface resistivity measurements and also tested in oxygen plasma and under fast (5 eV) directed anomic oxygen beam. Erosion yield measurements, surface morphology/roughness and composition change, time dependence of resistivity have permitted to assess the suitability of the pristine materials for atomic oxygen sensors. Joint fast atomic oxygen testing and change of electro-physical characteristics have been used to identify the detailed mechanism of surface conversion of the implanted materials under atomic oxygen leading to formation of self-protecting oxides-based surface modified layer

Takaomi Kobayashi; Department of Chemistry, Nagaoka University of Technology, 1603-1 Kamitomioka, Nagaoka, Niigata, JAPAN 940-2188

Polymer Surface Treated with Ozone by Using In-situ Instrumental Analyses

Short abstract: Ozone has been used as active species to treat surface of polymers and to decompose environmental chemicals. Such ozone effect can attribute to several non-equilibrium reactions because of its active nature. In these applications polymer materials have been conveniently utilized in the presence of ozone, although ozone also decomposes polymers. However, little is known the reaction processes of ozone and polymers. In the present work, talk focuses on reaction of ozone with polymers, which have been used as common polymers of polyethylene, polyvinylchloride, polystyrene and polyvinyl alcohol by using in-situ FT IR and mass spectrometry. Technical fundamentals and the application of ozone treatments of polymer are demonstrated.

Tadanori Koga, J. L. Jerome, M. H. Rafailovich and J. C. Sokolov; Department of Materials Science & Engineering, State University of New York at Stony Brook, Stony Brook, NY 11794-2275

Metalizable Polymer Thin Films in Supercritical Carbon Dioxide

We report an environmentally "green" method to improve adhesion at a polymer/metal interface by using supercritical carbon dioxide (scCO2). Spun-cast polystyrene (PS) and poly(methyl methacrylate) (PMMA) thin films on cleaned Si wafers were used for this study. Film thicknesses of both polymer films were prepared in the range varying from 100 Å to 1600 Å. We exposed the films to scCO2 in the P-T range corresponding to the density fluctuation ridge, where the excess swelling of both polymer films occurred, and then frozen the swollen structures by quick evaporation of CO2. A chromium (Cr) layer with the film thickness of 300-400 Å was deposited onto the exposed film by using E-beam Evaporator. X-ray reflectivity measurements showed that the interfacial width between the Cr and exposed polymer layers increased by a factor of about 2 compared to that without exposure to scCO2. In addition, the large interfacial broadening was found to occur irrespective of the thickness of both polymer films. After the XR measurements, the dewetting structures of the PS/Cr films induced were characterized by using atomic force microscopy. Contact angle measurements showed that a decrease in interfacial tension with exposure to scCO2 accompanied an increase in interfacial width. Furthermore, we show that addition of gold nanoparticles to the polymer matrices promotes the compatibility significantly.

Dr. Y. Koval; Physikalisches Institut III, der Universitaet Erlangen-Nurnberg, Erwin-Rommel Str. 1, 91058 Erlangen, GERMANY

Polymethylmethacrylate Modification by Low Energy Ion Bombardment

Under low-energy ion bombardment, a subsurface region of polymethylmethacrylate (PMMA)stratifies into graphitized, cross-linked and low-molecular weight layers. The top graphitized PMMA shows a substantial conductance. At low electric fields, the conductance is provided by a variable range hopping with a strong influence of Coulomb interactions. Such behavior is usual for conducting carbon-based materials (e.g. some conjugated polymers). At high electric fields, the graphitized PMMA reveals non-Ohmic behavior with the current-voltage characteristic typical for the conductance by Poole-Frenkel mechanism. It was found that an increase of the ions energy leads to a substantial enhancement of the graphitized layer conductivity. Radiation reactions in the subsurface region, which lead to the graphitization, contribute significantly to the ion etching of PMMA. We propose a model of ion etching of PMMA, which takes into account ion-induced reactions. Also we show that sputtering of the graphitized layer is the limiting factor for ion etching rate of PMMA. The model allows explaining peculiarities of ion etching of PMMA and predicting the etching rates of a wide range of C-H-O materials under the inert ions bombardment. On the PMMA surface, ion bombardment leads to appearance of the various topological features like bubbles, waves, and a net with a cell of nanometer size . The stratification of the subsurface region of PMMA was demonstrated to play an important role for the development of the surface topology.

U. Lommatzsch, M. Noeske, T. Fladung, J. Degenhardt, T. Wuebben, S. Strudthoff, G. Ellinghorst, O.-D. Hennemann, Fraunhofer Institute for Manufacturing and Advanced Materials, D-28359 Bremen, GERMANY

Pretreatment and Surface Modifications of Polymers by Atmospheric Pressure Plasma Jet Treatment

Plasma jets operating at atmospheric pressure have recently found widespread commercial use as a tool for the activation/pretreatment of surfaces. For this study the polymers PP, HD-PE, PVDF, PA6, and PET are activated by a commercially available plasma jet at atmospheric pressure. The plasma activation increases substantially the adhesive bonding strength for all polymers studied. The improvements in adhesion are tried to correlate to the plasma-induced changes of the surface.

In detail the effects of selected plasma treatment parameters (e.g. treatment time, treatment distance, excitation voltage, gas type) on the adhesive bonding strength are studied by measurements of the tensile lap shear strength. Modifications of the substrate surface are investigated by XPS, AFM, TOF-SIMS, and contact angle measurements. In addition the influence of time and storage conditions on the plasma-activated surface is studied.

The adhesion improvements can be related to (i) an increase in surface energy by 40-60 %, (ii) to the incorporation of oxygen- and nitrogen-containing groups with different functionalities, and (iii) to topological changes of the substrate surface. From using different feed gases it is derived that chemical modifications of the substrate occur in the plasma zone but also by reactions with ambient air after the treatment.

AFM 3-D surface images of PET before (left) and after (right) atmospheric pressure plasma jet treatment. The plasma treatment reduces surface roughness but, at the same time, improves substantially the adhesive bonding strength.

