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RF excited gas discharges of hexamethyldisiloxane (HMDSO) with and without oxygen and methane (CH4) without further carrier gas were examined to identify reaction parameters determining deposition rate and film properties of SiOx and a-C:H films, respectively. This evaluation is supported by the used reactor type which enables well-defined deposition conditions. Both symmetrical and asymmetrical electrode configurations are investigated. It is found that the deposition rate depends on the reaction parameter power input per gas flow where the gas flows of monomer and reactive carrier gases are added. Thus, O2 in conjunction with HMDSO can be considered as a film-forming gas. Even in asymmetrical discharges the concept of the reaction parameter W/F holds, as long as the increasing ion bombardment allows a continuous film growth. While W/F controls the chemical composition of the films, the potential drop across the plasma sheath influences the mechanical film properties. With these findings SiOx and a-C:H plasma coatings can be designed. [Copyright &y& Elsevier]

The plasma-based surface modification of polymer materials with desirable bulk properties is a useful way to obtain polymers with tailor-made surface properties. This is necessary because the surface properties of most engineering polymers in use today are less then optimum for many applications. New functionalities such as biocompatibility, adhesion, special functional groups as well as lubricative, friction and wear-and-tear properties are demanded. By optimization of the process parameters during a low pressure plasma treatment, most of these requirements can be fulfilled. A specific functionalization with, e.g., carboxyl, amino, epoxy or hydroxyl groups as well as the generation of ultra thin layers with those functionalities is possible. The most challenging problem is not only to find parameters which do not lead to a fragmentation of the monomeric structure, but moreover the adhesion of the thin films to the substrates must overcome a stability test without delamination. To optimize plasma processes, with their great variety of parameters influencing the obtained surface properties, several surface analytical techniques are indispensable. XPS, AES as well as AFM are helpful tools to characterize the modified sample surfaces and consequently optimize the set of parameters for the glow discharge treatment. With XPS the retention of the monomer structure can be controlled. AES depth profiling clarifies the elemental composition of gradient layers, necessary for a good adhesion of scratch-resistant coatings. AFM visualizes the surface morphology which is important for, e.g., the friction properties of plasma-coated substrates. [ABSTRACT FROM AUTHOR]

Graphical abstract Highlights • Poly-3-hydroxybutyrate (PHB) films were plasma-treated in NH 3 , Ar and NH 3 /Ar mixtures. • Surface chemistry and topography changes were observed in PHB films. • A significant decrease in contact angle and an increase in free surface energy were observed. • Fibroblast cell adhesion was significantly improved after Ar plasma treatment. Abstract Poly-3-hydroxybutyrate (PHB) films were plasma-treated using pure NH 3 , pure Ar or mixtures of the two different proportions (20%, 30%, 40%, 50%, 70% NH 3 in Ar). Surface chemistry and surface topography changes of PHB films were observed after plasma processing in all plasma regimes. The XPS results confirmed the absence of chemical modification in the case of pure Ar plasma treatment. Nitrogen-containing groups (e.g., N C O) were detected on the surfaces of P3HB films treated with NH 3 -containing plasma. The surfaces of the untreated P3HB films were hydrophobic, and plasma treatment turned the surfaces hydrophilic, irrespective of the treatment. A significant decrease in the contact angle and an increase in the free surface energy were observed. An insignificant surface ageing effect was observed when P3HB samples were exposed to air for 10 days. In NIH 3T3 mice fibroblast cells, cell adhesion was significantly improved after plasma treatment in an Ar atmosphere, which is likely related to the fact that there was a surface ξ potential of 88.6 mV at neutral pH, causing a cleavage of the polymer chains and an increase in surface roughness. [ABSTRACT FROM AUTHOR]

In this paper, parylene C coating with the thickness of 2 μm was deposited on different magnesium alloy substrates (AZ31, WE43 and AZ91). The structure and phase composition of parylene C coating was analysed by Fourier transformed infrared (FTIR) spectroscopy and X-ray diffraction (XRD). In addition, extensive surface characterization was done using atomic force microscopy. The corrosion performance of polymer-coated magnesium alloys was investigated by electrochemical measurements in Hanks’ balanced salts solution that simulates bodily fluids at 37 ± 0.5 °C. The depth-dependent mechanical properties including Young’s modulus and nanohardness of parylene C films were investigated using nanoindentation technique. The effect of the penetration depth on the properties on nano- and microscale level have been described in detail. The percentage of elastic recovery was used to characterize the elastic properties of the polymeric coatings. The results of XRD showed (020) preferred orientation of the monoclinic unit cell of the alpha phase of parylene C. The parylene C revealed a semicrystalline structure with nanocrystalline blocks of 4.9 nm. The parylene C film shows a uniform surface morphology with a higher roughness level at micro and nanoscales compared to magnesium alloy surfaces. All of the uncoated substrates exhibited a low corrosion resistance compared to the coated samples, indicating that the corrosion resistance of the magnesium alloys could be improved by parylene C coating. The resulting average nanohardness and Young’s modulus of the parylene C coatings deposited onto different substrates were in the range of 0.18–0.25 GPa and 4.19–5.14 GPa, respectively. Furthermore, a higher percentage of elastic recovery of the polymer coating indicated a higher elasticity as compared to the magnesium alloy surface. The polymer coating has revealed the ability to recover elastically. Therefore, parylene C coating can not only improve corrosion resistance, but also provide the ability to recover elastically, expanding the potential applications of this material to include various biointerface platforms. [ABSTRACT FROM AUTHOR]

