The influence of side groups and polarity of polymers on the kind and effectiveness of their surface modification by air plasma action

The changes of contact angle (θ) and surface free energy (γ_S) under low-temperature air plasma in the polymers of different chemical structure and polarity (polyethylene, PE; polypropylene, PP; poly(ethylene terephtalate), PET and poly(methyl methacrylate), PMMA) pointed out to the greater effect of short-time plasma action (5-15 s) on these parameters as compared to longer times of exposure.The non-reversion effect of θ changes caused by plasma in PE and PP suggests that the oxidation processes mainly decide about values in nonpolar polymers. The significantly greater θ changes in PE than those in PP indicate that the side groups present in the main chains impede oxidation of such a polymer by plasma.The reversion of θ changes in PET and in PMMA, and return of these values to almost the initial ones after 10 min storage proves that the main reason for θ changes in polar polymers is a certain alteration of the chain conformation.These changes, taking place after longer plasma treatment, suggest that the side ester groups in PMMA retard the above-mentioned conformational transformations. Then, in both kinds of polymers (polar and nonpolar) the structure of macrochain decides about the efficiency of reaction caused by plasma, and at the same time the side groups retard not only the oxidation processes but the conformational changes as well.     

Surface bio-modification of poly(hydroxybutyrate-co-hydroxyhexanoate) and its aging effect

In this work, poly(hydroxybutyrate-co-hydroxyhexanoate) (PHBHHx) film was fabricated by a solution-casting method and subsequently was modified by NaOH treatment to improve the surface hydrophilic property. Surface properties including hydrophilicity, surface appearance and functional groups were characterized by water contact angle measurement, scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). The results showed the hydrophilicity of PHBHHx film was obviously improved by the NaOH treatment due to the topography changes promoted by the NaOH-etching and the introduction of polar groups included hydroxyl and carboxyl on the topmost surface layers. However, the modified film exhibited an aging effect: the hydrophilicity decreases with time elapsed during storage. It was found that the aging rate was strongly dependent on the crystallinity of the film and the storage environment. The sample with high-crystallinity lost hydrophilic property slower than that with low-crystallinity. Hydrophilic and low-temperature environment also prevented the modified PHBHHx from fast losing of the hydrophilicity.     

Surface modification of low density polyethylene (LDPE) film by low pressure O2 plasma treatment

In this work, low pressure glow discharge O₂ plasma has been used to increase wettability in a LDPE film in order to improve adhesion properties and make it useful for technical applications. Surface energy values have been estimated using contact angle measurements for different exposure times and different test liquids. In addition, plasma-treated samples have been subjected to an aging process to determine the durability of the plasma treatment. Characterization of the surface changes due to the plasma treatment has been carried out by means of Fourier transformed infrared spectroscopy (FTIR) to determine the presence of polar species such as carbonyl, carboxyl and hydroxyl groups. In addition to this, atomic force microscopy (AFM) analysis has been used to evaluate changes in surface morphology and roughness. Furthermore, and considering the semicrystalline nature of the LDPE film, a calorimetric study using differential scanning calorimetry (DSC) has been carried out to determine changes in crystallinity and degradation temperatures induced by the plasma treatment. The results show that low pressure O₂ plasma improves wettability in LDPE films and no significant changes can be observed at longer exposure times. Nevertheless, we can observe that short exposure times to low pressure O₂ plasma promote the formation of some polar species on the exposed surface and longer exposure times cause slight abrasion on LDPE films as observed by the little increase in surface roughness.     

Surface modification and characterization of thermoplastic polyurethane

This work reports the modification of thermoplastic polyurethanes (TPUs) in order to enlarge their application range, for example, as biomaterials by increasing its hydrophilicity.A TPU was successfully modified by using three different strategies: ultra-violet irradiation (UV), gamma irradiation (GI) and interfacial modification (IM). The results suggested the possibility of modifying the polyurethane-based surface either with poly(ethylene glycol) (PEG) or hydroxylethyl methacrylate (HEMA) or hexamethylene diamine (HMD) or chitosan (CT) by using any of these methods. The properties of the grafted PU were evaluated by surface, structural and thermal analysis. The results suggest that, among the methods studied in this work, the modification by gamma irradiation (GI) seems to be the most promising, since this method gives high values of grafting yield and has the advantage of providing a clean modification, meaning that no initiator is needed.     