S. Markus, R. Wilken, S. Dieckhoff, O.-D. Hennemann, Fraunhofer Institute for Manufacturing and Advanced Materials (IFAM), D-28359 Bremen, GERMANY

Detection of Contaminations on Polymer Surfaces Using Laser Induced Breakdown Spectroscopy

LIBS (Laser Induced Breakdown Spectroscopy) is frequently used to analyse the elemental composition of liquids, solids and gases. Therefore a high power laser pulse is focussed on a sample whereby a small amount of material (0.1 ug to 1 mg of material) is ablated and forms a plasma above the surface. The emission from atoms and ions of this plasma is analysed by a spectrometer. The atomic spectral lines are used to determine the elemental composition and elemental concentration of the sample.

Regarding bonding and coating processes a maximum degree of surface cleanliness is an important requirement for high adhesive strengths. Due to the fact that contaminations in a range of a monolayer or even submonolayer with corresponding film thicknesses of less than one nm can cause adhesion failures, the detection of these small concentrations of surface contaminations is a challenge for the quality assurance in bonding technology. In addition, in many cases the detection of these species is also hampered by the similarity of the chemical composition of the contamination and the polymer material of the substrate itself.

The applicability of LIBS as a method to detect contaminations like that on polymer surfaces (PC (Polycarbonate), CFRP (Carbon Fibre Reinforced Plastics)) is investigated by comparison with XPS (X-ray Photoelectron Spectroscopy) and contact angle measurement as established methods for surface characterization. Surfaces of polymers were coated by thin films (10-100 nm) of different contaminants (silicone, mineral and hydraulic oil). The layer thicknesses were analysed by ellipsometry. LIBS signals obtained from contaminated surfaces were correlated with XPS and contact angle measurements.

LIBS turned out to be applicable for detecting contaminations on polymer surfaces that can cause detrimental effects on adhesion properties.

Carosena Meola, Giovanni Maria Carlomagno; Department of Energetics Thermofluidynamics and Environmental Control, University of Naples Federico II, P.le Tecchio 80, 80125 Napoli, ITALY

Infrared Thermography in Nondestructive Evaluation of Bonded Structures

Infrared thermography is a remote imaging system which transforms the thermal energy radiated from objects in the infrared band of the electromagnetic spectrum into a temperature map. Such feature is usefully exploited in many applications such as medicine, fluidynamics, agriculture, maintenance, and so forth. Notwithstanding this, infrared thermography is still not completely exploited; this is mainly because at first sight it seems too expensive and too difficult to use. The purpose of the present paper would be an overview on the use of infrared thermography for nondestructive evaluation of bonded structures.

Several different types of bonded structures were considered to include variation of materials and types of bond. In particular, materials were chosen between plastics, fibre reinforced composites, metals, concrete, and others and which were adhesively bonded, or welded. Such choice was made in an effort to show examples of application which could be of interest for practitioners in many different fields amongst others: aerospace, naval, automotive and civil engineering, architecture and cultural heritage. Two different thermographic techniques were used, which are: pulse thermography and lock-in thermography. The obtained results prove that infrared thermography, by using the most appropriate method (pulse, or lock-in), is capable of supplying information about the bondline thickness in adhesively bonded joints, the extent of the heat affected zone in welded joints, the presence of many types of defects in bonded structures such as disbonding, slag inclusions, detachments and materials modifications.

Carosena Meola1 and Giuseppe Giorleo2

1) Department of Energetics Thermofluidynamics and Environmental Control

University of Naples Federico II, P.le Tecchio 80, 80125 Napoli, ITALY

2) Department of Materials and Production Engineering

University of Naples Federico II, P.le Tecchio 80, 80125 Napoli, ITALY

Characterization of Polymer Induced Modifications

Today we are surrounded by plastics: shopping bags, furnitures, transport vehicles, packaging; almost everything is entirely, or partially, made of plastic. The suitability of plastic to each application is tailored through specific compounding and treatments. As an example, the weak polyethylene, through the crosslinking process, can be transformed into a superior material which may be resistant to temperature, pressure, corrosion, and which could be used in a large variety of applications.

Caution is indeed needed since treatments may induce undesired polymer modifications which could led to material degradation and premature failure of products, or otherwise to formation of toxins in materials destined to foodstuff, or medicine, packaging. Thus, testing of end products with effective techniques is vital to assess the suitability of a material to the specific use. Modifications induced in polymers by treatments like silane grafting, or irradiation, or other coupling agents are analysed. The attention is mainly focused on the characterization of:

Low density polyethylene (LDPE) crosslinked in two different ways: via silane grafting and electron beam irradiation. Such polyethylene is mainly used as thermoshrinking blanket insulation for low and medium voltage electrical cables and for communication cables.

Polyvinylalcohol crosslinked through bifunctional reagents. Such polymer is frequently used as a matrix for the immobilization of enzymes and cells. The investigated PVOH-based films were obtained adding to a PVOH-water solution the crosslinking agent (i.e., dialdheyde) and the catalyzer of the crosslinking reaction (HCl). Different amounts of the crosslinking agent were added to obtain films at different crosslinking degree.

Carosena Meola1, Antonino Squillace2, Francesco Bellucci2 and Vincenza Marzocchi2

1) Department of Energetics, Thermofluidynamics and Environmental Control

University of Naples Federico II, P.le Tecchio 80, 80125 Napoli, ITALY

2) Department of Materials and Production Engineering

University of Naples Federico II, P.le Tecchio 80, 80125 Napoli, ITALY

Coatings: Deposition Procedures and Testing

The deposition of a coating over a solid surface generates interfaces between dissimilar materials and involves considerations about wettability, interface evolution, and adhesion. The performance of a coating depends not only on the inherent characteristics of the coating (and substrate) but also on the coating-to-substrate adhesion. Wettability promotes adhesion through physical, chemical, and/or mechanical bonds acting across the interface between coating and substrate. Typical defects are microporosity, cracking, peeling, rusting and poor local adhesion over the substrate. These defects are generally caused by the modalities of application of coatings, conservation of the coated artefact and start up of the working conditions. Of paramount importance in many applications is the so-called pre-treatment which involves cleaning and preparation of the surface to be coated.