The surface properties of poly-3-hydroxybutyrate (P3HB) membranes were modified using oxygen and an ammonia radio-frequency (RF, 13.56 MHz) plasma. The plasma treatment procedures used in the study only affected the surface properties, including surface topography, without inducing any significant changes in the crystalline structure of the polymer, with the exception being a power level of 250 W. The wettability of the modified P3HB surfaces was significantly increased after the plasma treatment, irrespective of the treatment procedure used. It was revealed that both surface chemistry and surface roughness changes caused by the plasma treatment affected surface wettability. A treatment-induced surface aging effect was observed and resulted in an increase in the water contact angle and a decrease in the surface free energy. However, the difference in the water contact angle between the polymers that had been treated for 4 weeks and the untreated polymer surfaces was still significant. A dependence between cell adhesion and proliferation and the polar component of the surface energy was revealed. The increase in the polar component after the ammonia plasma modification significantly increased cell adhesion and proliferation on biodegradable polymer surfaces compared to the untreated P3HB and the P3HB modified using an oxygen plasma. [ABSTRACT FROM AUTHOR]

The oxygen and ammonia radio-frequency (RF) plasma treatment of poly(3-hydroxybutyrate) P3HB films was performed. We revealed significant changes in the topography, a decrease in the surface zeta potential from −63 to −75 mV after the oxygen–plasma treatment and an increase after ammonia plasma treatment from −63 to −45 mV at a pH of 7.4. Investigations into the NIH 3T3 fibroblast adhesion and growth demonstrated the best cell vitality and a higher cell number for the ammonia plasma treatment at 150 W. [ABSTRACT FROM AUTHOR]

The effect of the pulsed electron beam (PEB) treatment on the structure and morphology of the hydroxyapatite (HA) coating deposited on the surfaces of titanium substrates by radio frequency magnetron sputtering was elucidated. The structure, composition and morphology of the samples were characterized by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD). The results collected from SEM experiments demonstrated that the HA film was smooth and featureless. The samples were irradiated by PEB using an electron beam energy density of 0.1 J cm −2 , electron beam pulse duration of 50 μs, pulse repetition frequency of 5 Hz, and number of pulses N =50 and N =150. After PEB treatment with N =50, the coating exhibited a much finer uniform surface morphology, playing a crucial role in the enhancement of the mechanical properties of the HA-coated titanium substrate. The surface of the HA film treated with N =150 was still smooth and featureless. The XRD data demonstrated that PEB treatment of HA films produced only a slight decrease in the HA phase content. The combination of these two techniques opens the possibility of preparing high quality HA layers. [ABSTRACT FROM AUTHOR]

Silicon-doped hydroxyapatite-based (Si-HA) coatings were deposited via radio frequency (RF) magnetron sputtering on the surface of titanium that was treated with a pulsed electron beam. This study aimed to evaluate the effect of Si doping on the structure and mechanical properties of thin HA films. The content of the silicon was 1.2 and 4.6 at.% for the coatings prepared using the Si-HA precursor powders with a chemical formula Ca 10 (PO 4 ) 6 − x (SiO 4 ) x (OH) 2 − x where, x = 0.5 and 1.72. Pure HA (Ca 10 (PO 4 ) 6 (OH) 2 ) coatings were deposited for comparison. The as-deposited films were analysed with respect to their composition, state of chemical binding and microstructure using XPS, FTIR, XRD, and SEM. We hypothesized that the addition of Si would affect the mechanical features of the coatings due to microstructure changes. The effect of the introduction of Si on the nanohardness and the Young's modulus as well as the adhesion strength and scratch resistance of the HA coating was investigated using nanohardness testing and a scratch test, respectively. Examination of the coating microstructure using SEM and AFM revealed that Si doping influenced the surface morphology and led to a smaller grain size. The tendency to form an amorphous structure also increased with an increase in the Si content. A monotonous decrease in both the nanohardness and the elastic modulus was observed with an increase in the Si content. A maximum nanohardness of ~ 7 GPa was obtained for the Si-free HA coating, whereas the hardness decreased to ~ 4.3 GPa for the films with a Si content of 1.2 at.%. The addition of 4.6 at.% Si to the HA coating resulted in a reduction in the elastic modulus, whereas the nanohardness was very similar to that of the uncoated substrate. The adhesion behaviour of the coatings demonstrated different responses. In the case of pure HA coatings, failure occurred due to the low cohesion of the coating, whereas the crystalline Si-HA coatings with a Si content of 1.2 at.% deformed plastically without crack formation and without detaching from the titanium substrate, which resulted in a greater coating stability. [ABSTRACT FROM AUTHOR]

