Michael Tatoulian

On plasma processing of polymers and the stability of the surface properties for enhanced adhesion to metals

Abstract This paper deals with the plasma surface treatment of polymers in a low frequency bell jar reactor with non-symmetrical configuration of electrodes. The highly energetic character of this discharge due to its low excitation frequency and electrode configuration, as well as its small discharge volume makes it a very efficient and fast functionalization process. Amongst the different plasma gases used for the adhesion improvement of polypropylene to aluminum, ammonia has shown to be the most suitable one for this application. Since the NH and NH2 radicals play an important role in the kinetics of nitrogen incorporation in polymers, mixtures of N2 and H2 were also used as possible substitutes for ammonia. The former are more environmentally friendly and easier to handle in industry than ammonia. The efficiency of nitrogen rich mixtures in the case of the second application, i.e. adhesion improvement of copper to fluoropolymers has been compared to that of ammonia which still shows faster nitrogen incorporation. The last part of this paper is devoted to the study of the energetic character of plasmas of mixtures of He+NH3 by OES and electrical measurements in the whole range of composition of the two gases. The results show that an ammonia percentage ranging from 5 to 10% in plasmas of mixtures of He/NH3 represents a transition between two different discharge regimes. Plasmas of mixtures of He+2% NH3, characterized by highly energetic electrons, ions and probably metastables of helium give rise to enhanced adhesion of PP to aluminum which remains stable with time.

Functionalization of nitrocellulose membranes using ammonia plasma for the covalent attachment of antibodies for use in membrane-based immunoassays

A plasma process using NH 3 was developed in order to incorporate amine functions on the surface of nitrocellulose membranes for an oriented covalent attachment of antibodies through their oxidized carbohydrate moieties. An average covalent binding capacity of 60 μg/cm 2 of antibodies was reached. The potential use of this process in developing environmental immunochemical techniques was demonstrated.

On the long term antibacterial features of silver-doped diamondlike carbon coatings deposited via a hybrid plasma process

Environmental surfaces are increasingly recognized as important sources of transmission of hospital-acquired infections. The use of antibacterial surface coatings may constitute an effective solution to reduce the spread of contamination in healthcare settings, provided that they exhibit sufficient stability and a long-term antibacterial effect. In this study, silver-incorporated diamondlike carbon films (Ag-DLC) were prepared in a continuous, single-step plasma process using a hybrid, inductively coupled plasma reactor combined with a very-low-frequency sputtering setup. The average Ag concentration in the films, ranging from 0 to 2.4 at. %, was controlled by varying the sputtering bias on the silver target. The authors found that the activity of Escherichia coli was reduced by 2.5 orders of magnitude, compared with the control surface, after a 4-h contact with a 2.4 at. % Ag-DLC coating. The coatings displayed slow release kinetics, with a total silver ion release in the sub-ppb range after 4 h in solution, as measured by graphite furnace-atomic absorption spectroscopy. This was confirmed by Kirby-Bauer diffusion tests, which showed limited diffusion of biocidal silver with a localized antibacterial effect. As a slow and continuous release is mandatory to ensure a lasting antibacterial effect, the newly developed Ag-DLC coatings appears as promising materials for environmental hospital surfaces.

Influence of the 316 L stainless steel interface on the stability and barrier properties of plasma fluorocarbon films.

Coatings are known to be one of the more suited strategies to tailor the interface between medical devices and the surrounding cells and tissues once implanted. The development of coatings and the optimization of their adhesion and stability are of major importance. In this work, the influence of plasma etching of the substrate on a plasma fluorocarbon ultrathin coating has been investigated with the aim of improving the stability and the corrosion properties of coated medical devices. The 316 L stainless steel interface was subjected to two different etching sequences prior to the plasma deposition. These plasma etchings, with H(2) and C(2)F(6) as gas precursors, modified the chemical composition and the thickness of the oxide layer and influenced the subsequent polymerization. The coating properties were evaluated using flat substrates submitted to deformation, aging into aqueous medium and corrosion tests. X-ray photoelectron spectroscopy (XPS), time of flight-secondary ion mass spectrometry (ToF-SIMS), ellipsometry, and atomic force microscopy (AFM) were performed to determine the effects of the deformation and the aging on the chemistry and morphology of the coated samples. Analyses showed that plasma etchings were essential to promote reproducible polymerization and film growth. However, the oxide layer thinning due to the etching lowered the corrosion resistance of the substrate and affected the stability of the interface. Still, the deformed samples did not exhibited adhesion and cohesion failure before and after the aging.