Particular attention is devoted to aluminum anodization; the bare metal, the polished surface and the anodized surface are analysed with microscopy and infrared thermography. In particular, infrared thermography, as a remote imaging system, is helpful for assessing the pre-treatment uniformity and then the coating integrity, the sub-surface conditions of the coating system and for detecting many types of defects such as delamination, blisters and many others which are not noticeable by visual observation. Infrared thermography, if routinely used for inspection of parts in service, allows detection of corrosion at the incipient stage before catastrophic failure has occurred.

Renate Mix, K. Hoffmann, R. Decker, U. Resch-Genger, J. Friedrich

Federal Institute for Materials Research and Testing, Unter den Eichen 87, D-12205 Berlin, GERMANY

Covalent Coupling of Fluorophors to Surface-bonded Functional Groups

Plasma modification of polymer surfaces, particularly functionalization or plasma polymerization with functional group-carrying monomers are useful techniques to adjust the hydrophilicity, adsorption, and wetting properties of polymeric surfaces.

To an increasing degree chemical reactions are carried out at surface bonded functional groups to attach substances with special features to produce tailored surfaces for different applications.

Here, first results are presented showing the covalent coupling of fluorophors to functional groups on polymer surfaces based on different synthesis concepts.

The first attempt is based on oxygen plasma-treated polypropylene which was wet-chemically reduced to transform the different O-containing groups into OH-groups. The resulting surface hydroxyl groups were reacted with diisocyanates (HDI, TDI, MDI) followed by the reaction with water and dansyl chloride or NH2-functionalized fluorophors. Kinetic studies of the reaction of surface bonded OH groups with TDI and MDI provide information about the efficiency of the polyurethane coupling.

The second way is directed to the reaction of plasma polymerized allylamine deposited on PP. At first, the generated amino groups were coupled to 1,5-glutardialdehyde. The so produced aldehyde-terminated surfaces were reacted with different commercially available dansyl, rhodamine and fluorescein labels, as well as with diamines followed by the reaction with fluorescein-isothiocyanate.

Comparison of fluorescence spectroscopic and XPS investigations and efforts to correlate these results are presented.

R. Molina1 , J.P. Espinós2, E. Bertran1, P. Erra3 and A.R. González-Elipe2

1) Dpto. Física Aplicada y Óptica, Universidad de Barcelona, Avd. Diagonal 647, 08028, Barcelona, SPAIN.

2) Departamento de Química Inorgánica ,Instituto de Ciencia de Materiales de Sevilla (CSIC-Universidad de Sevilla), Avda. Americo Vespucio s/n, 41092 Sevilla, SPAIN.

3) Dpto. de Tecnología de Tensioactivos, IIQAB-CSIC, C/ Jordi Girona 18-26, 08034 Barcelona, SPAIN.

Surface Chemical Modification of Down Stream Plasma Treated Wool

The superficial hydrophobicity of keratin fibers plays an important role in many processes such as shrinkage, dyeing and polymer adhesion. For this reason plasma treatment is used as an ecological friendly process in order to confer hydrophilicity to keratin fibers. In this work, the surface chemical modification promoted by air plasma as a function of the treatment time by means of X-ray Photoelectron Spectroscopy (XPS) without previous exposure to the air atmosphere is studied. In order to know the contribution of the different air plasma active species, plasma treatments have been carried out with nitrogen, oxygen, oxygen/water vapor mixture, and water vapor.

The results have evidenced the effects induced by the different active species generated by plasma from the different components of the air. In general, the intensity of C-C peak decreases and the C-O, C=O and O-C=O peaks increase when a gas containing oxygen species is used. Simultaneously, the intensity of the S-S peak decreases and that of the sulphonate peak (SO3-) increases. The extent and characteristics of the oxidation and functionalisation of the hydrocarbon chains of the F-layer depend on the nature of gas. Thus, whereas treatments with plasmas of air and water vapor strongly affect the hydrocarbon chains of the F-layer, oxygen is less effective in the oxidation process. It has been also noted that the active species formed in the nitrogen plasma do not induce any significant change in the surface composition of the wool fibers.

Moreover, the "in-situ" XPS analysis of the treated samples has permitted to differentiate between the plasma effects produced "in situ" and those other linked to the air atmosphere exposure after the treatment. The X-ray analysis also reveals an evolution of the surface chemical composition as a function of the ageing time in air atmosphere.

J. Zeng and A. N. Netravali; Fiber Science Program, Cornell University, Ithaca, NY 14853-4401

Pulsed Excimer Laser Treatment of Vectran® Fibers and its Effect on Surface Characteristics and Adhesion to Epoxy Resin

Vectran®, liquid crystalline polyester fibers were treated with pulsed XeCl excimer laser (308 nm) to improve their surface topography and chemistry to improve their adhesion to epoxy resin. The treatments were carried out separately in air and diethelenetriamine (DETA) environments and the laser fluence and number of pulses were varied. The fiber surface was characterized using various techniques including SEM, AFM, XPS, dynamic wettability etc. and the fiber/epoxy interfacial shear strength (IFSS) was carried out using microbead test. The results suggest that the laser treatments in air were more sever than in DETA and caused significant periodic roll (wavy) structure on the fiber surface transverse to the fiber axis. AFM results indicated surface roughness to increase 3.5 times to control fibers in the case of air and about 2.5 times in DETA environment. The dispersion component of the surface energy increased from near zero for the control fibers to 8.8 mJ/m2 in the case of air and 18.0 mJ/m2 in the case of DETA. The XPS studies indicated oxygen on the surface of both and nitrogen on fibers treated in DETA environment. The IFSS of fibers treated in air increased by 75% from 19.5 MPa to 34.7 MPa at the fluence of 60 mJ/(pulse*cm2) and 75 pulses on each side (total of 150 pulses). For fibers treated in DETA, the maximum IFSS value obtained was 27.7 MPa was obtained at the fluence of 60 mJ/(pulse*cm2) and total of 60 pulses. It was concluded that the surface roughness was the predominant factor controlling the IFSS.

A. Priola and R. Bongiovanni; Department of Materials Science and Chemical Engineering, Politecnico Di Torino, C.so Duca degli Abruzzi, 24 10129 Torino ITALY

Design and Control of Surface Properties of UV-Curable Systems

The use of proper functional monomers as additives in UV-curable systems allows to design specific surface properties of the cured polymers. Under thermodynamically or kinetically driven conditions, these additives tailor the polymeric surfaces, as requested by the application. The mechanism is based on their selective segregation at the interfaces. The very fast UV-curing reaction allows to freeze and stabilize the structure and morphology created.

