Plasma for Modification of Polymers

The effect of nonpolymer-forming plasma (e.g., plasma of hydrogen, helium, argon, nitrogen) can be viewed as the following two reactions: 1) reaction of active species with polymer, and 2) formation of free radicals in polymer which is mainly due to the UV emitted by the plasma. The incorporation of nitrogen into the polymer surface by N₂ plasma and the surface oxidation by O₂ plasma are typical examples of the first effect. The latter effect generally leads to incorporation of oxygen in the form of carbonyl and hydroxyl and to some degree of cross-linking depending on the type of substrate; however, the degradation of polymer at the surface manifested by weight loss occurs in nearly all cases when polymers are exposed to plasma for a prolonged period of time. The effects of polymer-forming plasma is predominated by the deposition of polymer (plasma polymer); however, with some plasma-susceptible polymer substrates the effect of UV emission from polymer-forming plasma cannot be neglected. The mechanism of polymer formation can be explained by the stepwise reaction of active species and/or of an active specie with a molecule, and the chain addition polymerization of some organic compounds (e.g., vinyl monomers) is not the main route of polymer formation.

Plasma polymers contain appreciable amount of trapped free radicals; however, the concentration is highly dependent on the chemical structure of the monomer. In plasma polymerization, 1) triple bond and/or aromatic structure, 2) double bond and/or cyclic structure, and 3) saturated structure are three major functions which determine the rate of polymer formation and the properties of plasma polymers. The changes of some properties of plasma polymers with time are directly related to the concentration of trapped free radicals in plasma polymers. The amount of trapped free radicals in a plasma polymer is also influenced by the conditions of discharge; however, the UV irradiation from the polymer-forming plasma is not the main cause of these free radicals. Excess amount of free radicals are trapped during the process of polymer formation (rather than forming free radicals in the deposited polymer by UV irradiation). The properties of a plasma polymer is generally different from what one might expect from the chemical structure of the monomer, due to the fragmentation of atoms and/or functions during the polymerization process. This is another important factor to be considered for the modification of polymer surfaces by plasma polymerization.     

聚合物的表面光接枝改性

本文总结了利用紫外光接枝改性聚合物表面的研究进展，对接枝方法，接枝证明。接枝结构、实验条件对接枝的影响以及其广泛的应用几个方面进行了介绍。     

光化学反应在生物材料表面修饰中的应用

生物医用材料的表界面设计在组织工程、生物医疗器械、生物传感与检测、生物芯片等领域越来越重要,深入理解材料性质,尤其是表界面性质,对生物材料研发具有一定指导作用。在生物材料表界面修饰的各种方法中,光化学修饰方法简单高效,且具有时空可控性和非侵入性等优点,已成为生物材料表界面修饰中的热点研究领域之一。本综述在介绍近年来发展的生物材料表面光化学修饰方法的基础上,集中介绍其在组织再生材料(仿细胞外基质界面、硬度调控薄膜凝胶、图案化和梯度表面、光响应动态表面)、微液滴阵列表面、高通量生物芯片等领域的应用,并进一步展望了光化学表面修饰在生物医用界面研究中的关键挑战和发展方向。     

Atmospheric Pressure Plasma Surface Treatment of Polymers and Influence on Cell Cultivation

Atmospheric plasma treatment is an effective and economical surface treatment technique. The main advantage of this technique is that the bulk properties of the material remain unchanged while the surface properties and biocompatibility are enhanced. Polymers are used in many biomedical applications; such as implants, because of their variable bulk properties. On the other hand, their surface properties are inadequate which demands certain surface treatments including atmospheric pressure plasma treatment. In biomedical applications, surface treatment is important to promote good cell adhesion, proliferation, and growth. This article aim is to give an overview of different atmospheric pressure plasma treatments of polymer surface, and their influence on cell-material interaction with different cell lines.     

Symposium on Biomedical Polymers

ABSTRACT

Glycine functions were incorporated into 2–20 mol% N,N′-methylene-bis-acrylamide (NNMBA)-crosslinked polyacrylamides by transamidation with excess sodium salt of glycine. Complexation characteristics of glycine functions in different structural environments were investigated towards Co(II), Ni(II), Cu(II) and Zn(II) ions. The observed trend in complexation was found to be: Cu(II) > Ni(II) > Co(II) > Zn(II). The polymeric ligands and metal complexes were characterized by various spectral techniques. The polymeric ligands could be recycled several times and the metal ion desorbed resins showed specificity to the desorbed metal ion than other metal ions. This originates from the development of certain ‘pockets’ left by the desorbed metal ion or the ‘memory’ of the polymeric ligands for the desorbed metal ion. This lightly crosslinked systems showed much faster rebinding kinetics. The conditions of metal ion binding and rebinding were optimized to exploit the specific and selective separation of metal ions using metal ion desorbed systems. The specificity and selectivity characteristics depend on the degree of NNMBA crosslinking.     