Immobilization of Biomolecules on NH3, H2/NH3 Plasma-Treated Nitrocellulose Films

Detectors with covalently immobilized bioactive compounds able to interact with selected analytes are needed for various kinds of biosensors. Protein macromolecules can be immobilized covalently on surfaces with appropriate functional groups such as amine groups. Low pressure plasmas of NH3 and NH3/H2 mixtures were used to incorporate a maximum of 2.4 amine functions per nm2 of porous surface under specific conditions. A mechanism of the functionalization process was proposed using on-line emission spectroscopy and mass spectrometry analysis to monitor the reaction process. The physico-chemical modifications created on the plasma-treated material were investigated by surface analytical techniques such as X-ray photoelectron spectroscopy (XPS) and Scanning Electron Microscopy (SEM).

Controlled Distribution and Clustering of Silver in Ag-DLC Nanocomposite Coatings Using a Hybrid Plasma Approach.

Incorporation of selected metallic elements into diamond-like carbon (DLC) has emerged as an innovative approach to add unique functional properties to DLC coatings, thus opening up a range of new potential applications in fields as diverse as sensors, tribology, and biomaterials. However, deposition by plasma techniques of metal-containing DLC coatings with well-defined structural properties and metal distribution is currently hindered by the limited understanding of their growth mechanisms. We report here a silver-incorporated diamond-like carbon coating (Ag-DLC) prepared in a hybrid plasma reactor which allowed independent control of the metal content and the carbon film structure and morphology. Morphological and chemical analyses of Ag-DLC films were performed by atomic force microscopy, scanning electron microscopy, and X-ray photoelectron spectroscopy. The vertical distribution of silver from the surface toward the coating bulk was found to be highly inhomogeneous due to top surface segregation and clustering of silver nanoparticles. Two plasma parameters, the sputtered Ag flux and ion energy, were shown to influence the spatial distribution of silver particles. On the basis of these findings, a mechanism for Ag-DLC growth by plasma was proposed.

Fabricating a reactive surface on the fibroin film by a room-temperature plasma jet array for biomolecule immobilization

A simple dielectric barrier discharge (DBD) jet array was designed with a liquid electrode and helium gas. The characteristics of the jet array discharge and the preliminary polymerization with acrylic acid (AA) monomer were presented. The plasma reactor can produce a cold jet array with a gas temperature lower than 315 K, using an applied discharge power between 6 W and 30 W (Vdis ? Idis). A silk fibroin film (SFF) was modified using the jet array and AA monomer, and the treated SFF samples were characterized by atomic force microscopy (AFM), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), and contact angle (CA). The deposition rate of the poly acrylic acid (PAA) was able to reach 300 nm/min, and the surface roughness and energy increased with the AA flow rate. The FTIR results indicate that the modified SFF had more carboxyl groups (-COOH) than the original SFF. This latter characteristic allowed the modified SFF to immobilize more quantities of antimicrobial peptide (AP, LL-37) which inhibited the Escherichia coli (E. Coli) effectively.

