含二氮杂萘酮结构聚醚砜酮膜的微波等离子体处理研究

含二氮杂萘酮结构型聚醚砜酮(ＰＰＥＳＫ)是近年来本研究组开发成功的新型耐高温聚合物[1].该聚合物具有优异的力学性能和突出的耐热性,玻璃化转变温度(Ｔｇ)为265～305℃(随砜酮比不同而变化),其结构式如下:ＯＮＮＯＳＯＯＯＮＮＯＣＯ　　研究表明,用ＰＰＥＳＫ制成的气体分离膜对Ｏ2/Ｎ2、ＣＯ2/Ｎ2有良好的气体渗透性和透过选择性[2,3],但由于其亲水性不高进而限制了它在纳滤膜和反渗透膜等方面的应用,因此有必要对其进行改性.目前,常用的膜及膜材料改性的方法有磺化、氯甲基化季胺化、接枝等化学改性和低温等离子体与辐射等物理改性.其…     

Electropolymerization of DBSA‐doped polypyrrole films on PTFE via an electroless copper interlayer

We report on the electroless deposition of thin films of copper on poly(tetrafluoroethylene) (PTFE) and their use as substrates for electropolymerization of polypyrrole. Argon plasma‐treated PTFE films were modified by silanization using N‐[3(trimethoxysilyl)propyl]diethylenetriamine (TMS). The TMS‐modified PTFE films were subsequently activated by PdCl₂ for the electroless deposition of copper. The omission of the commonly used SnCl₂ sensitization step represents a significant process enhancement with environmental and cost benefits. The surface composition of the substrate (before and after surface treatments) and overlayer films was studied using high‐resolution x‐ray photoelectron spectroscopy. A combination of time‐of‐flight secondary ion mass spectrometry and water contact‐angle measurements was also used to study the PTFE surface after argon plasma treatment. The Cu/PTFE films were used as substrates for subsequent pyrrole electropolymerization in aqueous dodecylbenzene sulphonic acid (DBSA) solution. The DBSA‐doped polypyrrole overlayers were successfully deposited on the Cu/PTFE surface using a constant applied potential of 1.5 V. The resulting material exhibited a doping level of 39%, determined using chemical component analysis of the N 1s photoelectron peak. Copyright © 2003 John Wiley & Sons, Ltd.     

聚乙烯表面接枝聚合改性及抗凝血性的研究

聚乙烯(PE)膜经Ar等离子体预处理,无光引发剂紫外光照接枝甲基丙烯酸缩水甘油酯(GMA),然后进行肝素化处理,以改善PE的抗凝血性能。用正交实验确定接枝反应的最优条件。通过X-射线光电子能谱(XPS)、衰减全反射红外光谱(ATR-FTIR)、扫描电子显微镜(SEM)和接触角测定PE膜接枝GMA前后表面性能和表面形貌。用复钙时间、凝血酶原时间、部分凝血活酶时间、凝血酶时间和血小板粘附实验对其抗凝血性能进行评价,结果表明,被修饰PE膜的抗凝血性能显著提高。     

接枝丙烯酰胺改善聚乙烯膜表面亲水性的研究

利用等离子体技术和紫外照射接枝相结合在聚乙烯膜表面接枝丙烯酰胺(AAm)以改善其亲水性。通过衰减全反射红外光谱(ATR-FTIR)、X射线光电子能谱(XPS)和接触角测定验证了在无光引发剂的条件下,将等离子体预处理和紫外照射接枝结合起来可以有效地提高AAm的接枝效果,很好地改善PE膜表面的亲水性。探讨了等离子体复合参数W/(FM)、等离子体预处理时间、AAm单体浓度以及紫外照射时间对改善PE膜表面亲水性的影响,确定改善PE膜表面亲水性的最佳实验条件。     

微波等离子体诱导聚乙烯表面接枝甲基丙烯酸甲酯

聚乙烯（ＰＥ）通常作为性能优良的薄膜材料被广泛使用,但由于其表面能低,导致表面亲水性差,粘结性弱,染色性能、印刷性能等很不理想［１,２］．在高分子材料的各种表面改性方法中,接枝共聚是一种很有效的途径［３～５］．本文探讨了用微波冷等离子体激活聚乙烯表面...     

