Surface modification of polyethylene terephthalate film by CO2 laser‐induced graft copolymerization of acrylamide

Graft copolymerization of acrylamide onto polyethylene terephthalate (PET) using a CO₂ pulsed laser was performed to improve water wettability. After laser irradiation in air, the films were placed in the aqueous solution of monomer and then heated to decompose peroxides formed onto the irradiated PET film. Peroxide density was determined spectrophotometrically by means of the iodide method. The grafted PET surfaces were characterized by attenuated total reflectance infrared spectroscopy, scanning electron microscopy, and contact angle measurements. The electron micrographs showed that the grafting changed the surface morphology of the PET film, which is consistent with the infrared spectra of the grafted films. To evaluate the surface hydrophilicity, water drop contact angle was determined. The contact angle decreased as a result of graft polymerization. It was also found that the hydrophilicity is related to the surface morphology and grafting level. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 401–407, 2000     

Surface graft copolymerization of 2‐hydroxyethyl methacrylate onto low‐density polyethylene film through corona discharge in air

The corona discharge technique was explored as a means of forming chemically active sites on a low‐density polyethylene (LDPE) film surface. The active species thus prepared at atmospheric pressure in air was exploited to subsequently induce copolymerization of 2‐hydroxyethyl methacrylate (HEMA) onto LDPE film in aqueous solution. The results showed that with the corona discharge voltage, reaction temperature, and inhibitor concentration in the reaction solution the grafting degree increased to a maximum and then decreased. As the corona discharge time, reaction time, and HEMA concentration in the reaction solution increased, the grafting degree increased. With reaction conditions of a 5 vol % HEMA concentration, 50°C copolymerization temperature, and a 2.0‐h reaction time, the degree of grafting of the LDPE film reached a high value of 158.0 μg/cm² after treatment for 72 s with a 15‐kV voltage at 50 Hz. Some characteristic peaks of the grafted LDPE came into view at 1719 cm^?1 on attenuated total reflectance IR spectra (C?O in ester groups) and at 531 eV on electron spectroscopy for chemical analysis (ESCA) spectra (O_1s). The C_1s core level ESCA spectrum of HEMA‐grafted LDPE showed two strong peaks at ～286.6 eV (? C ? O? from hydroxyl groups and ester groups) and ～289.1 eV (O?C ? O? from ester groups), and the C atom ratio in the ? C? O? groups and O?C? O groups was 2:1. The hydrophilicity of the grafted LDPE film was remarkably improved compared to that of the ungrafted LDPE film. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2881–2887, 2001     

Functionalization of industrial polypropylene films via the swift‐heavy‐ion‐induced grafting of glycidyl methacrylate

Swift‐silver‐ion irradiation was explored as a means of forming chemically active sites on the surface of biaxially oriented polypropylene films. The active species, formed in air, was used to induce the graft copolymerization of glycidyl methacrylate in an aqueous solution. The surface structure, crystallinity, morphology, and hydrophilicity of the grafted samples were characterized with Fourier transform infrared, UV, wide‐angle X‐ray diffraction, scanning electron microscopy, and contact‐angle measurements. Glycidyl methacrylate could be grafted onto biaxially oriented polypropylene after swift‐heavy‐ion irradiation without an additional initiator. The contact angle of the modified films decreased with the grafting percentage of glycidyl methacrylate on the polypropylene. The swift silver ions induced significant grafting only in small regions (i.e., the latent tracks) of the polymer. Furthermore, as the fluence of swift heavy ions increased beyond an optimum value, the overlapping of the latent tracks reduced the grafting yield. The observed findings could be very useful in developing an initiator‐free grafting system. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Surface structure of low density polyethylene films grafted with acrylic acid using corona discharge

Chemical composition, morphology, and crystalline structure of low density polyethylene (LDPE) films surface grafted with acrylic acid (AA) using corona discharge were studied by attenuated total reflection infrared (ATR-IR), electron spectroscopy for chemical analysis (ESCA), scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and wide angle X-ray diffraction (WAXD) techniques. The grafted film surface is covered with grafted chains. After grafting for 3.0 h in 20% aqueous solution of AA, the depth of the grafted layer is more than 10 nm. A grain structure was observed on the grafted surfaces which was probably caused by the isolated dispersion of active sites generated by corona discharge, and these active sites initiated the graft copolymerization. However, surfaces of grafted films were smoother than that of ungrafted ones. DSC curves of grafted films show a small peak at about 100°C due to vaporization of adsorbed water. The longer the graft copolymerization time, i.e. the higher the graft degree of AA on LDPE, the higher the amount of adsorbed water. The position of each peak in WAXD patterns, crystal axial length, crystal plane distance and crystal grain size remain almost unchanged during the graft copolymerization time of 2.0 h. However, when the graft copolymerization time reaches 3.0 h, twin peaks at about 21.4° and 22.0° are observed, indicating that a different crystal form is formed at longer copolymerization time, i.e. at a higher graft degree.     