医用高分子材料表面的润滑改性进展

综述了医用高分子材料表面的润滑改性方法,对影响表面润滑性的因素进行了讨论,简述了材料表面润滑性的测定方法,润滑机理及润滑表面的形态,概述了表面润滑的医用高分子材料在临床中的应用。     

Recent Developments in the Surface Modification of Polymers

Summary. Selected trends and scientific achievements in the surface modification of polymers are reported. In this context, both UV-light triggered free radical polymerization-based techniques relevant to industrial processes and ring-opening metathesis polymerization-based chemistry, relevant for the manufacture of specialty materials, are addressed.     

量子点的聚合物表面修饰及其应用

量子点作为新型纳米发光材料备受关注,但由于光学稳定性和生物相容性的问题而在实际应用上受限。聚合物对量子点的修饰能够提供量子点合成的有效支撑基质,而且还可以改善量子点的稳定性和单分散性,进而可以拓展量子点应用于化学、物理以及生物学领域。基于聚合物修饰量子点的优势,本文简述了聚合物表面修饰量子点的方法、合成路线、步骤、特点以及发展现状。其中,双亲分子涂敷的量子点可以改善量子点的水溶性;多基配体包裹的量子点更具有稳定性和功能性;末端功能化聚合物表面修饰的量子点则可以合成更为先进功能的材料;胶封树枝状定域量子点具有单分散和优越发光特性。同时,还综述了各种表面修饰方法的最新研究进展,存在问题以及应用发展趋势。     

生物多糖进行医用高分子材料表面修饰的研究进展

综述了国内外应用生物多糖进行医用高分子材料表面修饰的研究状况,其中重点介绍了葡聚糖、肝素及类肝素类物质、壳聚糖等多糖在高分子材料表面修饰的研究近况.多糖是自然界中含量最为丰富的生物大分子,几乎存在于所有的生命体中,具有很好的生物相容性,而且某些生物多糖还具有特殊的生物活性,因此用生物多糖进行医用高分子材料的表面修饰受到了国内外研究学者的关注.大量研究表明,经过生物多糖表面修饰的高分子材料可获得良好的生物相容性和某些优良的医学应用性能.     

Modification of Active Carbon by Hydrophobic Plasma Polymers: II Fabric Substrates

Active carbon, used in various types of chemical protection devices, can absorb an extremely wide range of hazardous compounds. Unfortunately, this universal absorption includes ubiquitous water molecules, which can result in saturation and premature loss of efficacy. The purpose of this work has been to treat active carbon-impregnated fabric with appropriate low-pressure plasmas, so as to render the carbon surface hydrophobic, while minimally affecting its ability to absorb toxic gases or vapors (simultated here by CCl₄). The best results have been achieved using plasma polymerization of organosilicon (PP-HMDSO) thin films onto the fabric surface: This has been done in a pilot-scale microwave plasma reactor system, designed for treating continuously-moving flexible web materials up to 30 cm in width. Under optimal treatment conditions, a plasma exposure duration of 10 s (PP-HMDSO film thickness, d 40 nm) is found to be sufficient to reduce water absorption by 85%, while the corresponding reduction in CCl₄absorption is small (<20%). The treatment demonstrates long-term stability, and it holds promise for commercial implementation on existing roll coaters.     

Influence of Oxygen Plasma Modification on Surface Free Energy of PMMA Films and Cell Attachment

For any biomaterial placed into a biological medium, the surface properties of the material, such as porosity, crystallinity, presence and distribution of electrical charge and functional groups are very critical parameters that determine the acceptance or rejection of the material. Applications, especially tissue engineering require some surface modifications at the molecular level without disturbing the bulk properties of the implants in order to enhance the cell attachment on the material. An appropriate technique is the application of glow discharge plasma which employs no solvents, takes place at ambient temperatures, and alterations take place only at the surface by changing the surface chemistry along with surface free energy (SFE) and efficiency for cell-material interaction. In this study, poly(methyl methacrylate) (PMMA) film surfaces were modified with oxygen plasma. SFE and its dispersive and polar (acidic-basic) components of the modified surfaces were calculated by means of several theoretical approaches including geometric mean, harmonic mean and acid-base equations. The relation between SFE and its dispersive and polar components and cell attachment on surfaces were studied. The highest 3T3 cell attachment was obtained for the surface with the total SFE of 61.77 mJ/m² and polar component of 50.91 mJ/m² according to Geometric mean. The total SFE of this surface was calculated to be 61.06 mJ/m² and the polar component as 40.96 mJ/m² using the Harmonic mean method.     

生物医用材料表面仿细胞膜结构改性

细胞膜因其固有的生物相容性,可以作为体内植入材料及器件表面生物相容化改性的范例。大量研究结果表明,用细胞外层膜的亲水官能团－磷酰胆碱基团修饰材料表面,可显著提高材料的生物相容性,具有广阔的应用前景。本文综述了用含磷酰胆碱基团小分子及聚合物进行仿细胞膜结构改性的各种方法及其代表性工作;讨论了不同方法得到的仿细胞膜结构表面的性能;总结了几种有影响的生物相容性机理;对仿细胞膜结构表面改性研究及应用的前景做了展望。     

微波等离子体对聚乙烯材料的表面改性

对高分子材料进行表面修饰,可以赋予材料表面新的物理和化学性能,提高材料的亲水性、粘结性、电镀和生物匹配性等．在表面改性方法中,新近发展的等离子体改性技术由于具有操作简单,工艺干法化,不影响材料本体结构和性能等优点而日益受到人们的重视［１,２］．微波等...     

