Influence of oxygen and nitrogen plasma treatment on polyethylene terephthalate (PET) polymers

In this paper we present surface modification of polyethylene terephthalate (PET) polymer, which is commonly used as synthetic vascular graft. Surface modification was made by oxygen and nitrogen plasma at different treatment times. Plasma was created by means of an RF generator at a discharge power of 200 W and gas pressure fixed at 75 Pa. The surface of PET polymer was modified in order to achieve improved attachment of fucoidan, which is a bioactive coating with antithrombogenic properties. In our study we analysed chemical modification of plasma treated surfaces by X-ray photoelectron spectroscopy (XPS), while the changes in morphology and surface roughness were observed with atomic force microscopy (AFM). Our results indicate that attachment of fucoidan is improved by oxygen plasma treatment, especially due to surface roughening.     

A ZnO/PET assembly study: Optimization and investigation of the interface region

Zinc oxide thin films are deposited on polyethylene terephthalate (PET) by r.f. magnetron sputtering process from a ceramic target in oxygen–argon plasmas. Structural studies show that the thin films are highly oriented along the (0 0 2) direction of the würtzite phase when the oxygen partial pressure is lower than 0.2 Pa. The crystallinity is accentuated when the oxygen partial pressure of the sputtering gas is increased from 0 to 0.02 Pa. The composition of the films determined by Rutherford backscattering spectrometry (RBS) varies in a wide range and it is necessary to add a few amount of oxygen in the plasma composition to establish the stoichiometry. The oxygen partial pressure is found to influence also the microstructure and consequently the density of the coatings.Various cold plasmas are used to treat the polymer surface before the deposition of zinc oxide films. Wettability measurements show an increase in the polar component of the PET surface free energy whatever the nature of the plasma used for the treatment. This increase is more obvious with the carbon dioxide plasma. XPS examinations of the CO₂ plasma treated PET surface in optimized conditions show a functionalisation of the polymer surface. The carbon dioxide plasma treatments of PET surface are found to enhance the peeling energy. The adhesion level depends also on the sputtering parameters, mainly the oxygen partial pressure and the r.f. power which influence the coating properties. The zinc oxide/PET interface is studied by XPS at the different stages of deposition and at various take-off angles. AFM observations show a regular growth of zinc oxide layers with smooth topographies on PET films. The different findings obtained from C1s, O1s, Zn2p3/2, Zn3p peaks and Auger Zn L₃M_4.5M_4.5 peak are corroborated and discussed. New chemical bonds between the polymer and the further coming zinc oxide thin layer are evidenced.     

Silk fibroin immobilization on poly(ethylene terephthalate) films: Comparison of two surface modification methods and their effect on mesenchymal stem cells culture

Silk fibroin (SF) has played a curial role for the surface modification of conventional materials to improve the biocompatibility, and SF modified poly(ethylene terephthalate) (PET) materials have potential applications on tissue engineering such as artificial ligament, artificial vessel, artificial heart valve sewing cuffs dacron and surgical mesh engineering. In this work, SF was immobilized onto PET film via two different methods: 1) plasma pretreatment followed by SF dip coating (PET-SF) and 2) plasma-induce acrylic acid graft polymerization and subsequent covalent immobilization of SF on PET film (PET-PAA-SF). It could be found that plasma treatment provided higher surface roughness which was suitable for further SF dip coating, while grafted poly(acrylic acid) (PAA) promised the covalent bonding between SF and PAA. ATR-FTIR adsorption band at 3284 cm^? 1, 1623 cm^? 1 and 1520 cm^? 1 suggested the successful introduction of SF onto PET surface, while the amount of immobilized SF of PET-SF was higher than PET-PAA-SF according to XPS investigation (0.29 vs 0.23 for N/C ratio). Surface modified PET film was used as substrate for mesenchymal stem cells (MSCs) culture, the cells on PET-SF surface exhibited optimum density compared to PET-PAA-SF according to CCK-8 assays, which indicated that plasma pretreatment followed by SF dip coating was a simple and effective way to prepare biocompatible PET surface.     