This study investigated the effect of the substrate morphology introduced by various substrate preparation techniques, namely acid etching (AE) and pulsed electron beam (PEB) treatments, on the CaP film morphology and mechanical properties. The morphology, nanohardness, and Young's modulus of the CaP coating deposited via radio-frequency (RF) magnetron sputtering were investigated by X-ray photoelectron spectroscopy (XPS), atomic force microscope (AFM), scanning electron microscopy and nanoindentation studies. The Ca/P ratios of the CaP coating deposited via RF magnetron sputtering onto titanium substrates treated using AE and PEB according to XPS were 1.73 ± 0.03 and 1.72 ± 0.04, respectively, which is close to the Ca/P ratio of 1.67 typical for stoichiometric hydroxyapatite (HA). The AFM experiments and nanoindentation studies revealed significant differences in the morphology and mechanical responses of the CaP films deposited onto acid-etched titanium substrates treated with PEB. Deposition of the CaP coating onto the acid-etched surface resulted in a rough surface with the presence of an island-like morphology. The CaP coating onto a smooth titanium substrate treated by PEB exhibited grains with irregular shapes and decreased size. The nanoindentation hardness and the Young's modulus of the HA coating deposited onto titanium treated by the PEB treatment were determined to be 7.0 ± 0.3 and 124 ± 3 GPa, respectively, which are significantly higher than those of the CaP coating on the acid-etched titanium substrates. Moreover, the elastic strain to failure ( H / E ), the plastic deformation resistance ( H 3 / E 2 ), and the percent elastic recovery % R of the HA coating on titanium after surface irradiation with an electron energy density of 15 J·cm − 2 were determined to increase by ~ 23%, ~ 70% and ~ 53%, respectively, compared to the CaP coating on acid-etched titanium. [ABSTRACT FROM AUTHOR]

Abstract: In conventional plasma polymerization processes, the bulk properties of the treated substrates are maintained whereas the surface properties are changed to the ones of the coating polymer. In contrast, materials with ultrathin non-closed layers and domains of plasma deposited compounds can show combined properties (from the surface of the bulk material and the non-closed layer) or even completely new behavior. This can be seen by analyzing e.g. the wettability (contact angle), the tribological properties, chemical functionalities or biological interactions. Ultrathin closed and non-closed films (domains) of fluorocarbon polymer were produced by means of RF-CVD (radio frequency aided chemical vapor deposition, plasma polymerization) with CHF3 as monomer gas; argon was added as additional process gas. Our work has been carried out in a symmetric capacitively coupled reactor at 13.56 MHz in the low-pressure, glow-discharge regime. The influence of pulsing the plasma by varying on- and off-times on the surface properties were investigated on silicon wafers as substrates. The obtained functionalized surfaces were characterized by means of advancing and receding contact angle measurements, X-ray photoelectron spectroscopy (XPS) as well as atomic force microscopy (AFM). [Copyright &y& Elsevier]

Tailor-made surfaces of polymer materials are required, e.g. for the improvement of their printability or adhesion and for many applications concerning medical equipment or life science products. Polypropylene (PP) is one of the few common polymers widely used in technical applications. But often the surface chemistry has to be modified by introducing special chemical functionalities like carboxylic groups or by coating the PP with thin films, e.g. with poly(acrylic acid). The radio frequency plasma technique was used for functionalization and coating of PP by using acrylic acid as monomer gas. After optimization of the plasma parameters, high concentration of carboxylic groups as well as solvent-stable thin films with good adhesion to the PP substrates could be obtained. Characterization of the plasma-modified PP substrates was performed by using the captive bubble method, ESCA (Electron Spectroscopy for Chemical Analysis) and fluorescence spectroscopy in combination with derivatization techniques and FTIR (Fourier Transformation Infrared Spectroscopy). The thickness of the polymer films was analyzed by AFM (Atomic Force Microscopy). [Copyright &y& Elsevier]

We have developed novel antibacterial coatings from innocuous polyammonium compounds which are chemically coupled to a polymer surface. For immobilization we used two strategies: In the first strategy, the polymer surface is plasma activated to generate radicals. Then antibacterial monomers, such as diallyldimethylammonium chloride (DADMAC) are grafted to the surface by a radical polymerization. In the second strategy, the polymer surface is plasma treated to create oxygen functionalities. Antibacterial copolymers, such as DADMAC copolymers, are coupled to the activated surface. Microbiological data prove that the DADMAC copolymers reduce the settlement of bacteria such as Micrococcus luteus (gram positive) and Escherichia coli (gram negative) by a factor of 105–106. The layers were characterized by X-ray photoelectron spectroscopy (XPS) and contact angle measurements. The extremely thin coatings of only 2–3 nanometers thickness do not change the material properties of the substrate. [Copyright &y& Elsevier]