Effects of aromatic groups in polymer chains on plasma surface modification

Three polyester films with different repeating units—poly(lactic acid) (PLA), poly(ethylene terephthalate) (PET), and poly(oxybenzoate‐co‐oxynaphthoate) (PBN)—were modified by plasma, and the way in which the chemical compositions of the polymer chains influenced the plasma modification was investigated with contact‐angle measurements and X‐ray photoelectron spectroscopy (XPS). There were large differences in the compensated rates of weight loss among the three polyester films when they were exposed to Ar and O₂ plasmas. The PLA film showed the highest rate for weight loss of the three films, and the PBN film showed the lowest rate. The PET and PBN film surfaces were modified to become more hydrophilic by either argon or oxygen plasma. However, the PLA film surface was not made more hydrophilic by the plasmas. XPS spectra showed that the PLA film surface was not modified in its chemical composition, but the PBN film surface was modified in its chemical composition to form C? O groups in the PBN polymer chains. The reason that the PLA film surface was not modified but the PBN film surface was modified was examined. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 96–103, 2003     

Comparative studies on surface modification of poly(ethylene terephthalate) by remote and direct argon plasmas

Surface modification of poly(ethylene terephthalate) (PET) film by an argon (Ar) plasma was investigated as a function of the distance from the Ar plasma zone. Changes in distance between the PET film and the Ar plasma zone had a strong influence on the surface modification of the film. The direct Ar plasma treatment (distance between the PET film and Ar plasma zone = 0 cm) was effective in hydrophilic surface modification, but heavy etching reactions occurred during the modification. On the other hand, the remote Ar plasma treatment (distance between the PET film and Ar plasma zone = 80 cm) modified the PET film surfaces to be hydrophilic without heavy etching reactions, although the hydrophilicity of the PET was lower than that by the direct Ar plasma. The remote Ar plasma treatment was distinguished from the direct Ar plasma treatment from the viewpoint of degradation reactions. The remote Ar plasma treatment rather than the direct Ar plasma treatment was an adequate procedure for surface modification and caused less polymer degradation on the film surface. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 808–815, 2001     

Surface grafting polymerization and modification on poly(tetrafluoroethylene) films by means of ozone treatment

Surface modification on polytetrafluoroethylene (PTFE) films was performed with sequential hydrogen plasma/ozone treatments and surface-initiated polymerization. C-H groups were introduced to the surface of PTFE films through defluorination and hydrogenation reactions under hydrogen plasma treatment. The C-H groups then served as ozone accessible sites to form peroxide groups under ozone treatment. Grafting polymerization initiating from the peroxide groups was performed on the PTFE film surface with using acrylamide, acrylic acid, glycidyl methacrylate and 2-(2-bromoisobutyryloxy)ethyl acrylate (BIEA) as monomers. With utilizing the isobutylbromide groups on the surface of PTFE-g-PBIEA film as initiators, sodium 4-styrenesulfonate (NaSS) was polymerized onto the PTFE film surface via atom transfer radical polymerization, to bring arborescent macromolecular structure to PTFE film surface. The chemical structures of the macromolecules on PTFE film surfaces were characterized with FTIR-ATR, SEM-EDX and XPS. The surface hydrophilicities of modified PTFE films were significantly enhanced with the modification.     

Mechanism of gas transport in plasma treated glassy polymer films

The effect of oxygen- and Ar-plasma treatment on glassy polysulfone and polyimide films upon the gas diffusion process was investigated in the permeation of CO₂ and H₂. The plasma treatment apparently induced a reduction of only the diffusivity of Henry's law population, while the diffusion coefficient of the Langmuir population was not altered by plasma treatment. The oxygen- and Ar-plasma treatment on polysulfone films is favorable for permselectivity of H₂ relative to CO₂. Such a surface modification of polyimide films appears to be ineffective for improvement of permselectivity of H₂.     

Surface modification of PET films by a combination of vinylphthalimide deposition and Ar plasma irradiation

A new surface modification technique for PET films is proposed. This technique, called VPI modification technique, is a combination of two processes: The first step involves the deposition of vinylphthalimide (VPI) on the PET film surfaces, followed by Ar plasma irradiation of the VPI-covered film surfaces. The VPI modification technique led to large increases in the N/C atom ratio on the PET film surfaces. On the VPI-modified PET film surface, a new N_ls peak containing two components due to amide groups as well as imide groups appeared. The C_ls signal for the VPI-modified PET film surface also showed a new component due to ketone groups. These changes indicate that VPI reacted with the PET film surfaces to form nitrogen-containing groups. VPI modification made PET film surfaces hydrophilic. The VPI-modified film surfaces showed a decrease in water contact angle from 73 degrees to 48–56 degrees.     