Surface modification of aromatic polyamide film by oxygen plasma

The surface of poly(p-phenylene terephthalamide) (PPTA) films was modified by oxygen plasma, and the modified film surface was analyzed by an advancing contact meter and X-ray photoelectron spectroscopy (XPS). The advancing contact measurement showed that the oxygen plasma treatment made the surface of the PPTA film hydrophilic. The XPS analyses also showed the increase in the O/C and N/C atom ratio, especially the O/C atom ratio, at the PPTA film surface by the oxygen plasma treatment. A main oxygen functionality formed by the oxygen plasma treatment is a carboxylic acid group, and a main nitrogen functionality formed is a protonated amino group. The formation of the oxygen and nitrogen functionalities formed by the oxygen plasma treatment is not restricted to the surface of the PPTA film, but penetrates at least 35 Å deep from the film surface. The formation of these carboxylic acid and protonated amino groups is a result of the bond scission of the amide linkages in the PPTA film. Interactions of photons in the oxygen plasma rather than interactions of electrons and activated oxygen atoms contribute greatly to the bond scission. © 1995 John Wiley & Sons, Inc.     

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.     

Surface modification of PDMS by surface-initiated atom transfer radical polymerization of water-soluble dendronized PEG methacrylate

The current paper reports the synthesis of a highly hydrophilic, antifouling dendronized poly(3,4,5-tris(2-(2-(2-hydroxylethoxy)ethoxy)ethoxy)benzyl methacrylate) (PolyPEG) brush using surface initiated atom transfer radical polymerization (SI-ATRP) on PDMS substrates. The PDMS substrates were first oxidized in H₂SO₄/H₂O₂ solution to transform the Si-CH₃ groups on their surfaces into Si-OH groups. Subsequently, a surface initiator for ATRP was immobilized onto the PDMS surface, and PolyPEG was finally grafted onto the PDMS surface via copper-mediated ATRP. Various characterization techniques, including contact angle measurements, attenuated total reflection infrared spectroscopy, and X-ray photoelectron spectroscopy, were used to ascertain the successful grafting of the PolyPEG brush onto the PDMS surface. Furthermore, the wettability and stability of the PDMS-PolyPEG surface were examined by contact angle measurements. Anti-adhesion properties were investigated via protein adsorption, as well as bacterial and cell adhesion studies. The results suggest that the PDMS-PolyPEG surface exhibited durable wettability and stability, as well as significantly anti-adhesion properties, compared with native PDMS surfaces. Additionally, our results present possible uses for the PDMS-PolyPEG surface as adhesion barriers and anti-fouling or functional surfaces in biomedical applications.     

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...     

Surface modification of Kapton film by plasma treatments

Kapton films were treated with seven plasmas: Ar-, N₂-, O₂-, CO-, CO₂-, NO-, and NO₂- plasmas. Surface properties and chemical composition of the plasma-treated Kapton films were investigated from the contact angle measurement, and the IR and XPS spectra. The plasmas, especially NO- and NO₂-plasma, made the Kapton film surface hydrophilic. The XPS and IR spectra showed that the plasma led to the modification of the imide groups in the Kapton film to secondary amide and carboxylate groups.     

Surface modification of polypropylene membranes by γ-ray induced graft copolymerization and their solute permeation characteristics

Porous hydrophobic polypropylene (PP) membranes were subjected to the surface modification by the γ-ray induced graft copolymerization with hydrophilic 2-hydroxyethyl methacrylate (HEMA). The structural changes and surface morphologies of the modified PP membranes were characterized by a Fourier transform infrared spectroscopy (FT-IR), elemental analysis (EA) and field emission scanning electron microscopy (FE-SEM). Peroxides produced from γ-ray irradiation were determined by a 1,1-diphenyl-2-picryl hydrazyl (DPPH) method and the surface hydrophilicities of membranes were measured by a static contact angle measurement. The contact angle of the modified membranes reduced with the degree of grafting (DG) of HEMA onto the membrane surface, and it decreased up to about half of that before modification. The permeation behaviors of all membranes were investigated by a bovine serum albumin (BSA) filtration experiment. As a result, the DG of the modified membrane increased with the reaction time. However, in the case of irradiation dosage it showed the maximum value at 20 kGy. Also, the modified membrane showed a higher solution flux, lower BSA adsorption, and the better flux recovery after cleaning than that of the unmodified membrane. Particularly, 40.6% grafted membrane showed a two-fold increase in a BSA solution flux, 62% reduction in total fouling and three-fold increase in flux recovery after chemical cleaning.     

