Improvement of properties of silica‐filled styrene‐butadiene rubber composites through plasma surface modification of silica

The performance of plasma surface modified silica filler in styrene‐butadiene rubber (SBR) matrix has been analyzed. The conditions of plasma modification have been optimized by taking secant modulus as a standard parameter and the occurrence of the modification has been confirmed by surface area determination and Fourier transform infrared spectroscopy. The plasma‐modified surface of silica has been found to be composed of carbon–carbon double bonds and carbon–hydrogen bonds. Silane treatment also has been carried out on silica filler surface for a comparative assessment of its influence in the curing behavior and filler–rubber interaction. The cure reactions of all the rubber compounds have been found to be proceeded according to first‐order kinetics. A reduction in the cure reaction rate constant has been observed with the loading of unmodified and surface modified silica, emphasizing the cure deactivation of the matrix rubber by the silica filler. The filler dispersion, as revealed by scanning electron microscopy, has been found to be greatly improved by the plasma as well as silane treatment. The filler–rubber interaction has been found to be greatly improved by both surface treatments, but the best balance of mechanical properties has been observed with plasma surface modification only. Copyright © 2004 John Wiley & Sons, Ltd.     

Optical emission from tetrafluoromethane plasma and its relationship to surface modification of hexatriacontane

The optical emission from tetrafluoromethane plasma (2% argon included) has been studied by emission spectroscopy. The evolution ofCF ^*,CF ₂ ^* , andF emissions has been followed during the treatment of an organic surface. An-alkane, hexatriacontane, has been used as a model for high density polyethylene surface and treated in different plasma conditions. We found that the evolution of fluorinated species emissions in the plasma gas phase is not only a measurement of the reactive species concentrations, but also an indication of the surface modifications. The surface properties, such as surface energy and surface roughness are correlated to the emission intensity of reactives species in the plasma gas phase. A mild exposure to the plasma can result in a great decrease of surface energy corresponding to the fluorination. The surface roughness only changes under drastic plasma conditions.     

Evaluation of the stress-strain properties of surface layers in plasma-treated polymers

The surface treatment of poly(ethylene terephthalate) (PET) and poly(vinyl chloride) (PVC) films in cold plasma over 1–15 min was carried out. It was found that the subsequent deformation of the films is accompanied by a special type of surface structuring that has been previously observed for polymer films with a thin hard coating. It was shown that unlike metal coatings, the thickness of the modified surface layer slightly depends on the time of treatment in plasma. The previously developed approach to analysis of the emerging patterns makes it possible to evaluate the stress-strain properties of the coatings. It was first revealed that the tensile strength of the modified layer produced in PET by plasma treatment is ∼12.3 MPa and its elongation at break varies from 20 to 90%. The differences in the properties between the plasma-modified surface layers of the polymer and the metal coatings studied earlier are discussed.     

Plasma surface modification of organic materials: comparison between polyethylene films and octadecyltrichlorosilane self-assembled monolayers

Low-pressure low-frequency NH3 plasmas have been used for the surface modification of bulk polyethylene films and of octadecyltrichlorosilane (OTS) self-assembled monolayers deposited on oxidized silicon wafers. The incorporation of nitrogen-containing groups by the plasma treatment has been followed by contact angle measurements and by X-ray photoelectron spectroscopy. The surface degradation of the OTS monolayers due to plasma etching has been measured separately by optical ellipsometry with subnanometric accuracy. Our data show clear evidence for the existence of an optimum treatment time, yielding a high density of NH2 functional groups without significant variation of the structural features of the organic material. Self-assembled monolayers appear as excellent model systems to characterize the effects of plasma discharges on polyolefins. In particular, they allow testing the influence of molecular orientation, packing density, and crystallinity on the final results.     