Surface roughness and hydrophilicity enhancement of polyolefin‐based membranes by three kinds of plasma methods

The introduction of antibacterial property, conductivity, wettability and antithrombogenicity into polyolefin‐based membranes has evoked much attention, which can be achieved by coating hydrophilic polymers. Therefore, it is necessary to modify the roughness and hydrophilicity of polyolefin‐based membranes to enhance the coating ability. In this paper, three kinds of plasma methods, including inductively coupled (ICP) plasma, radio frequency low pressure (RFP) plasma and atmospheric dielectric barrier discharge (DBD) plasma, were used to modify the surface of the polyethylene (PE), polypropylene (PP) and polyester‐polypropylene (PET–PP) membranes. The surface roughness of the plasma‐modified PE, PP and PET–PP films was investigated by scanning electron microscopy (SEM) and atomic force microscope (AFM). The polar functional groups of films were observed by energy dispersive spectrometer (EDX) and X‐ray photoelectron spectroscopy (XPS). Besides, the hydrophilicity of the plasma‐modified PE, PP and PET–PP films was evaluated by water contact angle measurement. It was found that the surface roughness and hydrophilicity of plasma‐modified PE, PP and PET–PP films increased with the generation of oxygen‐containing functional groups (i.e. C―O, and C?O). The PET–PP membranes were treated by RFP plasma at different processing powers and times. These results indicated that plasma is an effective way to modify films, and the treatment time and power of plasma had a certain accumulation effect on the membranes' hydrophilicity. As for the roughness and hydrophilicity, the DBD plasma modifies the PE film, which is the optimum way to get the ideal roughness and hydrophilicity. Copyright © 2015 John Wiley & Sons, Ltd.     

Surface and Bulk Structure of Thin Spin Coated and Plasma-Polymerized Polystyrene Films

Polystyrene (PS) spin coated thin films were modified by O₂ and Ar plasma as well as by UV irradiation treatments. The modified PS samples were compared with plasma polymerized and commercial polystyrene. The effects of plasma (O₂ and Ar) and UV irradiation treatments on the surface and the bulk properties of the polymer layers were discussed. The surface properties were evaluated by X-ray Photoelectron Spectroscopy and Contact angle measurements and the bulk properties were investigated by FTIR and dielectric relaxation spectroscopy. As a result only one second treatment time was sufficient to modify the surface. However, this study was also dedicated to understand the effect of plasma and plasma irradiation on the deposited layers of plasma polymers. The dielectric measurements showed that the plasma deposited films were not thermally stable and underwent an undesired post-plasma chemical oxidation.     

Properties of the Teflon AF1601S Surface Treated with the Low-Pressure Argon Plasma

The stability of the surface properties of Teflon AF films were investigated after their exposure to the low-pressure argon plasma for various times. X-ray photoelectron and infrared spectroscopies, atomic force microscopy, scanning optical microscopy based on chromatic aberration, goniometry (the measurement of water contact angles), as well as electrokinetic method and ellipsometry were used to control changes in the chemical composition and surface properties of Teflon AF films taking place upon their plasma treatment. The stable hydrophilization of the surface of Teflon AF films resulted from plasma treatment was revealed.     

Influence of oxygen plasma treatment on poly(ether sulphone) films

Poly(ether sulphone) (PES) is one of the most widely used materials in the micro-electronics industry and a good candidate for the substrates of flexible optoelectronic devices. In this work, the influences of oxygen plasma treatment on the surface chemical composition, surface morphology and optical transparency of PES films were investigated by means of X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FESEM), atomic force microscopy (AFM) and UV-visible spectrophotometry. The possible relations between the optical transparency of the substrate and the surface roughness and chemical composition were also studied. The oxygen plasma treatment seriously changed the surface chemical composition and made the surface more rough. Considerable amounts of sulphate species were found on the plasma-treated surface and the surface roughness values (R_a) increased monotonically with the increase of the treatment time. The PES films treated by 5 min, 15 min, 30 min and 45 min oxygen plasma demonstrated transmission of approximately 98, 94, 68 and 46%, respectively, in the wavelength range of 400-780 nm. The oxygen plasma induced decline of optical transparency of PES films might be attributed to both the increase of surface roughness and the changes of chemical composition of the film surface.     

A study of atmospheric-pressure CHF3/Ar plasma treatment on dielectric characteristics of polyimide films

In this work, the influence of atmospheric-pressure CHF(3)/Ar plasma treatment on surface dielectric properties of polyimide films was investigated using X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and contact angle measurements. The dielectric characteristics of the films were studied using a dielectric spectrometer. From the results, it was found that the plasma treatment introduced fluorine functional groups onto the polyimide surfaces. F 1s/C 1s ratios of the polyimides were enhanced with the increase of plasma treatment time. Consequently, the fluorine groups led to a decrease of the surface free energy and dielectric constant of the polyimide films, which can largely be attributed to the decrease of the deformation polarizability or London dispersive component of surface free energy of the solid surface studied.     