疏水性聚丙烯酸酯人工晶状体的低温等离子体改性

通过低温等离子体表面改性技术对疏水性聚丙烯酸酯人工晶状体进行表面改性, 并对改性前后材料的表面结构、形貌和光学性能进行了表征. 静态水接触角结果显示, 经过氨等离子体处理后的人工晶状体亲水性效果最好, 同时最佳的改性时间为120 s, 改性功率为150 W. XPS分析结果进一步证实, 经等离子体处理后, 在人工晶状体表面引入了极性基团. 原子显微镜观察结果显示, 改性后材料表面更加凹凸不平, 粗糙度显著增加而透光率变化很小, 但过大功率改性的样品透光率明显下降. 时效性测试结果表明, 人工晶状体在改性14 d后疏水性恢复趋于稳定.     

Cell outer membrane mimetic modification of a cross-linked chitosan surface to improve its hemocompatibility

A novel strategy has been developed to improve the hemocompatibility of chitosan surface by cell outer membrane mimetic structure able to reduce protein adsorption and cell adhesion. Phosphorylcholine dichloride was synthesized and grafted onto a glutaraldehyde-cross-linked chitosan (CS-GA) film surface to prepare phosphorylcholine-coated CS-GA film (CS-GA-PC) through a heterogeneous reaction process. The spectroscopic and contact angle characterization show that a cell outer membrane mimetic structure was formed on the cross-linked chitosan surface, and the significantly improved hemocompatibility of the modified surface was shown by a suppression of 94% on platelet adhesion, a suppression of 60–70% for bovine plasma fibrinogen and bovine serum albumin adsorptions. These results demonstrated that this cell outer membrane mimetic surface modification with phosphorylcholine dichloride is a promising strategy to improve the hemocompatibility of chitosan.     

Ar等离子体对氟橡胶F2311表面的改性

利用氩气等离子对氟橡胶F2311进行表面亲水改性处理，通过接触角测量、X射线光电子能谱(XPS)对改性后的F2311进行分析，结果表明氩气等离子体处理可通过等离子体聚合在F2311表面形成含碳、氧、氮的覆盖层，可较好地改善F2311的表面亲水性，并有较好的表面动力学性质，获得的表面亲水性可以保持很长时间。     

Surface modification of non-woven fabric by DC pulsed plasma treatment and graft polymerization with acrylic acid

Direct-current pulsed plasma treatment (DPPT) followed by thermal-induced graft polymerization with acrylic acid (AA) was used to modify poly(ethylene terephthalate)/polyethylene (PET/PE) non-woven fabric (NWF) in this study. The water contact angle of plasma modified NWF decreased sharply with DPPT time in 4 s. The water content of the NWF increased with DPPT time and levelled off after 30 s. Chemical analysis by X-ray photoelectron spectroscopy (XPS) indicated that the surface property of modified NWF could be maintained for more than 8 months under ambient conditions and could be further improved by grafting with acrylic acid. The concentration of AA in PET/PE-g-AA NWF increased both with the monomer concentration and the plasma treatment time. The maximum grafting density was 1.17 μmol/cm² with 40 s DPPT and 20% (w/w) AA. Improved biocompatibility of the modified NWF was confirmed with 3T3 fibroblast cells where cell viability was analyzed by MTT assays. More cells were found to attach to the modified NWF with higher growth rates, indicating that an improvement in surface properties by DPPT followed by graft polymerization of AA is beneficial for cell attachment and growth. A much more uniform cell distribution was found within the modified NWF from confocal laser scanning microscope observations.     

Surface modification of chlorobutyl rubber by plasma polymerization

Radio frequency (r.f.) plasma polymerization of vinylidene fluoride (CH₂CF₂) has been used to modify the surface properties of chlorobutyl rubber. FTIR-ATR spectra of the treated rubbers and transmission spectra of plasma polymer films on NaCl windows indicated that as power increased the F/H ratio decreased. SIMS tests supported the FTIR results, and showed that the decrease in the F/H ratio was due to a decrease in the amount of F and an increase in the amount of H in the plasma polymer. Sliding friction measurements showed a reduction in the coefficient of friction (μ) from 3.7 for the untreated rubber to values ranging between 0.4 and 1.9 for the plasma-treated rubbers. There did not appear to be any correlation between the coefficient of friction and plasma power or monomer flow rate, and the average coefficient of friction for the plasma-treated samples was 0.9, which was lower than a commercially used silicone oil treatment (μ = 1.1–1.3). Repetitive sliding friction tests showed that the plasma- and silicone oil treated-chlorobutyl rubbers had the similar lubricating lifetimes. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 1651–1660, 1997     

Characterization of CO2 plasma treated polymeric membranes and quantification of flux enhancement