Surface modification of poly(aryl ether ether ketone) film by remote oxygen plasma

Surface modification of poly(aryl ether ether ketone) (PEEK) film surfaces by oxygen plasma treatment was investigated. Two procedures, the direct plasma treatment and the remote oxygen plasma treatment, were used as oxygen plasma treatments, and the efficiency of the hydrophilic modification was discussed. The direct and remote oxygen plasma treatments lead to degradation of the PEEK film as well as hydrophilic surface modification. The degradation disturbs the surface modification. The remote oxygen plasma treatment rather than the direct oxygen plasma is suitable for the hydrophilic surface modification of the PEEK film. The remote oxygen plasma treatment at 10 W for 60 s forms predominantly C—O groups rather than C=O groups as an oxygen-containing group on the PEEK surface and gives a highly hydrophilic surface with a contact angle of 44 degrees. © 1998 John Wiley & Sons, Inc. J Appl Polm Sci 68:271–279, 1998     

Morphology and glass transition of thin polylactic acid films

The aim of this study is to highlight the effect of the morphology of polylactic acid (PLA) thin films on the glass transition in this confined geometry. For that purpose, poly(L ‐lactic acid) and poly(D ‐lactic acid) polymer films were prepared on different surfaces such as mica and silicon surfaces by using two different solvents. The films exhibit different morphologies starting from individual macromolecular chains at very low concentration to homogeneous films at higher concentrations. Globular to elongated rodlike structures of the PLA macromolecules were observed according to the polarity of the surface and the solvent. The T_g of PLA enantiomeric film, determined by adhesion force using atomic force microscopy (AFM) as a function of temperature, was confirmed by ellipsometric measurements. Surprisingly, this value is independent of the morphology of thin enantiomeric film. A balance between the attractive surface effects and a decrease of the crystallinity of PLA on the mobility in the amorphous region will be discussed. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Surface modification of thermotropic poly(oxybenzoate‐co‐oxynaphthoate) copolyester by remote oxygen plasma for copper metalization

Poly(oxybenzoate‐co‐oxynaphthoate) (POCO) film surfaces were modified with remote oxygen plasma, and the effects of the modification on the adhesion between the copper layer and POCO were investigated. The remote‐oxygen‐plasma treatment led to a noticeable decrease in the contact angle, which was mainly due to the C? O functional groups on the surface. The modification of the POCO surface by remote oxygen plasma was effective in improving the adhesion with copper metal. The peel strength for the copper metal/POCO system was enhanced from 10 to 127.5 mN/5 mm by the surface modification. The failure mode of the copper metal/POCO system was an interface layer between the oxidized micro‐POCO fibril surface and the copper metal layer. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2400–2408, 2003     

Improved adhesion between Kapton film and copper metal by silane-coupling reactions

Kapton film, poly[(N,N′-oxydiphenylene)pyromellitimide], was modified by silane-coupling reactions using 3′(trimethoxysilyl)propoxy-2-hydroxypro-pyl-1,3-diazole (Si–imidazole) to improve the adhesion with copper metal. The Kapton film surface was first treated with argon plasma for 30 s, then dipped into a methanol solution of Si–imidazole (0.01 wt %), followed by heating at 110°C for 90 min. The Kapton surfaces, modified by the argon plasma and Si–imizadole coupling reactions, were analyzed by water contact-angle measurement, atomic force microscopy, and XPS. The Si–imidazole modification showed a large increase in adhesion between the copper metal and the Kapton film. The peel strength of the copper metal/Kapton film joint increased from 0.94 to 2.4 N/5 mm. The failure occurred at the interface between the Si–imidazole and the Kapton film layer. We conclude that the Si–imidazole modification is an effective treatment for improvement of the adhesion between copper metal and Kapton film. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 1645–1654, 1999     

A novel plasma-enhanced way for surface-functionalization of polymeric substrates

Summary In this contribution a novel, low-pressure RF-plasma-enhanced approach is suggested for the surface functionalization of polymeric substrates. The method takes advantage of the high reactivity Ar-plasma generated free radical sites located on PE substrate surfaces, which can promote under in situ conditions, heterogeneous chemical reactions with stable gas-phase molecules, such as 1,3 diamino propane, in the absence of plasma. The presence of covalently attached primary amine functionalities was demonstrated by fluorescamine-labeling technique, further oxallyl chloride-based derivatization, and immobilization of horseradish peroxidase. The existence of specific functionalities on modified PE surfaces at different derivatization stages, was evidenced by ESCA, ATR-FTIR, and enzyme assay tests. Received: 16 May 2001/Revised version: 17 July 2001/Accepted: 19 September 2001     

Plasma surface modification of poly(phenylene sulfide) films for copper metallization