Characterization of surface modified flax fibers and their biocomposites with PHB

Flax fiber was treated with acetic anhydride or with ethylene plasma to improve adhesion with poly(3-hydroxybutyrate) (PHB). The flax fiber surface became hydrophobic by the surface treatments. The ethylene plasma treated flax fiber has better thermal resistance and shows higher interfacial adhesion strength in flax/PHB biocomposite than the chemically modified flax fiber with acetic anhydride. Optimum conditions of the ethylene plasma treatment were found to be 0.5 cm³/sec of the ethylene flow rate and 50 W of the plasma power with 5 min of the treatment time.     

A two‐stage surface treatment for the long‐term stability of hydrophilic SU‐8

The use of SU‐8 photoresist as a structuring material for portable capillary‐flow cytometry devices has been restricted by the near‐hydrophobic nature of the SU‐8 surface. In this work, we evaluate the use of chemical and plasma treatments to render the SU‐8 surface hydrophilic and characterise the resulting surface utilising a combination of techniques including contact angle goniometry, atomic force microscopy and X‐ray photoelectron spectroscopy. In particular, for low‐power plasma treatments, we find that the chemistry of the plasma used to modify the SU‐8 surface and the incorporation of O₂ on that modified surface are paramount for improved surface wettability, whilst plasma‐induced surface roughness is not a necessary requirement. We demonstrate a technique to obtain a hydrophilic SU‐8 surface with contact angle as low as 7° whilst controlling and significantly reducing the level of surface roughness generated via the applied plasma. An additional chemical treatment step is found to be essential to stabilise the activated SU‐8 surface, and incubation of the samples with ethanolamine is demonstrated as an effective second‐stage treatment. Application of the optimised two‐stage surface treatment to cross‐linked SU‐8 is shown to result in a smooth hydrophilic surface that remains stable for over 3 months. Copyright © 2015 The Authors Surface and Interface Analysis Published by John Wiley & Sons Ltd.     

Atmospheric‐pressure spin plasma jets processing of polymethylmethacrylate surface using experimental design methodology

Atmospheric‐pressure spin plasma jets (APSPJs) have been developed to induce surface modifications on polymethylmethacrylate (PMMA). In this study, an experimental design methodology was used to investigate the influence of process parameters [such as radio frequency (RF) power, processing gap, and number of treatment cycles] on the characteristics of PMMA surface treated by APSPJs. It was observed from the atomic force microscope (AFM) and scanning electron microscope (SEM) results that the surface morphology of PMMA treated by direct plasma is much rougher than that treated by remote plasma. The direct plasma used in APSPJs processing created a substantial amount of nanostructure grains. Moreover, the measured XPS results showed that the O/C ratios of the PMMA surface were substantially increased and subsequently water contact angle decreased on direct plasma treatment. This decrease is due to an increase of oxygen‐containing functional groups on the PMMA surface by the APSPJs processing. From the statistical analysis, the RF power and the processing gap were found to play a major role in enhancing the hydrophilic properties of PMMA surface. In contrast, the number of treatment cycles played only a secondary role in this case. Finally, in this study the APSPJs processing was demonstrated to be an effective method for surface modification of PMMA by controlling processing parameters during the treatment process. Copyright © 2009 John Wiley & Sons, Ltd.     

Characterization of surface modifications of stainless steel samples after electron and ion bombardment by SEM, AES, and XPS

The interaction of inert or reactive gas plasmas with the surface of stainless steel has been investigated with the aim, to modify the surface and hence to reduce the outgassing rate of the material, an important factor for the production of an ultrahigh vacuum. The plasma treatments investigated may be an alternative to the common used in situ baking. The samples have been exposed to electrons, argon and oxygen ions either in a DC glow discharge or in a microwave discharge. The DC glow discharge in Ar/O₂, the most effective plasma treatment reduces the outgassing rate by a factor of 10. After this treatment the surfaces of the samples have been investigated with respect to the topography and the chemical composition (depth profile) by Secondary Electron Microscopy (SEM), Auger Electron Spectroscopy (AES) and X-ray Photoelectron Spectroscopy (XPS), respectively. The surface modifications resulting from the different treatments of the samples have been correlated to the outgassing rate.     