Surface modification and ageing of PMMA polymer by oxygen plasma treatment

We present a study on ageing of polymethyl methacrylate (PMMA) polymer treated with oxygen plasma. Oxygen plasma was created with an RF generator operating at a frequency of 27.12 MHz and a power of 200 W. The oxygen pressure was 75 Pa. The samples were treated for different time from 5 s to 60 s. The chemical modifications of the surface after plasma treatment were monitored by XPS (X-ray photoelectron spectroscopy), while the wettability and ageing effects were studied by WCA (water contact angle measurements). The samples were aged in dry air or in water. In the case of dry air, the least pronounced ageing was observed for the sample treated for 60 s. For samples aged in water, however, the lowest ageing rate was observed for the sample treated for 5 s. The samples were ageing slightly faster in water than in air. We also investigated the temperature effect on ageing of plasma treated samples. A set of samples was stored in a refrigerator at 5 °C and the other set was placed into an oven at 50 °C. The ageing rate of the samples stored at 5 °C was significantly lower than for the samples stored at 50 °C, so cooling the samples help keeping the required surface properties.     

Electrocoating of stainless steel coronary stents for extended release of Paclitaxel

The purpose of this study was to examine chemical, mechanical and Paclitaxel release properties of the new coating onto the stainless steel coronary stents.MethodsStainless steel coronary stents were coated with electrically polymerizable pyrrole derivative, applying cyclic voltammetry technique in a simple three electrode cell, while stent represented a working electrode. Resulted polymer coating were examined by cyclic voltammetry (electrical parameters), SEM (morphology images), goniometer (hydrophobisity of the surface), prophilometer ( thickness of the polymer coating). Polymer stability was examined by placing the coated stent into 1:1 solution of fetal calf serum:seline solution up to 1 year and under the mouse skin for 1 week. Paclitaxel loading were carried out by immersion into drug solution and its release was detected by HPLC.Results and conclusionReproducible one step method for coating different pyrrole derivatives on stainless steel coronary stents provided thin (single micrometers), uniform coating with various morphology and hydrophobisity. These surface properties allow to load appropriate amount of Paclitaxel and to release it slowly up to a month.     

Growth of permanganate conversion coating on 2024-Al alloy

The growth of permanganate conversion coating on aluminum 2024-T3 alloy has been studied by characterizing, with scanning Auger microscopy, scanning electron microscopy, X-ray photoelectron spectroscopy (XPS) and energy-dispersive X-ray spectroscopy, the coatings formed by immersion of the alloy in the coating bath (containing KMnO₄ and Na₂B₄O₇, pH 9.1) for different periods of time and at different temperatures. At room temperature, during the first 1-5 min of immersion, MnO₂ deposits are formed only on the second-phase intermetallic particles (of Al-Cu-Mg and Al-Cu-Fe-Mn types), but the coating starts to develop on the Al matrix surface after 5-10 min. The coating slows down and stops after about 150 min, with a thinner deposit over the alloy matrix. The process is accelerated at higher temperatures, for example at 68 °C it self-limits after about 3 min. The electrochemical growth process appears to follow that established for the chromate conversion coatings, although XPS does not detect significant MnO₄⁻ incorporation into the permanganate coatings.     

Roll‐to‐Roll Cohesive,Coated, Flexible,High‐Efficiency Polymer Light‐Emitting Diodes Utilizing ITO‐Free Polymer Anodes