Plasma and Electrospray deposition to improve the biocompatibility of stents

Metallic Intravascular stents are medical devices used to scaffold a biological lumen, mostly diseased arteries, after balloon angioplasty. They are commonly made of 316L stainless steel or Nitinol, two alloys containing Nickel, an element classified as potentially toxic and carcinogenic. Although they are largely implanted, the long-term safety of such metallic elements is still controversial, since the corrosion processes may lead to the release of several metallic ions. In order to avoid the metallic ion release in the body and to improve the biocompatibility of metallic stents with their biological environments, polymer coatings have been deposited by two different technologies, i.e. plasma surface modifications and Electrospraying. The role of the polymer coating is then to encapsulate the stainless steel device, and to favour the chemical grafting of Phosphorylcholine, a molecule known for its hemocompatible properties.1 In this talk, the state of the art on low pressure and atmospheric pressure plasmas for deposition of organic coatings will be given and we will present the advantages and drawbacks of each process. Then, we will present an original technology that combine a Dielectric Barrier Discharge and an electrospraying system to deposit well-defined Polyacrylic acid and Polyallylamine films. The advantage of such system is the possibility to limit the extent of the monomer fragmentation and to give rise to rapid deposition of a highly functionalised plasma polymer layer, and also the possibility to cover three dimensional objects, such as stents. Thus, the theory of EHDA technology will be explained: special attention has been paid to define the Electrospray parameters (Voltage, flow of precursor, nozzle-substrate distance…) which control the size distribution of the charged droplets and as a consequence, the structure of the film coating. The film coatings have been analysed with XPS and by ATR. Moreover, special attention will be paid on the stability of the coating which is related to both spraying conditions as well as to the preliminary plasma treatment. The potentiality and the features of the EHDA process will be then presented.

Fluidized bed plasmas reactor for catalyst synthesis and pretreatment. Application for pollution abatement in stationary and mobile sources

The preparation of automotive catalysts and commercial oxidation catalysts in stationary sources use a large amount of noble metal precursors. Moreover, during their preparation high energy (gas and temperature) is necessary for treatment processes. In order to develop a higher sustainable process, the plasma-assisted catalysts synthesis could be a solution. The use of plasmas for catalysis is already well developed and plasma treatment was already used in a low pressure system to replace the thermal calcination steps of the catalysts. Fluidized bed reactors offer the possibility to lead to homogenous treatment and have the additional advantage of excellent heat transfer rates between the gas and the particles, so that it can modify the catalytic properties of the prepared materials. The aim of our work is to prepare plasma-assisted catalysts dedicated to pollution abatement in stationary or mobile sources. For stationary sources, the first prepared catalysts are palladium based catalysts, which were chosen since the main reducing agent in combine heat power is methane. In the case of mobile sources, we have worked with silver based catalysts since ethanol could be chosen as a sustainable alternative reducing agent to replace ammonia. After the preparation of the different catalysts, the low fluidized bed plasma reactor was used to modify Pd/ γ-alumina and Ag/γ-alumina catalysts. A comparison with “classical calcination” in air at 500°C was performed in order to show the advantages of plasma treatments. The first catalytic results show that plasma treated catalysts lead to higher pollutant abatement than classically prepared ones. Thus, concerning the plasma process, we have studied the role of the plasma treatment time as well as the nature of the gas treatment. The characterization of the catalysts is in course in order to understand the influence of plasma treatment parameters on catalytic results.

Plasma Surface Modification of 316L Stainless Steel for Cardiovascular Stent Coating

Coronary stents are metallic (316L stainless steel) devices employed during balloon angioplasty to reopen and prevent the re-obstruction of a diseased narrowed area within a coronary artery. To reduce restenosis rate, bare metal stent coating is a promising solution. The coating can act as an anticorrosive barrier against the aggressive properties of biological environment, improving the long-term safety of the device. The goal of this study is to develop a dry process to isolate metallic surface from the biological environment by depositing a thin plasma polymerized allylamine (CH2=CH-CH2-NH2) film on the metallic surface. Plasma polymerized allylamine films were deposited on flat electropolished 316L stainless steel samples in a low pressure plasma reactor (70 kHz). Chemical composition of the coatings has been analysed as a function of the discharge power and treatment time. Moreover, special attention has been paid on the stability of the coating after immersion during 24 hours in D.I. water. Finally, to mimic stent expansion conditions, a “small punch test” has been used to investigate the adhesive properties of the coating. Our results demonstrate that is possible to deposit a stable, cohesive and adhesive plasma polymerized allylamine thin film which can be used as a coating for cardiovascular stents