Superhydrophobicity of PHBV fibrous surface with bead-on-string structure

A poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) fibrous surface with various bead-on-string structures was fabricated by electrospinning. PHBV was electrospun at various concentrations and then CF4 plasma treatment was employed to further improve the hydrophobicity of the PHBV fiber surfaces. The surface morphology of the electrospun PHBV mats was observed by scanning electron microscopy (SEM). The surface properties were characterized by water contact angle (WCA) measurements and X-ray photoelectron spectroscopy (XPS). The surface morphology of the electrospun PHBV fibrous mats with the bead-son-string structure varied with the solution concentration. The WCA of all of the electrospun PHBV mats was higher than that of the PHBV film. In particular, a very rough fiber surface including porous beads was observed when PHBV was electrospun from the solution with a concentration of 26 wt%. Also, its WCA further increased from 141 degrees to 158 degrees after CF(4) plasma treatment for 150 s. PHBV can be rendered superhydrophobic by controlling the surface morphology and surface energy, which can be achieved by adjusting the electrospinning and plasma treatment conditions.     

Effects of oxygen plasma on cellulose surface

These studies aimed to investigate in detail changes on cellulose surfaces treated with low pressure oxygen plasma at various exposure times. Modifications of cellulose films were studied in respect to topography effects by means of atomic force microscopy and scanning electron microscopy. Chemical effects of plasma treatment were studied using X-ray photoelectron spectroscopy and X-ray diffractometry. Results show that the topographical evolution of the surfaces to rougher ones is not at all gradual. Local maxima of fractionation and the surface size regularity were investigated using surface fractal analysis and Wenzel roughness factors, respectively. It was shown, that plasma treatments decompose the cellulose material by formation of highly functionalized molecules. Such plasma-initiated and supported reactions taking place on the sample surface. The bulk phase and in particular, the crystalline domains are not influenced by plasma treatments. The studies provide useful information to understand the plasma reaction on amorphous and crystalline regions of cellulose surfaces and allow to predict effects of the plasma treatment on physical and chemical properties of much more complex cellulose systems such as cotton fibres and fabrics.     

Fabrication and characterization of poly(methylmethacrylate) microfluidic devices bonded using surface modifications and solvents

The fabrication of polymer microchips allows inexpensive, durable, high-throughput and disposable devices to be made. Poly(methylmethacrylate) (PMMA) microchips have been fabricated by hot embossing microstructures into the substrate followed by bonding a cover plate. Different surface modifications have been examined to enhance substrate and cover plate adhesion, including: air plasma treatment, and both acid catalyzed hydrolysis and aminolysis of the acrylate to yield carboxyl and amine-terminated PMMA surfaces. Unmodified PMMA surfaces were also studied. The substrate and cover plate adhesion strengths were found to increase with the hydrophilicity of the PMMA surface and reached a peak at 600 kN m(-2) for plasma treated PMMA. A solvent assisted system has also been designed to soften less than 50 nm of the surface of PMMA during bonding, while still maintaining microchannel integrity. The extent to which both surface modifications and solvent treatment affected the adhesion of the substrate to the cover plate was examined using nanoindentation methods. The solvent bonding system greatly increased the adhesion strengths for both unmodified and modified PMMA, with a maximum adhesion force of 5500 kN m(-2) achieved for unmodified PMMA substrates. The bond strength decreased with increasing surface hydrophilicity after solvent bonding, a trend that was opposite to what was observed for non-solvent thermal bonding.     