Attachment and phospholipase A2-induced lysis of phospholipid bilayer vesicles to plasma-polymerized maleic anhydride/SiO2 multilayers

This article describes a method by which intact vesicles can be chemically attached to hydrolyzed maleic anhydride films covalently bound to plasma-polymerized SiO2 on Au substrates. Surface plasmon field-enhanced fluorescence spectroscopy (SPFS) combined with surface plasmon resonance spectroscopy (SPR) was used to monitor the activation of plasma-deposited maleic anhydride (pp-MA) film with EDC/NHS and the subsequent coupling of lipid vesicles. The vesicles were formed from a mixture of phosphatidylcholine and phosphatidylethanolamine lipids, with a water-soluble fluorophore encapsulated within. Vesicle attachment was measured in real time on plasma films formed under different pulse conditions (plasma duty cycle). Optimum vesicle attachment was observed on the pp-MA films containing the highest density of maleic anhydride groups. Phospholipase A2 was used to lyse the surface-bound vesicles and to release the encapsulated fluorophore.     

Plasma polymerization. IX. A systematic investigation of materials synthesized in inductively coupled plasmas excited in perfluoropyridine

The RF plasma polymerization of perfluoropyridine was investigated for a range of operating parameters. The stoichiometries of the resulting thin films indicated a predominance of rearrangement mechanisms in their formation in which both nitrogen and fluorine were retained at approximately the same level as in the starting monomer. In appropriate cases a comparison was drawn with plasma polymers produced under comparable conditions from perfluoro and pentafluorobenzenes. Although the plasma polymer films from the benzenes have a low critical surface tension, that for the pyridine system changes with time, and the surface becomes completely wettable with water. This is attributed to surface hydrolysis of the plasma polymer films produced from perfluoropyridine.     

骨髓基质干细胞在等离子体处理PEGDA基凝胶表面的黏附和增殖

通过低温等离子体技术对聚乙二醇双丙烯酸酯(PEGDA)/甲基丙烯酸β-羟乙酯(HEMA)共聚物水凝胶生物材料进行表面改性,以骨髓基质干细胞(BMSc)为细胞模型,考察了细胞在等离子体表面改性前后的水凝胶材料的黏附和增值行为,材料的表面性能通过 X 射线光电子能谱、接触角和扫描电镜进行表征.研究结果表明,材料表面经氩等离...     

Determination of amine and aldehyde surface densities: application to the study of aged plasma treated polyethylene films

The aim of this work was to test and to compare different methods reported in the literature to quantify amine and aldehyde functions on the surface of polyethylene (PE) films treated by ammonia plasma and to specify their stability against time. A low pressure ammonia plasma reactor was used to functionalize PE films with amine groups, which could be subsequently used for further immobilization of biomolecules. In order to determine the density of amine groups on the surface of treated films, various molecule probes and spectrophotometric analytical methods have been investigated. Two methods using (i) sulfosuccinimidyl 6-[3'-(2-pyridyldithio)-propionamido] hexanoate (sulfo-LC-SPDP) and (ii) 2-iminothiolane (ITL) associated with bicinchoninic acid (BCA) have been proved to be reliable and sensitive enough to estimate the surface concentration of primary amine functions. The amount of primary amino groups on the functionalized polyethylene films was found to be between 1.2 and 1.4 molecules/nm2. In a second step, the surface concentration of glutaraldehyde (GA), which is currently used as a spacer arm before immobilization of biomolecules, has been assessed: two methods were used to determine the surface density of available aldehyde functions, after the reaction of GA with the aminated polyethylene film. The concentration of GA was found to be in the same range as primary amine concentration. The influence of aging time on the density of available amino and aldehyde groups on the surfaces were evaluated under different storage conditions. The results showed that 50% of the initial density of primary amine functions remained available after storage during 6 days of the PE samples in PBS (pH 7.6) at 4 degrees C. In the case of aldehyde groups, the same percentage of the initial density (50%) remained active after storage in air at RT over a longer period, i.e., 15 days.     

Improving surface quality of polyethylene terephthalate film for large area flexible electronic applications

Lamination is a method utilized to protect flexible electroluminescence device against environmental hazards, such as dust, moisture, and water vapor. The materials are typically joined together using adhesive or cohesion of the materials during the lamination process. Polyethylene terephthalate (PET) is commonly used as the substrate film where electroluminescence patterns are printed. However, PET film has a relatively low surface energy and high contact angle, which would cause relatively weak laminating strength. This paper discusses the use of atmospheric plasma as a surface treatment method to modify PET and laminating films’ interface to improve bonding and laminating quality. Experimental results revealed that atmospheric plasma process reduced the contact angle of both PET and laminating films. Functional groups favoring hydrophilicity were found on the films’ interface after the atmospheric plasma treatment. These effects consequently increased surface energies of both films and favored bonding between the films. The treated films thus had increased laminating strength by approximately six times without compromising the transparency quality.     