This paper reports solution‐processed, high‐efficiency polymer light‐emitting diodes fabricated by a new type of roll‐to‐roll coating method under ambient air conditions. A noble roll‐to‐roll cohesive coating system utilizes only natural gravity and the surface tension of the solution to flow out from the capillary to the surface of the substrate. Because this mechanism uses a minimally cohesive solution, the roll‐to‐roll cohesive coating can effectively realize an ultra‐thin film thickness for the electron injection layer. In addition, the roll‐to‐roll cohesive coating enables the fabrication of a thicker polymer anode film more than 250 nm at one time by modification of the surface energy and without wasting the solution. It is observed that the standard sheet resistance deviation of the polymer anode is only 2.32 Ω/□ over 50 000 bending cycles. The standard sheet resistance deviation of the polymer anode in the different bending angles (0 to 180°) is 0.313 Ω/□, but the case of the ITO‐PET is 104.93 Ω/□. The average surface roughness of the polymer anode measured by atomic force microscopy is only 1.06 nm. Because the surface of the polymer anode has a better quality, the leakage current of the polymer light‐emitting diodes (PLEDs) using the polymer anode is much lower than that using the ITO‐PET substrate. The luminous power efficiency of the two devices is 4.13 lm/W for the polymer anode and 3.21 lm/W for the ITO‐PET. Consequently, the PLEDs made by using the polymer anode exhibited 28% enhanced performance because the polymer anode represents not only a higher transparency than the ITO‐PET in the wavelength of 560 nm but also greatly reduced roughness. The optimized the maximum current efficiency and power efficiency of the device show around 6.1 cd/A and 5.1 lm/W, respectively, which is comparable to the case of using the ITO‐glass.     

Web fabrication and characterization of unique winged shaped,area-enhanced fibers via a bicomponent spunbond process

High surface area fibers are sought after for a variety of applications such as liquid and air filtrations, medical and biopharmaceutical applications. Typically, higher specific surface area is achieved by resorting to using smaller fibers. This paper focuses on the development of a new shaped bicomponent spunbond structure for achieving high surface area. The fibers used in the spunbond process comprise a sacrificial sheath polymer and the shaped core polymer. Nonwovens were directly produced by using these fibers in a spunbond process. The spunbond webs were mechanically bonded by high energy water-jets and subsequently, the sheath polymer was removed in a 6 wt% NaOH solution at 90 °C. The final fibers showed a unique cross-sectional shape having 32 flaps or wings held together with a reasonable backbone. We report the results for a variety of polymer combinations including PP, PET, PBT, and PLA as the core and PLA and EastONE^TM as the sheath. The fiber morphologies were observed by SEM and showed 7–12 micron of the minor and 12–21 microns of the major with various core polymers used. The surface area of these fibers was compared to those of other shaped fibers.     

X-ray photoelectron spectroscopy and corrosion studies of zinc phosphate coated on 7075-T6 aluminium alloy

Coated layers which formed on 7075-T6 aluminium alloy surfaces after treatment in zinc phosphate (ZPO) suspensions adjusted to different pH values (3.5, 5.0, 6.6, 10.5 and 13.0) were characterized by X-ray photoelectron spectroscopy (XPS). Comparative XPS tests were also made after the treated surfaces were exposed to a 3.5% NaCl solution for 5 h. The processes of coating from solution, oxidation, etching and bulk diffusion were all involved, although in different proportions, in the different treatments. The amounts of zinc and phosphorus in the uppermost layers were enhanced when the coating was at pH values of 5.0, 10.5 and 13.0, and in each case a mixed ZnO _x -AlO _x -ZPO structure was apparently formed. The coating prepared at pH=13.0 appeared to provide the best corrosion protection.     

Contact angle analysis of low-temperature cyclonic atmospheric pressure plasma modified polyethylene terephthalate

Polyethylene terephthalate (PET) films are modified by cyclonic atmospheric pressure plasma. The experimentally measured gas phase temperature was around 30 °C to 90 °C, indicating that this cyclonic atmospheric pressure plasma can treat polymers without unfavorable thermal effects. The surface properties of cyclonic atmospheric pressure plasma-treated PET films were examined by the static contact angle measurements. The influences of plasma conditions such as treatment time, plasma power, nozzle distance, and gas flow rate on the PET surface properties were studied. It was found that such cyclonic atmospheric pressure plasma is very effective in PET surface modification, the reduced water contact angle was observed from 74° to less than 37° with only 10 s plasma treatment. The chemical composition of the PET films was analyzed by X-ray photoelectron spectroscopy (XPS). Atomic force microscopy (AFM) was used to study the changes in PET surface feature of the polymer surfaces due to plasma treatment. The photoemission plasma species in the continuous cyclone atmospheric pressure plasma was identified by optical emission spectroscopy (OES). From OES analysis, the plasma modification efficiency can be attributed to the interaction of oxygen-based plasma species in the plasma with PET surface. In this study, it shows a novel way for large scale polymeric surface modification by continuous cyclone atmospheric pressure plasma processing.     