Manipulating the surface properties of polyacrylamide with nitrogen plasma

Polyacrylamide (PAL) was physically adsorbed onto a hydroxylated silicon surface to form a uniform PAL film and the up-top PAL thin film was treated by nitrogen (N₂) plasma for surface modification. The atomic composition of the modified surface of the PAL film adsorbed on silicon substrate was analyzed with Fourier Transform Infrared Spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). The surface energy of PAL film was calculated from the data of contact angle of three-probe liquid. The FTIR results show an increase of peak intensity at 1214 cm⁻¹ (NH₂ stretch vibration) after the nitrogen plasma treatment, which confirms that the nitrogen was grafted to the PAL surface in the process of N₂-plasma treatment. The XPS results show that the ratio of relative intensity of N1s to O1s increases with increasing the plasma treatment time, which further affirms the formation of the amine groups on the PAL surface after the nitrogen plasma treatment. The surface tension increases with increasing the plasma grafting time. However, the surface energy decreases rapidly at the early stage when stored in air and approaches to an equilibrium value. It suggests that some physically-adsorbed ions and alkyl radicals on PAL surface can rapidly lose their activities. The increase of the surface tension of the plasma treated PLA films is due to the amine groups covalently grafted to PAL surface.     

Steel surface processing by a continuous optical discharge plasma

The influence of a continuous optical discharge (COD) plasma generated in flowing argon and argon-nitrogen mixture on alloy and carbon steel surfaces has been investigated. Changes in the structure, element composition, and microhardness of steel surface layers under the action of a COD plasma and laser beam were observed. In the presence of a COD plasma the microhardness distribution in hardened zone reaches its maximum at the metal surface and is different from that measured for samples processed by laser beam only.     

Amination of Poly(ethylene-terephthalate) polymer surface for biochemical applications

Amine functionalization of Poly(ethylene-terephthalate) (PET) films for covalent binding of peptides is described. Ammonia plasma treatments have been used to graft nitrogen-containing functional groups onto the PET surface. The samples were then analyzed by X-ray photoelectron spectroscopy (XPS) and a parametric study was performed to define the best plasma grafting conditions. For biological tests, samples were sterilized by steam autoclaving: this induces a four to fivefold loss of the nitrogen functional groups on the polymer surface. XPS does not differentiate easily between the various nitrogen groups present on the surface so it is difficult to estimate the amount of surface amine groups available for direct coupling of bioactive molecules (proteins, peptides, nucleic acids, ...). To obtain a direct measurement of the amines present, we assayed for cysteine fixation through its carboxylic group by detection of the thiolaminoacid by XPS. We obtained cysteine fixation, showing the presence of grafted primary amine functions on PET surface after ammonia plasma treatment. Radiochemical assays were also made to quantify the amount of amine groups on plasma treated PET. XPS, cysteine fixation and radiochemical assays all show the presence of amine functions on ammonia plasma treated PET.     

Effects of coating composition and surface pre-treatment on the adhesion of organic-inorganic hybrid coatings to low density polyethylene (LDPE) films

Organic-inorganic hybrid coatings, obtained through the sol-gel chemistry from tetraethoxysilane and polyethylene-poly(ethylene glycol) block copolymer, have been prepared in different compositions and applied to untreated and plasma treated LDPE films by spin coating. The mechanical properties of the coatings and the adhesion between coating and substrate have been characterized by fragmentation test. An increase in coating strength, elongation at break and adhesion has been observed with increasing the organic fraction in the hybrid coating. A plasma treatment of the LDPE surface, just before the application of the coating, lead to an increase of the adhesion between coating and substrate (interfacial shear strength), leaving almost unaffected coating strength and strain at fragmentation onset.     

Analysis of functional groups on the surface of plasma-treated carbon nanofibers

Plasma chemically modified carbon nanofibers were characterized by X-ray photoelectron spectroscopy with regard to the content of carbon, oxygen, and nitrogen and the contribution of carboxylic groups or ester, carbonyl and hydroxylic groups or ether on the surface. Unfortunately, X-ray photoelectron spectroscopy only provides an average value of the first 10 to 15 molecular layers. For comparison, depth profiles were measured and wet chemical methods were applied to estimate the thickness of the functionalized layer and the distribution of oxygen-containing functional groups within the near-surface layers. The results indicate that the fiber surface is covered by a monomolecular oxygen-containing layer and that plasma treatment allows a complete oxygen functionalization of the uppermost surface layer. The best conditions for plasma treatment found within the set of parameters applied to generate complete functionalization are: plasma gas O(2)/Ar ratio 1:1, gas pressure 1-1.5 hPa, plasma power 80 W, treatment time >or= 5 min. Additionally, three quick and easy methods are presented to estimate the efficiency of plasma treatment with regard to surface functionalization: pyrolysis, contact angle measurements, and light permeability measurements of aqueous carbon nanofiber suspensions.     