For the surface in contact with air, wettability, chemical resistance, gloss, stain resistance are important. These properties can be assured using appropriate surfactant monomers. Concerning the surface in contact with the substrate, adhesion is the key parameter for the performance of the systems. To promote adhesion, functionalised monomers able to react or interact with the groups present on the substrate can be introduced.

These topics will be presented considering UV-curable systems based on acrylic and epoxy resins, containing fluorinated or polysiloxane structures, coated on different substrates.

L.Cernakova1, D.Kovacik2, J. Rahel2, M. Cernak2, and P. Tsai3

1) Faculty of chemical and food technology, Slovak Technical University, Radlinskeho 9, 812 37 Bratislava, SLOVAKIA

2) Department of Experimental Physics, Comenius University Bratislava, Mlynska dolina F2, 842 48, SLOVAKIA

3) Textiles and Nonwovens Knoxville Development Center (TANDEC), The University of Tennessee Knoxville, TN 37996-1950, USA

Low-cost High-speed Plasma Activation and Post-plasma Grafting of Polymer Materials

In-line surface activation of polymer webs using atmospheric-pressure non-equilibrium plasmas is emerging as the most environmentally acceptable and economically viable concept in meeting the needs of converters and end use suppliers. However, the complexity, slow speed and high operational cost of the existing atmospheric-pressure plasma treaters made them impractical for this particular application. The crux of this technique is the availability of a robust, reliable and cost effective plasma source, which can be used in tandem with existing high-speed production lines without the use of expensive helium gas.

The Diffuse Coplanar Surface Barrier Discharge - DCSBD [1] generates thin (on the order of 0.1 mm) diffuse plasma layers of the order of 100 W/cm3 power density, resulting in extremely short exposure times well below 1 sec. At such high power densities the macroscopically uniform plasma can be generated easily and in an economic way in any, even in strongly electron-attaching, reactive gas mixtures, like ambient air or oxygen.

DCSBD plasma source has been successfully tested for the surface plasma activation, post-plasma grafting, and plasma polymerization of a wide scale of polymeric webs [2], including the surface activation, permanent hydrophilization, and chitosan grafting of PP and PLA nonwovens for hygiene applications. The results to be presented indicate that for this particular applications the cost efficiency achieved by this technique is unmatched by any other known finishing technology.

[1] M. Simor, J. Rahel, P. Vojtek, M. Cernak, A. Brablec, Appl. Phys. Letters 81 (2002)2716

[2] M. Cernak, US Patent Appl. No. 20040194223

E. Sancaktar, J. Kim and D. Ahn; Department of Polymer Engineering

The University of Akron, Akron, OH44325-0301

The Effects of Excimer Laser Ablation on Surface Morphology and Crystallinity of Uniaxially Stretched Poly(ethylene terephthalate) Films

In order to evaluate the effects of excimer laser ablation on surface morphology and crystal structure, poly(ethylene terephthalate) (PET) films uniaxially stretched 100% and 300%, (UPET100 and UPET300, respectively) were prepared from PET cast films (UPET-CAST). When the 100%- and 300%-stretched PET films were irradiated by excimer laser (TPET100 and TPET300, respectively), channel-type surface microstructures were obtained by means of surface melt processes. From the scanning electron microscope (SEM) images, it was observed that more prominent channel-type surface microstructures perpendicular to the stretching direction were readily developed by excimer laser irradiation at higher stretching ratio, owing to the enhanced contrast between amorphous and crystalline parts. According to the wide angle X-ray diffraction (WAXD) patterns and the thermograms obtained by differential scanning calorimetry (DSC), the degree of crystallinity and perfection of crystal structure increased with excimer laser treatment due to the etching rate difference between the random amorphous domains and highly oriented domains. Another important factor in determining the surface morphology and crystal structure was free volume effect generated by evaporation of broken chain during excimer laser irradiation. The presence of significant amount of free volume was confirmed by the fact that glass transition temperatures (Tg) and onset temperatures of cold crystallization (Tc,onset) decreased after excimer laser treatments. In addition, by virtue of free volumes located in the highly oriented domains, the perfection of crystal structure as well as the degree of crystallinity increased at low environmental temperature, where melting process was highly restricted. From these experimental results, we were able to predict the ablation mechanisms of PET films by excimer laser irradiation. The channel-type microstructures could be initiated by the difference of etching rate between randomly oriented amorphous domains and highly oriented domains at first few pulses. After the initiation step, the surface microstructures would be propagated by means of surface melt flow and cooperative molecular motion without melting. In other words, the surface microstructures would grow via the surface melt flow when the thermal energy given by laser irradiation was high enough to melt the PET crystals in fusion layer. On the other hand, the surface microstructures and the more perfect crystal structures would be formed through a cooperative molecular motion facilitated by enlarged free volumes when the thermal energy corresponding to the temperature between Tg and melting temperature(Tm) were introduced to the heated layer.

E. Schollmeyer1, J. Zorjanovi1,, R. Zimehl1, O. Petracic2, W. Kleemann2, T. Textor1, Th. Bahners1 and D. Knittel1

1) Deutsches Textilforschungszentrum Nord-West e. V., 47798 Krefeld, GERMANY

2) Laboratorium für Angewandte Physik, Gerhard-Mercator-Universität, 47048 Duisburg, GERMANY

Synthesis of Superparamagnetic Filaments

Ferromagnetic materials like iron oxides behave superparamagnetic if the volume of the magnetic crystals falls below a critical size. Superparamagnetic particles offer a high potential for several applications in different areas such as ferrofluids, color imaging, controlled transport of anti-cancer drugs or for the separation of bio molecule from solution.

In this lecture we would like to introduce a method for the stabilization of maghemite and magnetite particles in a polysiloxane matrix for the coating of synthetic textile materials (like polyester, PETP). The aim of this work is to produce flexible materials with "switchable" magnetic qualities.