XPS study of oxygen plasma activated PET

A study on oxygen plasma functionalization of polyethyleneterephthalate (PET) is presented. Samples were exposed to a weakly ionized, highly dissociated RF oxygen plasma with an electron temperature of 5 eV, a density of positive ions of 8×10¹⁵ m⁻³ and a density of neutral oxygen atoms of 4×10²¹ m⁻³. The oxygen pressure was 75 Pa and the discharge power was 200 W. The wettability of plasma-modified samples was determined by measuring the contact angle of a water drop, while the appearance of the functional groups on the sample surface was determined by using a high-resolution X-ray photoelectron spectrometer (XPS). Already in the order of seconds of the plasma treatment the samples were covered by the surface functional groups. These results were explained by the high flux of oxygen atoms onto the sample surface. The stability of functional groups on the plasma-modified PET surface stored in a dry plastic box was monitored by using XPS as a function of the ageing time. After 1 day of ageing, the concentration of newly formed functional groups decreased by about 15%.     

Immobilization of protein streptavidin to the surface of PMMA polymer

Immobilization of the protein streptavidin to the surface of polymethyl methacrylate (PMMA) polymer was studied by X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). Different protocols were used to attach streptavidin to the PMMA surface: physical adsorption and chemical coupling. The influence of oxygen plasma treatment on the efficiency of streptavidin binding was studied. The presence of streptavidin coating on the PMMA surface was demonstrated by the appearance of N1s signal in the XPS spectra of coated PMMA samples. The XPS results have shown that oxygen plasma treatment improves binding of streptavidin to the PMMA surface. XPS results also showed that chemical coupling is more efficient than physical adsorption. In the case of physical adsorption, rinsing of the sample with water caused noticeable decrease of nitrogen concentration, while in the case of chemical coupling the nitrogen concentration was stable. AFM measurements showed that after deposition of streptavidin coating the originally smooth surface changed to dendrite structure.     

Low-temperature processing method of preparing for transparent graphene oxide electrode film with better electrical properties

Graphene oxide films were prepared by a facile ball milling process. The milling time and the amount of the acryl type polymer dispersion agent were controlled to obtain well dispersed graphene oxide solution in ethanol. Consequently, the transparent and conducting graphene oxide film which had 69% transmittance and 1.5 x 10(6) ohm/sq surface resistance was produced by bar coating the solution on a PET substrate. The electrical property of the graphene oxide film could be further improved to 2.1 x 10(5) ohm/sq by hydrazine vapor reduction.     

A new method for deposition of nano sized titanium nitride on steels

Active screen plasma nitriding is a new and common method for deposition of Iron nitride. Since techniques such as Chemical Vapor Deposition (CVD), Physical Vapor Deposition (PVD) and Plasma Assisted Chemical Vapor Deposition (PACVD) are usually applied in order to deposit the titanium nitride and each of these methods has its own problems, in this research active screen plasma nitriding method was introduced as a novel approach for deposition of nano sized titanium nitride. H11 tool steel samples were coated by plasma nitriding method at 550 °C for 5, 7.5 and 10 h, using three gas mixtures consisted of H₂/N₂ = 3, 1 and 1/3. Scanning Electron Microscopy (SEM) and X-ray Diffraction (XRD) and X-ray Photoelectron Spectroscopy (XPS) were employed to investigate the coating properties such as grain size, layer thickness and chemical composition. Results showed that the proportion of H₂ in the gas mixture was a crucial point in order to obtain a perfect coating. By increasing the coating time, the grain size and the layer thickness increased. XPS results showed that the coating was mainly consisted of TiN + TiN_0.1 together with a small amount of TiO₄.     