Characterization of film surface treated with ECR plasma by Doppler broadening

Doppler broadened positron annihilation measurements were carried out using the positron beam technique on plasma treated polyethylene films as a function of incident positron energy. In addition, surface properties of the treated films also have been measured using other conventional techniques such as FT-IR, SEM and AFM. The surface tension of the films was also determined using sessile drop method. The S-parameter is seen to decrease on the surface upon plasma treatment that introduces polar groups such as hydroxyl and carbonyl on the surface. The results are discussed.     

Effect of reactive oxygen species generated with ultraviolet lamp and plasma on polyimide surface modification

Understanding the effect of reactive oxygen species (ROS), such as singlet oxygen molecule and atomic oxygen, on polyimide (PI) film properties, such as wettability, morphology, and chemical bonding state, is essential for further development of PI‐based surfaces. We investigated the effect of different ROS generated during ultraviolet (UV) and plasma treatment in oxygen gas on surface modification of Kapton PI. Different surface modification techniques, UV and plasma treatment, are known to generate different ROS. In this work, we demonstrate the effect of different ROS on PI surface modification. From the diagnostics of ROS by means of electron spin resonance and optical emission spectroscopy, we confirmed that during UV treatment, excited singlet oxygen molecules are the main ROS, while plasma treatment mainly generated atomic oxygen. The wettability of PI surface treated by UV and plasma resulted in hydrophilic PI surfaces. XPS results show that the wettability of PI samples is mainly determined by their surface O/C ratio. However, chemical bonding states were different: while UV treatment tended to generate C=O bonds, while plasma treatment tended to generate both C―O and C=O bonds. Singlet oxygen molecules are concluded to be the main oxidant during UV treatment, and their main reaction with PI was concluded to be of the addition type, leading to an increase of C=O groups on the surface of PI film. Meanwhile, atomic oxygen species were the main oxidant during plasma treatment, reacting with the PI surface through both etching and addition reaction, resulting in a wider variety of bonds, including both C―O and C=O groups.     

Expanded poly(tetrafluoroethylene) membrane surface modification using acetylene/nitrogen plasma treatment

In this article, expanded poly(tetrafluoroethylene) (e-PTFE) membrane surface modification was carried out using acetylene/nitrogen plasma treatment (p-e-PTFE). The variation in surface morphology of the p-e-PTFE membranes was confirmed by FTIR-ATR, scanning electron microscopy (SEM), and contact angle measurements. It was found that the surface hydrophilicity increased with increasing nitrogen content in the feed gas mixture, RF power, and plasma treatment time. The surface pore size decreased with increasing RF power and plasma treatment time. The water contact angles of the modified e-PTFE membrane decreased from 125.8° to 34.1° through the acetylene/nitrogen plasma treatment.     

Examination of the electrochemical reactivity of screen printed carbon electrode treated by radio-frequency argon plasma

The surface of screen printed carbon electrode (SPCE) with partially blocked surface was treated by argon plasma in order to improve their electrochemical performances. The argon plasma was generated by a radio-frequency electrical discharge at low pressure. Study of the electrode surface by scanning electronic microscopy (SEM) has revealed a significant change of the morphology of the SPCE surface after plasma pre-treatment. The electrochemical reactivity of the SPCEs was characterized using cyclic voltammetry. A drastic enhancement of the SPCEs electrochemical reactivity was highlighted after plasma pre-treatment. The effect of biasing the SPCE surface during the plasma treatment has been investigated and showed that depending on the nature of plasma treatment, the same electrode could show a radial or planar diffusion.