Radiation‐induced graft copolymerization of MMA monomer onto UHMWPE: Adhesion improvement

Graft copolymerization of methyl methacrylate monomer onto ultra high molecular weight polyethylene (UHMWPE) and acid‐etched UHMWPE was conducted using preirradiation method in air in the presence of a Mohr salt and sulfuric acid to improve adhesion to the bone cement. The grafted samples were characterized by Fourier transform infrared (FTIR) spectroscopy, gravimetric method, goniometry, and interfacial bonding strength measurements. The FTIR results showed the presence of ether, carbonyl, and hydroxyl groups for grafted films. The gravimetric results showed that the chromic acid etching and graft copolymerization had a synergetic effect so, the irradiated, then chromic acid etched at room temperature and grafted sample (Rad etch25) had the highest grafting degree. The interfacial bonding strength between UHMWPE and poly methyl methacrylate bone cement was considerably improved by graft copolymerization and chromic acid etching. The surface morphology was studied by scanning electron microscopy. The substitution of polar groups into the backbone of UHMWPE by chromic acid etching and graft copolymerization changed its contact angles with water and methylene iodide and increased its surface energy, as evidenced by contact angle measurements. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Platelet adhesion on laser‐induced acrylic acid–grafted polyethylene terephthalate

To improve blood compatibility, acrylic acid (AAc) was grafted onto a polyethylene terephtalate (PET) film surface using lasers. The PET surface was irradiated with a CO₂ pulsed laser, and then graft copolymerization was carried out in an aqueous solution of AAc in the presence of Mohr's salt. Different techniques such as attenuated total reflectance Fourier transform infrared spectroscopy (ATR‐FTIR), scanning electron microscopy (SEM), and contact angle measurements were used to characterize the modified PET surface. The ATR‐FTIR spectra confirmed the creation of new functional groups on the PET surface, and contact angle measurements revealed that the hydrophilicity of the PET surface increased as a result of the AAc graft polymerization. The electron micrographs showed that the grafting changed the surface morphology of the PET film. To evaluate the blood compatibility in vitro, the number of platelets adhering to the modified PET surface was determined using lactate dehydrogenase (LDH) activity measurement. The data from LDH method indicated that the extent of platelet adherence on the unmodified PET was much higher than that on the AAc grafted PET. The morphology of adhered platelets on the PET surface was investigated by SEM. The results showed that platelet adhesion and activation onto the PET surface was reduced because of AAc graft polymerization. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3191–3196, 2002     

Corona-induced graft polymerization of ethyl acrylate onto cellulose film

Ethyl acrylate was readily grafted from an aqueous solution onto cellophane film previously treated in a corona discharge at atmospheric pressure. The effect was found when the corona treatment was carried out not only in air but also in pure nitrogen. The observed grafting was not promoted but depressed by the presence of ferrous ion, which indicated that peroxide radicals were not initiating the graft. A high grafting efficiency was obtained, and the grafted surface was covered with a smooth uniform layer of polymer.     

Some Effects of Corona Discharge Treatment of Biaxially-Oriented Polypropylene Film

The effects of the unit corona-treatment energy on the contact angle of various liquids, on the surface free energy, on the extent of oxidation of a surface layer, and on the adhesion of acrylic adhesive were studied using a biaxially-oriented polypropylene (BOPP) film. The surface free energy was determined with the van Oss-Chaudhury-Good (VCG) approach as well as with the wettability method. The extent of oxidation of the surface layer of the corona-treated BOPP film was evaluated with X-ray photoelectron spectroscopy. The adhesion strength of joints between the BOPP film and the acrylic adhesive was measured using the 180°-peel test.

In the range of the unit corona-treatment energy up to 1.2 kJ/m², a rapid increase in the surface free energy with the treatment energy is observed. In the range above that value, the surface free energy rises relatively slowly. The extent of oxidation of the surface layer and the adhesion strength of joints between the BOPP film and the acrylic adhesive are approximately in direct proportion to the unit energy of the corona treatment. A five-fold growth of the adhesion strength of the studied joints within the examined range of the treatment energy was found.     

Some Effects of Corona Discharge Treatment of Biaxially-Oriented Polypropylene Film

The effects of the unit corona-treatment energy on the contact angle of various liquids, on the surface free energy, on the extent of oxidation of a surface layer, and on the adhesion of acrylic adhesive were studied using a biaxially-oriented polypropylene (BOPP) film. The surface free energy was determined with the van Oss-Chaudhury-Good (VCG) approach as well as with the wettability method. The extent of oxidation of the surface layer of the corona-treated BOPP film was evaluated with X-ray photoelectron spectroscopy. The adhesion strength of joints between the BOPP film and the acrylic adhesive was measured using the 180°-peel test.