A new method for deposition of nano sized titanium nitride on steels

Active screen plasma nitriding is a new and common method for deposition of Iron nitride. Since techniques such as Chemical Vapor Deposition (CVD), Physical Vapor Deposition (PVD) and Plasma Assisted Chemical Vapor Deposition (PACVD) are usually applied in order to deposit the titanium nitride and each of these methods has its own problems, in this research active screen plasma nitriding method was introduced as a novel approach for deposition of nano sized titanium nitride. H11 tool steel samples were coated by plasma nitriding method at 550 °C for 5, 7.5 and 10 h, using three gas mixtures consisted of H₂/N₂ = 3, 1 and 1/3. Scanning Electron Microscopy (SEM) and X-ray Diffraction (XRD) and X-ray Photoelectron Spectroscopy (XPS) were employed to investigate the coating properties such as grain size, layer thickness and chemical composition. Results showed that the proportion of H₂ in the gas mixture was a crucial point in order to obtain a perfect coating. By increasing the coating time, the grain size and the layer thickness increased. XPS results showed that the coating was mainly consisted of TiN + TiN_0.1 together with a small amount of TiO₄.     

Influence of pH on the synthesis and characterization of CuO powder for thick film room-temperature NH3 gas sensor

CuO films of 51 μm thickness have been fabricated from nanocrystalline powder, which has been synthesized by a sol–gel auto-combustion method at different pH values of the precursor solution. Studies reveal that the pH value of the precursor solution strongly affects the decomposition rate of the metal–citrate complex formed by precursors (cupric nitrate and citric acid). Structural characterization of the powder samples shows a considerable change in agglomeration behavior, crystallite size and strain with variation in pH value of the precursor solution. Studies show that high pH reaction conditions results in the production of highly porous CuO nanoparticles with lowest crystallite size of 27 nm. Thick films of the synthesized material show an extremely high response of 0.941 to few parts per million level of ammonia at room temperature as well as possesses good stability for a long period of time. The adsorption of ammonia on the sensor surface obeys Elovich equation and the reaction kinetics followed is of first order. The lowest potential barrier of 0.50 MΩ and highest rate constant of 0.0136 s⁻¹ have been found for ammonia adsorption on the sensor surface in case of film fabricated from CuO powder synthesized at high pH value of precursor.     

Ascorbic acid sensor based on molecularly imprinted polymer-modified hanging mercury drop electrode

Ascorbic acid sensor based on molecularly imprinted polymer (MIP) is reported for sensitive and selective analysis, without any cross-reactivity or matrix effect, in aqueous, blood serum and pharmaceutical samples. The sensor was developed by the direct coating of ascorbic acid-imprinted polymer, prepared from melamine and chloranil, on the surface of a hanging mercury drop electrode (HMDE) at + 0.4 V (vs. Ag/AgCl). The molecular recognition of ascorbic acid was highly specific using non-covalent (hydrophobically driven hydrogen-bonding and electrostatic) interactions. The analyte was preconcentrated and oxidised instantaneously in the imprinted polymer layer giving voltammetric signal on cathodic stripping at optimised operational conditions: accumulation potential + 0.4 V (vs. Ag/AgCl), polymer deposition time 120 s, template accumulation time 120 s, pH 7.0, scan rate 10 mV s^? 1, pulse amplitude 25 mV. The proposed MIP sensor is able to enhance sensitivity substantially so as to detect serum ascorbic acid level as low as 0.26 ng mL^? 1 (R.S.D. 0.5%, S/N 3) for the diagnosis of hypovitaminosis C (Vitamin C deficiency).     