Hemocompatibility of poly(acrylonitrile-co-N-vinyl-2-pyrrolidone)s: swelling behavior and water states

Hemocompatibility is an essential aspect of blood contacting polymers. Knowledge of the relationship between polymer structure and hemocompatibility is important in designing such polymers. In this work, the effect of swelling behavior and states of water on the hemocompatibility of poly(acrylonitrile-co-N-vinyl-2-pyrrolidone) (PANCNVP) films was studied. Platelet adhesion and plasma recalcification time tests were used to evaluate the hemocompatibility of the films. Considering the importance of surface properties on the hemocompatibility of polymers, static water contact angles were measured by both sessile drop and captive bubble methods. It was found that, on the film surface of PANCNVP with a higher NVP content, adhered platelets were remarkably suppressed and the recalcification time was longer. The total water content adsorbed on the PANCNVP film was determined through swelling experiments performed at temperatures of interest. Differential scanning calorimetry and thermogravimetric analysis were used to probe the states of water in the films. Based on the results from these experiments, it was hypothesized that the better hemocompatibility of PANCNVP films with higher NVP contents was due to their higher free water content, because water molecule exchange at the polymer/liquid interface, facilitated by a high free water content, is unfavorable for the formation of surface bound water, which causes poor hemocompatibility. [diagram in text].     

SURFACE MODIFICATION OF BLEND FILMS COMPOSED OF SILK FIBROIN AND POLY（ETHYLENE GLYCOL） MACROMER AND THEIR IN VITRO ANTITHROMBOGENICITY

In order to improve the blood compatibility of silk fibroin (SF), poly(ethylene glycol) macromer (PEGM) in different amounts was added to the SF film to incorporate C=C group into the surface of blend films which were then modified by SO2 gas plasma treatment. ATR-FITR and XPS were used to analyze the chemical change which had occurred on the film‘s surface. When the content of sulfur on the surface of blend films surpasses 1.59%, the antithrombogenicity of plasma treated films increases remarkably due to surface sulfonation. This result implies that SF with blend of PEGM after SO2 plasma treatment have potential use for making blood-contacting biomaterials.     

Treatment and Stability of Sodium Hyaluronate Films in Low Temperature Inductively Coupled Ammonia Plasma

Surface of sodium hyaluronate films was modified in the inductively coupled low temperature ammonia plasma. The amount of bonded nitrogen was measured by the XPS method. The optical emission and temperature of the sample surface were measured during sample processing. Increased processing time and increased discharge power caused a rise of nitrogen concentration on the surface of hyaluronan films, though this effect is limited due to surface saturation and sample destruction at elevated discharge power.     

Grafting of poly(ethylene oxide) to the surface of polyaniline films through a chlorosulfonation method and the biocompatibility of the modified films

Poly(ethylene oxide) (PEO) could be grafted on the surface of polyaniline (PANI) films by chlorosulfonating the films with chlorosulfonic acid followed by reacting the modified films with PEO in a pyridine solution. The modified PANI films were examined by X-ray photoelectron spectroscopy and water droplet contact angles. The surface of the PEO grafted to hydrophobic PANI films became hydrophilic and the amounts of bovine serum albumin and human blood plasma platelet adsorbed onto it were decreased by more than 80%. For comparison purposes, and because the water wetting angle can be used as a measure of biocompatibility, wetting angle experiments have been also carried out for Pluronic triblock copolymer grafted to PANI and PEO or Pluronic molecules entrapped on the surfaces of PANI films. PANI was selected as substrate because one can easily change its surface properties by PEO grafting and because being conductive can be used as a sensor.     

TiOx Films Deposited by Plasma Enhanced Chemical Vapour Deposition Method in Atmospheric Dielectric Barrier Discharge Plasma

The plasma enhanced chemical vapour deposition method applying atmospheric dielectric barrier discharge (ADBD) plasma was used for TiO_x thin films deposition employing titanium (IV) isopropoxide and oxygen as reactants, and argon as a working gas. ADBD was operated in the filamentary mode. The films were deposited on glass. The films?? chemical composition, surface topography, wettability and aging were analysed, particularly the dependence between precursor and reactant concentration in the discharge atmosphere and its impact on TiO_x films properties. Titanium in films near the surface area was oxidized, the dominating species being TiO₂ and substoichiometric titanium oxides. The films exhibited contamination with carbon, as a result of atmospheric oxygen and carbon dioxide reactions with radicals in films. No relevant difference of the film surface due to oxygen concentration inside the reactor was determined. The films were hydrophilic immediately after deposition, afterwards their wettability diminished, due to chemical reactions of the film surface and chemical groups involved in the atmosphere.