Low-temperature CO₂ plasma is used for the treatment of poly-ethersulfone (PES), polyamide (PA) and poly-phenylene ethersulfone (PPE) ultrafiltration membranes. This has led to significant enhancement of the wetting characteristics of the membrane surface as is shown by contact angle measurements and Fourier transform infrared (FTIR) spectrum analysis of the treated membranes. Changes in the physical characteristics of the surface, such as tensile property, surface roughness, etc. are quantified by tensile strength measurement and atomic force microscopy (AFM), respectively. An increase in the measured values of the di-electric constants further highlights the hydrophilic modification of the surface. A series of ultrafiltration experiments using a BSA solution of known concentration under different operating conditions is performed and the deposition thicknesses over the membrane surface during ultrafiltration are measured directly using image analyzing microscopy. The results clearly demonstrate that a plasma treated PES membrane is more hydrophilic with smoother surface and resists fouling leading to significant enhancement of permeate flux.     

采用XPS与接触角法研究氟聚合物表面结构与性能

本文采用接触角和变角XPS方法对FA共聚物的表面能、 表面微相结构做了进一步的研究.     

Nafion膜表面亲水性研究

Ｎａｆｉｏｎ膜在电化学体系中的应用越来越广泛,而其表面亲水性往往直接影响着使用性能．本文介绍一种适宜于表征Ｎａｆｉｏｎ膜表面亲水性的接触角测量方法,即束缚气泡法,并讨论了该膜与水溶液接触角的滞后现象、溶液表面张力的影响,简介了用全氟表面活性剂改善Ｎａｆｉｏｎ膜表面亲水性的尝试．     

纳米结构表面浸润性质的分子动力学研究

采用分子动力学方法研究了氩纳米液滴在铂金属及其模型固体表面的浸润现象,获得了液滴在平滑表面和三角纳米结构阵列表面的接触角和展布特性.研究表明,液滴与壁面的势能作用较强时,液滴与纳米结构表面为均匀浸润,但是由于迟滞效应,接触角受表面纳米结构的影响不明显;势能作用较弱时,纳米结构间隙中存在类似蒸汽的低密度相,液滴与纳米结构表面为非均匀浸润,接触角受纳米结构的影响而增大;表面纳米结构可以使表面具有超疏水性.     

Surface modification with well-defined biocompatible triblock copolymers Improvement of biointerfacial phenomena on a poly(dimethylsiloxane) surface

To improve interfacial phenomena of poly(dimethylsiloxane) (PDMS) as biomaterials, well-defined triblock copolymers were prepared as coating materials by reversible addition-fragmentation chain transfer (RAFT) controlled polymerization. Hydroxy-terminated poly(vinylmethylsiloxane-co-dimethylsiloxane) (HO–PV_lD_mMS–OH) was synthesized by ring-opening polymerization. The copolymerization ratio of vinylmethylsiloxane to dimethylsiloxane was 1/9. The molecular weight of HO–PV_lD_mMS–OH ranged from (1.43 to 4.44) × 10⁴, and their molecular weight distribution (M_w/M_n) as determined by size-exclusion chromatography equipped with multiangle laser light scattering (SEC-MALS) was 1.16. 4-Cyanopentanoic acid dithiobenzoate was reacted with HO–PV_lD_mMS–OH to obtain macromolecular chain transfer agents (macro-CTA). 2-Methacryloyloxyethyl phosphorylcholine (MPC) was polymerized with macro-CTAs. The gel-permeation chromatography (GPC) chart of synthesized polymers was a single peak and M_w/M_n was relatively narrow (1.3–1.6). Then the poly(MPC) (PMPC)–PV_lD_mMS–PMPC triblock copolymers were synthesized. The molecular weight of PMPC in a triblock copolymer was easily controllable by changing the polymerization time or the composition of the macro-CTA to a monomer in the feed. The synthesized block copolymers were slightly soluble in water and extremely soluble in ethanol and 2-propanol.

Surface modification was performed via hydrosilylation. The block copolymer was coated on the PDMS film whose surface was pretreated with poly(hydromethylsiloxane). The surface wettability and lubrication of the PDMS film were effectively improved by immobilization with the block copolymers. In addition, the number of adherent platelets from human platelet-rich plasma (PRP) was dramatically reduced by surface modification. Particularly, the triblock copolymer having a high composition ratio of MPC units to silicone units was effective in improving the surface properties of PDMS.

By selective decomposition of the Si–H bond at the surface of the PDMS substrate by irradiation with UV light, the coating region of the triblock copolymer was easily controlled, resulting in the fabrication of micropatterns. On the surface, albumin adsorption was well manipulated.