Firstly the polyester materials were functionalized with amino groups by incorporation of dodecylamine in the polyester matrix. Then the iron oxide particles (particles coated with silica and uncoated) were stabilized in 2-propanol with GPTMS. Because the amino groups react with the epoxy groups of GPTMS the polyester surfaces were coated by dip-coating. Finally the polyester material was heated for 3 hours at 130░C. The particles sizes were determined by transmission electron microscopy and the x-ray diffraction. The magnetic studies of coated polyester materials were performed by use of a super-conducting quantum interference device (SQUID) magnetometer in the temperature range between 10 to 300 K.

Eckhard Schollmeyer; Deutsches Textilforschungszentrum Nord-West e.V. (DTNW), D-47798 Krefeld, FRG

Electrokinetic Investigations on Polymer Fibres

In the present paper at first some electrokinetic effects are discussed by means of linear nonequilibrium thermodynamics introduced for this purpose by Prigogine. After a critical examination of the capillary bundle models, which are used to determine the zeta-potentials of fibres, two methods are proposed to yield comparable zeta-potential of different fibres: A plug model derived analytically for fibres arranged parallel to the streaming fluid and a model for selective adsorption of ionic species derived by means of thermodynamics in analogy to Nernst's equation.

Some relations between electrokinetic properties are shown. First by means of phenomenological equations, the electroviscose effect is explained to be due to the electroosmotic backstreaming. It is shown that in principle the equivalence of streaming-current- and streaming-potential-methods to get zeta-potentials is included in these equations. This equivalence was used first by Smoluchowski to derive his equation for the zeta-potential for the special case of a single capillary. The equation he found concerning the relations between both zeta-potential and streaming-potential and streaming current between the ends of a capillary was extended by different authors to bundles of capillaries and then to plugs. It is discussed, which of the extensions are correct and which properties should be included in a so-called "porosity factor".

From a mathematical treatment of the surface conductivity in case of capillaries it is shown that zeta-potentials can be obtained in principle by measuring the conductivity of the system plug-electrolyte. For this system a procedure is deduced to calculate approximately the porosity factor from measurements of the electrical resistance.

An apparatus is described to measure streaming-potentials as well as streaming-current at different concentrations of the solid. Zeta-Potentials calculated according to Smoluchowski's equation can be corrected by conductance measurements using Ag/AgCl-eletrodes directly in dilute aqueous solutions containing more than 10-3 mol/l KCl. They are in good agreement with the real dependence of zeta-potentials from the "porosity" of the plug. For KCl concentrations smaller than 10-3 mol/l, this correction must be done separately from measurements of streaming-potential according to the method of Fairbrother and Mastin at higher electrolyte concentrations.

Among the different porosities given by Konzeny-Carman, Goring and Mason, Biefer and Maso, and Fairbrother and Mastin, the latter describes best the dependence of the zeta-potential on the concentration of solid for any kind of plug. These results and the limits of the approximation method are discussed.

It is shown that the conductivity of an arrangement of fibres in a liquid depends rather insensitively on the zeta-potential (s) calculated according to the Smoluchowski equation. The reason suggested also makes doubtful the theoretical deduction of the Fairbrother-Mastin method to correct the porosity dependence of the s-potential.

An investigation of the porosity dependence of the three independent coefficients of the phenomenological equations of arbitrary fibres gives an explanation for the fact, that this relation is found to fit in the most cases with the porosity dependence of the s-values. A different arrangement of fibres forming a plug shows that the use of the Smoluchowski equation cannot be expanded from capillaries to plugs using simple corrections.

Finally the time dependence of the streaming current and the streaming potential is discussed and compared with the velocity of the streaming fluid and with the electrical properties of the measuring cell.

More over a thermodynamic description of the zeta-potential is proposed, which leads under special conditions to the application of Nernst's equation on the Gouy-Chapman-layer. Thus the behaviour of the streaming current can be explained by adsorption of different electrolytes at solids. Finally, a relation of electrokinetic effects with redox electrodes is proposed, which might be able to result in the determination of absoulte thermodynamic normal potentials.

An equation is derived to relate the streaming current of an arrangement of cylinders parallel to a streaming fluid with the zeta-potential of the solid-liquid interface. The derivation is in analogy to the principles used by Smoluchowski to caculate the streaming current of a single capillary, i.e. a laminar streaming fluid and the applicability of Poisson's equation. It is shown that both equations are identical.

E. Schollmeyer, D. Knittel, T. Textor, T. Bahners, R. Zimehl and J. Zorjanovi; Deutsches Textilforschungszentrum Nord-West e. V.

Adlerstr. 1, 47798 Krefeld, GERMANY

Nanotechnology to Functionalization of Textile Materials

Particles with particle sizes in the area of 1 to 100 nm enjoy a great popularity in research and in industrial applications. These particles and many materials, they are combined of nano particles have another physical and chemical behavior than material with a macroscopic structure. Such inorganic nano particles (e. g. metal oxide semiconductor) show special nano effects that also can be used to functionalize textile materials. The aim of this lecture is to show some of the aspects to permanent and directly linking of nano particles (particles size < 100 nm) about chemical bonds on the polymer surfaces.

One of the processes to realize this is the in-situ deposition by sol gel or LPD technology. TiO2 (rutile or anatase) or ZnO can be deposited directly on the polymer surface about covalent bonds to come to materials with completely changed properties (such as UV protection or photo catalyst). An anther way to linking of particles on the textile materials (e. g. polyester) is based on a more-step reaction schema: firstly the particles must be stabilized of colloid chemistry ways. The stabilization of particles can be achieved by steric stabilization with (3-glycidyloxypropyl) trimethoxysilane (GPTMS). The polyester materials also have to be functionalized. For this work the polyester were functionalized with amino groups by incorporation of 1-dodecylamine in the polyester matrix. Because the amino groups react with the epoxy groups of GPTMS the polyester surfaces were coated by dip-coating. Finally the polyester material was heated at 130░C. On this way polymer surfaces can be coated with nano particles (such as TiO2, SiO2, ZnO, Al2O3) about covalent bonds to come to materials with completely changed properties. The studies have shown that on this way e. g. the abrasion resistant and UV protection of textile materials can be improved.