聚对苯二甲酸乙二酯的等离子体表面改性研究

阐述了等离子体原理,综述了等离子体对聚对苯二甲酸乙二酯表面改性的研究工作,大量的实验数据表明了这种方法可以成功改善各种性能。等离子体处理后PET材料表面粗糙度增加,并产生化学基团,因此可改善以下各种性能:润湿性、粘接性、染色性、抗静电性,对人体的生物相容性,添加TiO2的杀菌性,PET表面化学镀金属的性能。PET表面的刻蚀作用,导致其重量的减轻,可替代部分碱减量处理。     

Surface Modification and Contact Interaction of Particles

Abstract

The effects of particle surface modification by ambient media and surfactant adsorption on the cohesive forces in the immediate contacts between individual particles have been studied with the CF (cohesive force) apparatus. The values of the free energy of interaction in direct coagulation contacts between particles of various types in liquids of different polarity and in the presence of various surfactants have been measured. They cover a broad range of several orders of magnitude; these interactions define the rheological properties of concentrated thixotropic systems and their stability with respect to peptization. A similar experimental technique has been used for studying active media influences on various physico‐chemical processes of particle bridging and formation of the phase contacts responsible for the mechanical properties of related solid structures and their resistance to fracture. The effect of the adsorption induced decrease in strength and durability of such porous structures with phase contacts and compact solids is considered.     

Surface Interactions of Radicals During Plasma Processing of Polymers

Surface interactions of radical species were investigated using the imaging of radicals interacting with surfaces (IRIS) technique during plasma surface modification of polymers. Three plasma systems were investigated by spatially probing the laser induced fluorescence of individual radical species and determining their surface scattering coefficients, S. The behavior of CF₂ moieties on polymer surfaces was studied using the fluorocarbon plasmas C₂F₆ and hexafluoropropylene oxide (HFPO). Three types of surface interactions were observed, surface generation of CF₂ (S > 1), surface loss of CF₂ (S < 1), and unit scattering (S = 1). Surface loss of CF₂ was seen in HFPO plasmas, while CF₂ was generated in C₂F₆ systems. The differences between these systems is believed to be the result of different overall surface interactions, specifically film deposition in the HFPO system and etching in the C₂F₆ system. Using NH₃ plasmas, the surface interactions of NH₂ radicals with polymers was also investigated. Here, NH₂ is generated at the surface of polyethylene and polytetrafluoroethylene substrates, but is consumed on polyimide substrates. Ion effects were also investigated by placing a grounded mesh in the path of the molecular beam to remove charged species.     

基于硅胶表面修饰的分子印迹技术研究进展

综述;基于硅胶表面修饰的分子印迹技术研究进展     

Plasma Surface Modification of Fluoropolymers Studied by ToF-SIMS

Surface modification by plasma treatment is an efficient way of improving metal adhesion to polymers. Here, Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS) is used to characterize the surfaces of Teflon PFA and Teflon AF1600 films, following plasma treatments in H₂, O₂ and N₂ gases. This work is complementary to our previous study using XPS, and is particularly directed toward the identification of incorporated hydrocarbons which could seriously affect metal adhesion. Plasma treatments strongly modify the surfaces of fluoropolymers, causing the ablation of a part of the fluorocarbon structure, with H₂ being the most effective gas. The hydrocarbon content of such surfaces is not negligible, and a comparison with hydrocarbon levels on untreated surfaces suggests that a substantial fraction of this material was incorporated on plasma treatment; this is particularly so in the case of H₂ plasma treatment. Due to expected strong matrix effects caused by significant changes in surface chemistry and structure following the various plasma treatments, the use of SIMS absolute intensity values is discussed in terms of data treatment artifacts. Moreover, due to the differences in secondary ion yields between characteristic hydrocarbon and fluorocarbon SIMS peaks, the use of peaks normalized to the total intensity is also impractical. Here, positive mode absolute intensities and negative mode peak intensity values, when normalized to I_tot - I(H^–) - I(F^–), give valuable information, as in the comparison of hydrocarbon and N incorporations.     

医用聚氯乙烯膜的等离子体表面改性

用两种不同气氛的辉光放电等离子体工艺对医用软质聚氯乙烯（ＰＶＣ）膜进行了表面改性研究。结果表明，聚合性气氛的等离子体改性效果明显优于非聚合性气氛。平整致密的聚合膜对ＰＶＣ增塑剂——邻苯二甲酸二辛酯的迁移和扩散起了阻挡作用，也使膜表面亲水性和表面张力极性成份增大，液固相界面张力减小，生物相容性得以改善。