Poly(phenylene sulfide) (PPS) films were modified by Ar, O₂, N₂ and NH₃ plasmas in order to improve their adhesion to copper metal. All four plasmas modified the PPS film surfaces, but the NH₃ plasma modification was the most effective in improving adhesion. The NH₃ plasma modification brought about large changes in the surface topography and chemical composition of the PPS film surfaces. The peel strength for the Cu/plasma-modified PPS film systems increased linearly with increasing surface roughness, R _a or R _rms, of the PPS film. The plasma modification also led to considerable changes in the chemical composition of the PPS film surfaces. A large fraction of phenylene units and a small fraction of sulfide groups in the PPS film surfaces were oxidized during the plasma modification process. Nitrogen functional groups also were formed on the PPS film surfaces. The NH₃ plasma modification formed S—H groups on the PPS film surfaces by reduction of S—C groups in the PPS film. Not only the mechanical interlocking effect but also the interaction of the S—H groups with the copper metal may contribute to the adhesion of the Cu/PPS film systems.     

Surface modification of poly(vinylidene fluoride) film by remote Ar, H2, and O2 plasmas

The surface modification of poly(vinylidene fluoride) (PVDF) film induced by remote Ar, H₂, and O₂ plasmas have been investigated using contact angle measurement, X-ray photoelectron spectroscopy, and scanning probe microscope. The contact angle of water shows an improvement in the PVDF surface wettability during short plasma exposure time. Three remote plasmas treated PVDF sheet surfaces occurred dehydrofluorination and oxidation reactions simultaneously. Remote hydrogen plasma was the most effective in defluorination reactions and remote oxygen plasma was unfavorable to abstract fluorine atoms.     

Surface and Interfacial Studies of Plasma-Modified Composite Surfaces

Model epoxy and bismaleimide compounds in thin film form were used to simulate epoxy and bismaleimide composite surfaces, in order to study compositional changes and interfacial reactions induced by oxygen plasma treatment. X-ray photoelectron spectroscopy (XPS) and infrared reflection-absorption spectroscopy (IR-RAS) were used to probe chemical changes which occurred. XPS and IR-RAS were found to be complementary techniques in determining the nature of functional groups incorporated into surfaces by plasma treatment. IR-RAS analysis of the model surfaces following exposure to a liquid epoxy resin revealed that while adsorption of the liquid epoxy occurred on both plasma-treated and nonplasma-treated surfaces, the oxygen plasma-treated surface alone was capable of initiating ring-opening reactions in the epoxy. However, this effect was not observed unless immediate contact was made between the plasma-treated surface and the liquid epoxy resin, illustrating the short-lived reactivity of the functional groups on the plasma-treated surface.     

Reinforced soy protein isolate–based bionanocomposites with halloysite nanotubes via mussel‐inspired dopamine and polylysine codeposition

Fully renewable soy protein isolate (SPI)–based film with rigid strength and sufficient water resistance is difficult to attain. In this study, the mussel‐inspired surface chemistry of ?‐poly‐L‐lysine (?‐PL)/dopamine was exploited for codeposition onto halloysite nanotubes (HNTs) to engineer a multinetwork of HNT/SPI bionanocomposite films via physicochemical bonds. A series of ?‐PL/dopamine aqueous solutions at different concentration ratios were employed. The ?‐PL with abundant cationic amine groups could prevent the overoxidation of dopamine on HNT surfaces, thus maintaining sufficient free catechol groups for highly active reactions that improve the biphase interfacial adhesion. Moreover, HNTs surface entangled by ?‐PL chains could be more compatible with peptides. This codeposition of ?‐PL/dopamine on HNT (DLHNT) surfaces was analyzed by X‐ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, X‐ray diffraction, and thermogravimetric analysis. Compared to the control SPI film, the tensile strength of the nanocomposite film (DLHNTs0.5/SPI) was increased from 5.9 MPa to 8.25 MPa, the Young's modulus was improved by 166.4%, and the moisture absorption was reduced to 56.1% (87.2% of the control). In summary, a facile and mild bioinspired surface chemistry of ?‐PL/dopamine codeposition onto HNT surfaces was performed to prepare SPI‐based nanocomposite films with improved interfacial adhesion and benign compatibility. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46197.     