Thomas Schuman, Maninder Singh, and James Stoffer; University of Missouri-Rolla, Department of Chemistry and Materials Research Center, Rolla, MO 65409

An In-mould Application of Adhesion Promoter to Polyolefin Substrates

Adhesion promotion treatment of olefinic plastic surfaces is necessary due to their low surface energy. A corona, flame, plasma, or post fabrication spray treatment of the polymer surface increases the surface energy available for wetting and adhesive interactions. A potentially simple process would involve application of an adhesion promoter chemistry at the time of object fabrication, e.g., during a moulding process. Mould application of several common chlorinated polyolefins (CPOs) onto the surface of polypropylene (PP) and a commercial thermoplastic polyolefin (TPO) was made using a 30 ton injection moulding machine into a standard ASTM dogbone mould using optimized moulding conditions. Adhesion promotion on the order of that observed by convention applications was observed as a function of the specific CPO used. Though adhesion gradually decreased as a function of the number of mould injection cycles, a single mold treatment uniformly applied adhesion promoter to parts over several consecutive mould injection cycles, which was shown by surface analysis. Thus, a single mould treatment of adhesion promoter material resulted in several, adherent, molded parts. The molded part surface finish appeared unaffected though occasionally sticky release was observed for thermoplastic polyolefin substrates.

Thomas Schuman1 and Shelby Thames2

1) University of Missouri-Rolla,Department of Chemistry and Materials Research Center, Rolla, MO 65409

2) The University of Southern Mississippi, School of Polymers and High Performance Materials, Hattiesburg, MS 39402

Role of Solvent in Producing Adhesion to Molded Polymer Surfaces

Adhesion is of paramount importance to durability and quality of any coating system. The industrial trends towards usage of waterborne coatings affects surface wetting and adhesion of coatings to molded polymer surfaces, which are typically hydrophobic and many are apolar and inert. What is the role of solvent in achieving adhesion to plastics? Information presented by Ryntz, Stoffer, Foster, Winnik, and deGenne in the characterization of polymer interfaces and/or adhesion to plastic surfaces has led to limited understanding, i.e., solvents play a role in surface adhesion development in addition to wetting. A different approach found that adhesion-promoting solvents generated surface topographies different than the as-molded interface and different than solvent exposures were adhesion was not improved. Interestingly, the quality of the solvent to promote adhesion was not measured by how "good" the solvent was for the polymer material, e.g., as suggested by solubility parameter or swelling. Instead, the ability to cause a significant change in the molded plastic surface topography was related to the measured adhesion. Poor adhesion by the coating was measured when exposure of the plastic surface to the coating solvents alone left an unaltered, as-molded surface topography. Measured improvements in adhesion thus appeared to result from improved surface area contact or altered fracture mechanics, and not necessarily improved polymer chain mobility or polymer entanglement.

Gerhard Seyfriedsberger1, Wolfgang Kern2

1) Polymer Competence Center Leoben GmbH, A-8700 Leoben, AUSTRIA

2) Graz University of Technology, Institute for Chemistry and Technology of Organic Materials, A-8010 Graz, AUSTRIA

Surface Modification of Polymers Towards Antimicrobial Properties

The modification of polymer surfaces is a common technique to tailor their surface properties. The present work aims at polyethylene surfaces with antimicrobial properties. In one approach LLDPE surfaces were modified with SO3H groups via photosulfonation. Antimicrobial properties were then achieved by immobilization of antimicrobially active polycations onto the sulfonated LLDPE surface (ionic interaction). In another approach a bulk modification of LLDPE with polymer-based biocides was carried out. For the physico-chemical characterisation of the modified LLDPE surfaces FTIR spectroscopy, surface roughness measurements (confocal microscopy), zeta potential and contact angle techniques were applied. Antimicrobial properties of sample surfaces towards E.Coli and Staph. Aureus were determined with the film adherence method (Japanese Industrial Standard JIS Z 2801). This standardised test evaluates remaining colony forming units (cfu) at surfaces. The biofilm formation potential of the LLDPE surfaces was assessed following the (preliminary) standard CEN TC164/WG3/AHG3. In all cases, polyethylene surfaces with highly antimicrobial properties were achieved while maintaining the mechanical properties of polyethylene. Moreover, the test-samples displayed a large reduction of biofilm formation. Polymer modification strategies, mechanisms of antimicrobial activity, assays and characterisation techniques are discussed together with regard to practical application.

Sam Siau, Alfons Vervaet, Andre Van Calster and Daniël Baert; Department of ELIS, University Ghent, Sint-Pietersnieuwstraat 41, 9000 Gent, BELGIUM

The Development of Epoxy Polymer Surface Roughness Due to Wet Chemical Treatments and its Relevance to Adhesion of Electrochemically Deposited Copper

The mechanisms that influence the kinetics of surface roughness development due to various chemical treatments are investigated. A sequence of sweller solutions and oxidizers are considered. The surface of the polymer consists of a number of functionalities that break the polymer chain down and are transmitted through the chain as the polymer is etched. These groups are unevenly distributed atop of the surface, causing a difference in etching speed, which creates the roughness on the surface. Prior to the treatment the surface of the epoxy polymer layer is almost perfectly flat.

Usage of a sweller agent increases the number of break down groups on the surface and hence increases the speed of roughness formation. The activation of the surface due to a sweller agent saturates and is caused by a reaction between the sweller present inside the free volume of the polymer and the polar groups of the polymer chains. The surface topography of the oxidized epoxy polymer layer develops into a fractal surface due to small fluctuations in the number of polymer break down groups. For limited oxidation treatment times there is direct correlation between AFM measured surface line length increase and the peel strength of electrochemically deposited copper.

G. Szeiffova 1, B. Alince, 2, J. Gigac 1 and R. Tino 3

1) Pulp and Paper Research Institute, Lamacska 3, Bratislava, SLOVAKIA

2) Pulp and Paper Research Centre, McGill University, Montreal, QC, CANADA

3) Department of Chemical Technology of Wood, Pulp and Paper, FChPT, Slovak University of Technology, Radlinskeho 9, Bratislava, SLOVAKIA

Modification of Surface Charge of Pulp Fibers and the Effect on Wet Web Strength

Breaking of paper during wet end operations causes high cost expenses in papermaking. Tensile strength of paper depends on the solid content. After the free water removal, there is an area where wet swollen fibers does not create chemical bonding yet and surface tension of water is not the force holding fibers together anymore. This is the area of interest - around 30 % of solid content. Our work tries to understand the processes and mechanism of fibers consolidation. The idea was to overcome the electrostatic repulsion by inter-fiber bridging adding various cationic polymers common used in papermaking. Next step was to change the surface charge of fibers followed by trying to bridge modified fibers by negative polymers. The deposition of polymers onto cellulose fibers was studied as well as the effect of surface tension of water and beating on tensile strength.. The wet web strength of blank paper and strength of paper made from treated fibers was compared.

