A Comparison of PE Surfaces Modified by Plasma Generated Neutral Nitrogen Species and Nitrogen Ions

The surface modification of polyethylene (PE) by neutral nitrogen species (ground and excited state N₂ as well as atomic N; modified nitrogen plasma treatment) has been compared to the effect of nitrogen ion bombardment using X-ray Photoelectron Spectroscopy (XPS) and contact angle measurements. XPS results indicate that a greater nitrogen concentration was grafted during the modified nitrogen plasma treatment of PE, an effect that was attributed to surface sputtering during ion beam modification. The distribution of nitrogen-containing functionalities was strongly dependent upon the treatment strategy; the modified nitrogen plasma treatment lead predominantly to imine groups being formed at the PE surface, while amine groups were the dominant species produced during ion beam modification. The presence of electron irradiation during the modified nitrogen plasma treatment of PE did not modify the rate of nitrogen incorporation or change the nature of N-containing functional groups produced but did lead to a systematic decrease in contact angle.     

Easy Synthesis of Ageing-Resistant Coatings with Tunable Wettability by Atmospheric Pressure Plasma

This study presents a simple and dry approach to synthesize stable, thin organic coatings with tunable wettability by injecting appropriate quantities of propargyl methacrylate (propaMA) and acrylic acid (AA) into a dielectric barrier discharge operating at atmospheric pressure. Deposition rates of up to 11 nm s^?1 can be achieved, thanks to the high reactivity of the propaMA monomer in the discharge. The AA monomer exhibits a weaker reactivity but, as evidenced by IRRAS and XPS analyses, allows introducing polar groups into the coating, thereby modifying the surface wettability. The surface is thus shown to be tunable from highly hydrophobic (WCA = 140°, pure propaMA coatings) to highly hydrophilic (WCA = 15°, pure AA coatings) by adjusting the monomer ratio in the discharge. These coatings have been deposited on polypropylene (PP) substrates, and the resulting WCA is shown to remain constant for at least 64 days, ageing that is remarkably slow compared with plasma functionalization that usually leads to rapid hydrophobic recovery.     

Evidence of the synergetic role of charged species and atomic oxygen in the molecular etching of PTFE surfaces for hydrophobic surface synthesis

The transformation of a poly(tetrafluoroethylene) (PTFE) hydrophobic surface into a superhydrophobic one using a low pressure RF plasma is explored using optical emission spectrometry (OES), X-ray photoelectron spectroscopy (XPS), water contact angle (WCA) measurements, mass measurements, and atomic force microscopy (AFM). It is shown that the increase in contact angle is due to an increase of roughness provoked by a chemical etching of the surface. We propose a molecular mechanism for etching that requires the simultaneous presence of atomic oxygen and negatively charged species (electrons) at the PTFE surface.     

Etching processes of polytetrafluoroethylene surfaces exposed to He and He-O2 atmospheric post-discharges

A comparative study of polytetrafluoroethylene (PTFE) surfaces treated by the post-discharge of He and He-O(2) plasmas at atmospheric pressure is presented. The characterization of treated PTFE surfaces and the species involved in the surface modification are related. In pure He plasmas, no significant change of the surface has been observed by X-ray photoelectron spectroscopy (XPS), dynamic water contact angles (dWCA) and atomic force microscopy (AFM), in spite of important mass losses recorded. According to these observations, a layer-by-layer physical etching without any preferential orientation is proposed, where the highly energetic helium metastables are the main species responsible for the scission of -(CF(2))(n)- chains. In He-O(2) plasmas, as the density of helium metastables decreases as a function of the oxygen flow rate, the treatment leads to fewer species ejected from the PTFE surfaces (in agreement with mass loss measurements and the detection of fluorinated species onto aluminum foil). However, the dWCA and AFM measurements show an increase in the hydrophobicity and the roughness of the surface. The observed alveolar structures are assumed to be caused by an anisotropic etching where the oxygen atoms etch mainly the amorphous phase.     

In‐depth diffusion of oxygen into LDPE exposed to an Ar–O2 atmospheric post‐discharge: a complementary approach between AR‐XPS and Tof‐SIMS techniques

The in‐depth oxygen diffusion into a low density polyethylene film is performed in the post‐discharge of an atmospheric plasma torch, supplied in argon as carrier gas and with or without oxygen as reactive gas. The chemical and structural properties of the polymer surface and bulk are studied in terms of plasma parameters (treatment time, power, and reactive gas flow rate). A good correlation between XPS and Fourier transform infrared spectroscopy analyses is demonstrated. The penetration depth of oxygen into the bulk of the polymer is investigated by angle resolved‐XPS and time‐of‐flight SIMS. It is shown that, depending on the plasma conditions, oxygen could penetrate up to 20–40 nm into the low density polyethylene during the atmospheric plasma treatment. Copyright © 2014 John Wiley & Sons, Ltd.     

Operations research methods in preventing domino accidents in the chemical process industry

This text summarizes the results related to Operations research contained in the PhD thesis defended by the author in June 2006 under the supervision of Karel Soudan at the Universiteit Antwerpen in Belgium. The thesis is written in English and is available from the author upon request (Reniers in shaping an integrated cluster safety culture in the chemical process industry, 415 p, 2006a). This work investigates the optimization of major accident precautions in the chemical process industry. An integrated cluster safety culture is shaped by developing three separate capabilities (procedural, human, and technological) and by both integrating and optimizing them using the well-known Deming loop. The technological (Operations research) part develops a cluster management decision support system. The latter tool offers prevention planning guidance in taking adequate precaution measures to overcome complex domino effect risks.      

Synthesis of superhydrophobic PTFE-like thin films by self-nanostructuration in a hybrid plasma process

Superhydrophobic poly(tetrafluoro-ethylene) (PTFE) like thin films were grown on silicon wafers using a plasma-based hybrid process consisting on sputtering a carbon target in an Ar/CF₄ atmosphere. The influence of the bias voltage applied to the substrate (V_Bias) as well as of the gas mixture composition (%CF₄) on the chemical composition, the wettability and the morphology of the deposited thin films were evaluated.The chemical composition measured by X-ray Photoelectron Spectroscopy (XPS) has revealed that the F/C atomic ratio is always lower than for conventional PTFE (F/C = 2) and that it decreases when V_Bias increases (from F/C = 1 for V_Bias = ? 100 V to F/C = 0.75 for V_Bias = ? 200 V). This behavior is associated with the preferential sputtering of the fluorine atoms during the plasma-assisted growth of the films. Consecutively, a self-nanostructuration enhanced when increasing V_Bias is observed. As a consequence, the water contact angle (WCA) measurements range from 70° up to 150° depending on (i) the fluorine concentration and (ii) on the magnitude of the nanostructuration. In addition, for the films presenting the highest WCAs, a small hysteresis between the advancing and receding WCAs is observed (< 10°) allowing these films to fulfill completely the requirements of superhydrophobicity. The nanostructuration is probably due to the chemical etching by fluorine atoms of the fluorinated group.In order to get more understanding on the wettability mechanisms of these surfaces, the topography of the films has been evaluated by atomic force microscopy (AFM). The data have revealed, for all films, a dense and regular structure composed by conic objects (A_vH is their average height and A_vD is the average distance between them) for which the dimensions increase with V_Bias. A correlation between A_vH/A_vD, defined as the “morphological ratio”, with the WCA was established. Theoretical evaluations of the WCA using the Wenzel and Cassie equations with, as inputs, the features of the deposited thin film surfaces measured by AFM suggest that the wetting regime is intermediate between these two ideal situations.