甲基硅酸钠刻蚀聚多巴胺涂层构建超疏水木材及表征

利用聚多巴胺(PDA)涂层黏附和去质子化的特性,采用甲基硅酸钠(SMS)刻蚀PDA涂层,进一步采用十八烷基三甲氧基氯硅烷(OTS)对其进行低表面能处理制备了稳固型超疏水木材(Wood@PDA-SMS-OTS)。采用接触角(CA)测定仪、SEM、XPS分别对试样进行了表征。结果表明,水在Wood@PDA-SMS-OTS试样表面的静态CA最高为157.4°,滚动角(SA)为4.3°;SEM图像表明,SMS成功刻蚀了PDA涂层,同时水解生成疏水性的低聚或半聚的甲基硅氧烷覆盖在PDA涂层表面,形成了明显的微纳米粗糙结构;XPS分析表明,PDA在木材的表面形成均匀的涂层,SMS在刻蚀PDA涂层的同时,其水解生成的聚合物成功负载在PDA的表面,含长链结构的OTS接枝在木材的表面,使木材具有超疏水性能;超疏水木材表面经过24 h的水流冲刷、超声波震荡、酸碱腐蚀及有机溶剂等处理后,仍具有较强的超疏水稳固性。      

Electrosynthesis and characterisation of poly(safranine T) electroactive polymer films

The phenazine safranine T has been electropolymerised by potential cycling at carbon film electrodes in nitrate-containing solutions at different pH: 2.0, 5.5, and 7.0, as well as from chloride solution, pH 5.5. The electroactive polymer obtained, poly(safranine T), has been analysed by cyclic voltammetry in different electrolyte solutions and its morphology examined using scanning electron microscopy. The surface coverage was calculated and found to be the highest for the film formed in chloride solution, pH 5.5, with 8.7 nmol cm^− 2. The other films had lower coverages, from 5.3 to 7.8 nmol cm^− 2, and are similar to those obtained for other phenazine dye polymers. Although the fastest polymerisation occurred in solutions at pH 5.5, the best electrochemical properties resulted from electropolymerisation at pH 2.0. Analysis of the cyclic voltammograms showed that in most cases the electrochemical processes at the polymer coated electrodes are limited by surface reactions. Scanning electron microscopy data confirmed the results obtained by cyclic voltammetry and showed that the most compact film was obtained in chloride solution.     

A comparison of reactive plasma pre-treatments on PET substrates by Cu and Ti pulsed-DC and HIPIMS discharges

PET web samples have been treated by magnetically enhanced glow discharges powered using either medium frequency pulse direct current (p-DC) or low frequency high power pulse (HIPIMS) sources. The plasma pre-treatment processes were carried out in an Ar–O₂ atmosphere using either Cu or Ti sputter targets. XPS, AFM and sessile drop water contact angle measurements have been employed to examine changes in surface chemistry and morphology for different pre-treatment process parameters. Deposition of metal oxide onto the PET surface is observed as a result of the sputter magnetron-based glow discharge web treatment. Using the Cu target, both the p-DC and HIPIMS processes result in the formation of a thin CuO layer (with a thickness between 1 and 11 nm) being deposited onto the PET surface. Employing the Ti target, both p-DC and HIPIMS processes give rise to a much lower concentration of Ti (< 5 at.%), in the form of TiO₂ on the PET treated surface. The TiO₂ is probably distributed as an island-like distribution covering the PET surface. Presence of Cu and Ti oxide constituents on the treated PET is beneficial in aiding the adhesion but alone (i.e. without oxygen plasma activation) is not enough to provide very high levels of hydrophilicity as is clear from sessile drop water contact angle measurements on aged samples. Exposure to the plasma treatments leads to a small amount of roughening of the substrate surface, but the average surface roughness in all cases is below 2.5 nm. The PET structure at the interface with a coating is mostly or wholly preserved. The oxygen plasma treatment, metal oxide deposition and surface roughening resulting from the HIPIMS and p-DC treatments will promote adhesion to any subsequent thin film that is deposited immediately following the plasma treatment.