Daliana G. Abreu1, Wagner Dasilva1,2 Alan Entenberg3, Thomas Debies2

and Gerald A. Takacs1

1) Department of Chemistry, Center for Materials Science and

Engineering, Rochester Institute of Technology, Rochester, NY, 14623

2) Xerox Corporation, Webster, NY 14580

3) Department of Physics, RIT, Rochester, NY, 14623

Chemistry at the Cu-fluoropolymer Interface: Relevance to Adhesion

Fluoropolymers, like Teflon(r)PTFE (polytetrafluoroethylene), FEP fluorinated thylene-propylene co-polymer) and PFA polytetrafluoroethylene-co-perfluoropropyl vinyl ether), have been extensively used in space applications, protective coatings, microelectronic packaging and biotechnology. However, their low surface energy properties present considerable challenges for adhesion when bonding to other materials, such as, the conductor copper.

During recent investigations of the surface modification of PTFE, FEP and PFA using vacuum UV photo-oxidation, the adhesion of sputtered Cu to the modified surface was found to increase with treatment for PTFE while FEP and PFA demonstrated good practical adhesion at short treatment times and cohesive failure at long treatment times. Therefore, this study was conducted to investigate: (1) the depth of polymer on the failure surface with argon ion etching and (2) the chemistry near the interface with X-ray photo-electron spectroscopy (XPS). In addition, results will be reported on the surface modification of untreated PTFE, FEP and PFA with thin films of Cu formed from two sources having different energies of metallization; thermal evaporation and sputter deposition.

Takeshi Tanaka; Department of Electronics and Photonic Systems Engineering, Hiroshima Institute of Technology, Hiroshima 731-5193, JAPAN

Surface Modification of Polymer Thin Films by PBII

Plasma source ion implantation (PSII) is a rapidly advancing technique that is highly suitable for the surface treatment of three-dimensional workpieces. Many plasma sources have been employed to produce ions for implantation, including filament discharge, rf discharge, microwave discharge and metal arc discharge. PSII using an external pulsed inductively coupled plasma (ICP) source has been shown to be an effective method for modifying the surface characteristics of polymer films and forming amorphous carbon layers on films and bottles . In this study, we have reviewed the barrier effectiveness of polymer films modified using this technique, and have characterized the amorphous carbon layers by various methods to investigate their crystal structure, chemical bonding, and surface morphology.

Susanne Temmel1, Wolfgang Kern2, Thomas Luxbacher3

1) Polymer Competence Center Leoben GmbH, A-8700 Leoben, AUSTRIA

2) Graz University of Technology, Institute for Chemistry and Technology of Organic Materials, A-8010 Graz, AUSTRIA

3) Anton Paar GmbH, A-8054 Graz, AUSTRIA

Surface Modification of Polyethylene by Photosulfonation

The present work is focused on the surface modification of LDPE by UV irradiation with a Hg lamp in the presence of sulfur dioxide and air. This process, also called photosulfonation, results in the introduction of sulfonic acid groups onto the polymer surface. To characterize the modified LDPE surfaces, FTIR-spectroscopy, contact angle testing as well as zeta potential measurements were applied. An FTIR spectroscopic examination of photosulfonated LDPE surfaces showed new bands typical of -SO3H groups (1170 and 1037 cm-1). These FTIR signals were getting stronger with increasing UV irradiation time but remained constant after prolonged UV irradiation. Contact angle measurements showed a similar trend: the contact angle q of water (sessile drop) decreased from q = 99░ to about q = 30░ and then remained constant. This indicates highly polar surfaces. The zeta potential z of the modified LDPE surfaces shifted to less negative values with increasing UV irradiation time (from z = -35 mV to z = -18 mV at pH = 8). This result is explained by an increase of the hydrophilicity of the LDPE surface. Concomitantly the isoelectric point was shifted to lower pH values (from IEP = 4 to IEP ~ 2) which indicates an increasing amount of -SO3H groups present at the sample surface. Moreover, LDPE samples were cross-linked by e-beam irradiation and then subjected to the photosulfonation process. Cross-linked LDPE offers a higher degree of modification with -SO3H groups. This is explained by a lower amount of extractable components as a result of radiation-induced network formation.

A. Kokkinis1, I. Raptis1 , J. C. Statharas2 and E. S. Valamontes3

1) Institute of Microelectronics, NCSR "Demokritos", 153 10 Ag. Paraskevi GREECE.

2) Department of Mechanical Engineering, Technological and Educational Institute of Chalkis, 34400 Psahna, Euboea, GREECE.

3) Department of Electronics, Technological Educational Institute of Athens, 12210 Aegaleo, GREECE.

Dissolution Properties of Ultrathin Photoresist Films with Multiwavelength Interferometry

According to the ITRS, a significant decrease in lateral resolution and thickness of resists is anticipated for the forthcoming decade. In order to study in-situ the dissolution of thin resist films, a set-up based on multiwavelength interferometry was developed. Using this set-up and an appropriate fitting algorithm, based on the interference function, the resist thickness vs. time is calculated.

Figure 1: Multiwavelength dissolution rate monitoring apparatus.

In the present work, the dissolution of PMMA films in a 20-300nm thickness range is studied. First results showed, that in the case of ultra thin films of high molecular weights (996K, 350K), dissolution proceeds smoothly after an initial surface inhibition period, while thicker films present a more complex dissolution curve. In the case of low molecular weight (15K) the surface inhibition period is negligible and dissolution proceeds smoothly for the whole thickness range examined. PMMA films exposed with various DUV doses exhibit similar behaviour with the unexposed films in terms of dissolution inhibition.

Further research on PMMA dissolution properties using additional developer solutions and broader PAB temperature range is in progress.