Surface modification of aromatic polyamide film by remote oxygen plasma

Surface modification of poly(p-phenylene terephthalamide) (PPTA) film by a remote oxygen plasma treatment has been investigated from a viewpoint of comparison with a direct oxygen plasma treatment. We call the modification procedure in a space far away from the oxygen plasma zone “the remote oxygen plasma treatment,” and the modification procedure in a space just in the oxygen plasma zone (a conventional oxygen plasma treatment) “the direct oxygen plasma treatment.” In a space far away from the plasma zone, oxygen radicals rather than electrons and oxygen ions are predominant, and the PPTA film can be modified by the remote oxygen plasma treatment into a hydrophilic surface without heavy degradation of the PPTA film. The PPTA film surfaces modified by the remote oxygen plasma treatment were analyzed with contact angle measurement, scanning microscopy, atomic force microscopy, and X-ray photoelectron spectroscopy. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 831–840, 1997     

Surface modification of PET films by pulsed argon plasma

The rf power was modulated (discharge on‐time of 10 μs and discharge off‐time of 50–500 μs), for pulsed argon (Ar) and oxygen (O₂) plasmas used to irradiate PET film surfaces to modify the film surfaces. From data regarding the contact angle for the modified PET film surfaces and chemical analyses with XPS, effects of the rf power modulation on the surface modification are discussed. The pulsed Ar and O₂ plasmas are effective in modification of the PET film surface. There is no difference in the contact angle between the pulsed plasma and the continuous plasma. Furthermore, the pulsed Ar plasma is advantageous in formation of hydroxyl groups on the PET film surfaces. The rf power modulation has a possibility to modify into peculiar surfaces. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2845–2852, 2002     

The effect of TiO2 morphology on the surface modification of poly (ethylene terephthalate) for electroless plating

In this study, a surface modification of the poly (ethylene terephthalate) (PET) film using TiO₂ photocatalytic treatment was investigated. In order to enhance the adhesion strength between the PET film and the electroless copper film, the effects of TiO₂ crystal forms, TiO₂ particle sizes, and TiO₂ content, as well as treatment condition, upon the surface contact angle, surface characterization, and adhesion strength were investigated. Anatase TiO₂ with a particle size of 5 nm had a high catalytic activity and dispersibility in aqueous solution. After the optimal photocatalytic treatment, the surface contact angle of the PET film decreased from 84.4° to 19.8°, and the surface roughness of the PET film increased from 36 to 117 nm. The adhesion strength between the PET film and the electroless copper film reached 0.89?KN?m^?1. X-ray photoelectron spectroscopy analyses indicated the carbonyl group was formed on the PET surface after photocatalytic treatment, and the surface hydrophilicity was improved. Consequently, TiO₂ photocatalytic treatment is an environmentally friendly and effective method for the surface modification of the PET film.     

聚乳酸的改性及应用进展

综述了近几年聚乳酸生物降解材料的改性进展。改性方法分为化学改性和物理改性。化学改性包括共聚、交联、表面修饰等，主要是通过改变聚合物大分子或表面结构改善其脆性、疏水性及降解速率等；物理改性主要是通过共混、增塑及纤维复合等方法实现对聚乳酸的改进。     

Water vapor solubility of poly(lactic acid) films modified the surface by vacuum ultraviolet irradiation

Surface modification of poly(lactic acid) (PLA) film is performed via 172 nm excimer lamp irradiation. Effects on water vapor solubility and physical properties via vacuum ultraviolet (VUV) irradiation are studied systematically. After VUV irradiation, water vapor solubility increases approximately 11–43% in the low‐pressure region and approximately 20–38% in the high‐pressure region as surface hydrophilicity increased. The increase is attributed to hydrogen bonding with the carboxyl groups because of VUV radiation. The modified layer is significantly swelling after water vapor sorption. The hydrophilic layer forms a thickness of 2–3 μm from the irradiated surface via VUV radiation, but no changes are observed inside the irradiated film. Therefore, PLA film solubility after irradiation is enhanced by hydrophilicity and the swelling effect of the surface. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42200.     

Surface modification of polyimide film by coupling reaction for copper metallization

In this study, Upilex-S [poly(biphenyl dianhydride-p-phenylene diamine)], one of polyimide films, was modified by coupling reactions with N,N-carbonyldiimidazole (CDI) to increase adhesion to copper for flexible copper clad laminate (FCCL). Imidazole groups show strong interaction with copper metal to make charge transfer complexes. Because polyimide film did not have active site with coupling agent, the film surfaces were modified by aqueous KOH solutions and reacted with dilute HCl solutions.Surface modified Upilex-S was analyzed by X-ray photoelectron spectroscopy (XPS) to examine the surface chemical composition and film morphology and investigated by scanning electron microscopy (SEM) and atomic force microscopy (AFM). Changes in the wettability were evaluated by measuring contact angle with the sessile drop method. After deposition of copper on surface modified Upilx-S, the adhesion strength of the copper/polyimide system was measured by a 90° peel test using the Instron tensile strength tester. The peel strength of the copper/polyimide system increased from 0.25 to 0.86 kg_f/cm by surface modification. This result confirmed that the CDI coupling reaction is an effective treatment method for the improvement of the adhesion property between copper metal and polyimide film.