Benoit Viallet; INSA, 135 avenue de Rangueil, 31077 TOULOUSE cedex 4, FRANCE

Adhesion Improvement of Epoxy-Siloxane Resist on a BCB Layer: Application to Nanoimprint Lithography

Nanoimprint lithography (NIL) are low cost technologies used to reproduce nanometer size patterns. In the approach involving a curable polymer, the adhesion between this polymer and the underlying layer is an important issue. The imprinted polymer used in this study is an epoxy-siloxane and the underlying layer is made with poly-bis*(*benzocyclobutenyl*)*divinyltetramethylsiloxane (BCB). BCB is a resist used in microelectronics and optoelectronic for its low dielectric constant, its transparency up to 1700 nm, its high chemical resistance and thermal stability.

The poor adhesion between epoxy-siloxane and non treated BCB does not allowed NIL with nanometer size patterns. The effect of different surface treatments : UV/ozone, O_2 plasma, SF_6 /O_2 plasma and adhesion layers deposition on the quality of imprinted patterns has been studied. The degradation of surface layer of BCB by UV/ozone photochemical treatment has been analyzed by various methods: XPS, SIMS, chemical solubility and contact angle. This analyze reveals the creation of three layers: an oxidized surface with a near SiO_2 composition, a polymer degraded layer and the non modified BCB. The application of surface treatments on inorganic surfaces (LaF_3 , GaAs) will also be presented and a comparison will be done between organic and inorganic surface.

Zhi-Kang Xu, Zhen-Gang Wang, Xiao-Jun Huang; Institute of Polymer Science, Zhejiang University, Hangzhou 310027, P. R. CHINA

Surface Modification of Polyacrylonitrile-Based Membranes by Chemical Reactions

Membranes were prepared from poly(acrylonitrile-co-maleic acid) (PANCMA) and poly(acrylonitrile-co-2-hydroxyethyl methacrylate) (PANCHEMA) containing carboxyl groups and hydroxyl groups respectively. To suppress the protein adsorption and platelet adhesion on these membrane surface, chemical reactions were used to immobilize biocompatible macromolecules (such as poly(ethylene glycol) (PEG) and heparin) on the PANCMA membrane and to generate phospholipid moieties on the PANCHEMA membranes. It was found that the carboxylic groups can be conveniently conversed into anhydride and then esterified with PEG. The antifouling property and biocompatibility of PANCMA membrane are effectively improved by the immobilization of PEG on the membrane surface, in which PEG-400 modified membrane shows the best performance. Moreover, membranes tethered with heparin shows the best blood compatibility. On the other hand, a novel approach for the surface modification of PANCHEMA membranes by introducing phospholipid moieties is presented, which involved the reaction of the hydroxyl groups on the membrane surface with 2-chloro-2-oxo-1,3,2-dioxaphospholane (COP) followed by the ring-opening reaction of COP with trimethylamine. It was found that the bovine serum albumin adsorption and platelet adhesion were suppressed significantly with the introduction of phospholipid moieties on the membranes surface. These results demonstrated that the described process was an efficient way to improve the surface biocompatibility for the acrylonitrile-based copolymer membrane.

V. Zaporojtchenko, J. Zekonyte, U. Schuermann and F. Faupel; Faculty of Engineering, Chair for Multicomponent Materials, Chirstian-Albrechts University Kiel, Kaiserstrasse 2, 24143 Kiel, GERMANY

Metallization of Polymer Surfaces after Ion Beam Treatment. Mechanism of Adhesion Improvement and Degradation

Ion beam treatment of polymers induces different phenomena in the near surface layer of polymers, and promotes adhesion to metals. Using XPS, FTIR, TEM and AFM surfaces of different polymers ( PS, PP, PMMA, BPA-PC, etc.) were examined after low energy ion-beam treatments with oxygen, nitrogen and argon ions in the ion fluence range from 1012 to 1016 cm-2 to clarify the following points: removal of the surface layers, chemical reaction after treatment in vacuum and after exposition to air, identification of adsorption-relevant species for metal atoms, formation of cross-links in the outermost polymer layer. Depending on the ion-polymer interaction these effects contribute in a synergistic manner to significant or negligible enhancement of the metal-polymer adhesion. The early stages of metal-polymer interface formation during metallization play also a crucial role in the metal-polymer adhesion. Therefore, the influence of the ion fluence and ion chemistry as well as substrate temperature on the condensation of metals, film growth and peel strength were measured. For some polymers, the peel strength showed a maximum at a certain fluence depending on ion chemistry. The locus of failure changed at the same time from interfacial failure for untreated polymer surfaces to cohesive failure in the polymer for modified surfaces. A multilayer model of the metal-polymer interface after ion treatment is discussed.

Ze Zhang1, Lê H. Dao2, Dominic Tessier2, Xiaoping Jiang1, Robert Guidoin1, Martin King3

1) Department of Surgery, Faculty of Medicine, Laval University and Saint-François d'Assise Hospital Research Center, Quebec City, Quebec, CANADA

2) INRS-Energy-Materials-Telecommunication, University of Quebec, Varennes, Quebec, CANADA

Polypyrrole-Grafted Polyester Fabrics: Preparation, Electrical stability and Biocompatibility

Conductive polypyrrole (PPy) has been shown to support cell growth and to modulate cellular behaviors through electrical stimulation. However, because of its highly conjugated chemical structure, pure PPy is unprocessable. In this study, PPy was grafted onto the surface of poly(ethylene terephthalate) (PET) fabrics through a three-step method, including phosphonylation or plasma treatment to active fabric surface, grafting of 1-(3-hydroxypropyl) pyrrole, and copolymerization of pyrrole monomers with the grafted pyrrole groups. The surface chemistry and morphology of the grafted PPy were studied with XPS and SEM. The electrical stability of the PPy-grafted PET fabrics was investigated using an in vitro model. Finally, the biocompatibility of the PPy-grafted fabrics was analyzed through cell culture and animal experiments. The results showed that a very thin and stable PPy layer formed on the surface of the PET microfibres, rendered the composite fabrics electrically conductive with a surface resistivity in the range of 10-3-10-5 ohm/square. The decay of electrical conductivity in aqueous condition was related to the dedoping and oxygen uptake of the PPy. The PPy-grafted fabrics proved biocompatible.