In the range of the unit corona-treatment energy up to 1.2 kJ/m², a rapid increase in the surface free energy with the treatment energy is observed. In the range above that value, the surface free energy rises relatively slowly. The extent of oxidation of the surface layer and the adhesion strength of joints between the BOPP film and the acrylic adhesive are approximately in direct proportion to the unit energy of the corona treatment. A five-fold growth of the adhesion strength of the studied joints within the examined range of the treatment energy was found.     

低温等离子体处理及丙烯酸接枝改性膨化聚四氟乙烯薄膜

采用He等离子体对膨化聚四氟乙烯(ePTFE)薄膜进行表面亲水处理,并引发接枝丙烯酸单体实现持久亲水改性.实验探究了不同等离子处理工艺和接枝工艺对ePTFE薄膜亲水性能的影响,并利用接触角、X光电子能谱(XPS)进行表征.研究结果表明,等离子体预处理后,ePTFE薄膜表面的接触角由145°降至102°;再接枝丙烯酸单体...     

Structure and adhesion properties of linear low‐density polyethylene powders grafted with acrylic acid via ultraviolet light

The structure and adhesion properties of linear low‐density polyethylene (LLDPE) powder grafted with acrylic acid (AA) via ultraviolet light (UV) were studied by Fourier transform infrared spectroscopy (FTIR), electron spectroscopy for chemical analysis (ESCA), scanning electron microscopy (SEM), and water contact angle, peel strength, and graft degree measurements. The results show that the chemically inert LLDPE powder can be graft‐copolymerized with AA via this photografting method. The graft degree increases with the ultraviolet irradiation time. The hydrophilicity of the grafted LLDPE powder and the peel strength of high‐density polyethylene (HDPE)/steel joint with the grafted LLDPE powder used as hot‐melt adhesive are improved considerably, as compared to that with the ungrafted LLDPE powder. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2549–2553, 2006     

Surface modification of polyurethane by plasma-induced graft polymerization of poly(ethylene glycol) methacrylate

A new approach, plasma-induced graft polymerization of poly(ethylene glycol) methacrylate (PEGMA), was used to introduce PEG graft chains with hydroxyl end groups onto a polyurethane (Tecoflex) surface. After argon plasma treatment and subsequent exposure to air, graft polymerization onto Tecoflex films was allowed to proceed in deaerated aqueous solutions of PEGMA at 60°C. The virgin, plasma-treated, and grafted films were characterized comparatively by means of attenuated total reflection infrared spectroscopy, X-ray photoelectron spectroscopy, atomic force microscopy, measurement of contact angle, and protein adsorption. The Tecoflex film undergoes etching during argon plasma treatment, surface oxidation when exposed to air after plasma treatment, and surface restructuring in response to environment upon storage in air. The plasma-induced graft polymerization of PEGMA proved to be successful in introducing PEG graft chains with reactive hydroxyl end groups onto the surface. Grafted films with different surface grafting density of PEG were prepared. Grafted films with higher PEG content exhibit higher hydrophilicity, smoother topography, and lower fibrinogen adsorption. The hydroxyl end groups built onto the surface offer further possibilities of improving its biocompatibility by immobilizing bioactive molecules. © 1996 John Wiley & Sons, Inc.     

Low‐temperature thermal graft copolymerization of 1‐vinyl imidazole on fluorinated polyimide films with simultaneous lamination of copper foils

A simple technique of thermal graft copolymerization of 1‐vinyl imidazole (VIDZ) on pristine and argon plasma pretreated fluorinated polyimide (FPI) films with simultaneous lamination of copper foils was demonstrated. The simultaneous thermal grafting and lamination process was carried out in the temperature range of 80–140°C under atmospheric conditions and in the complete absence of a polymerization initiator. Three different FPI samples of different chemical structures were employed in the present study. An optimum T‐peel strength about 15 N/cm was achieved for the copper/FPI laminate. The adhesion strength, however, decreased with increasing fluorine content in the FPI film. The onset of cohesive failure occurred in the FPI film for assemblies with T‐peel strength greater than 6 N/cm. The T‐peel strengths are reported as a function of the argon plasma pretreatment time of the FPI films and thermal lamination temperature. The adhesion strengths were compared to that of the similarly prepared copper/polyimide (Kapton HN) laminate. Time‐dependent water contact angle (Θ) measurements indicated that the surfaces of FPI films are significantly more hydrophobic and more resistant to water diffusion or hydration than the Kapton HN films. The surface compositions of the pristine FPI films, as well as the delaminated FPI films and copper foils were studied by X‐ray photoelectron spectroscopy. The thickness of the graft VIDZ polymer layer was in the order of 200 nm, as derived from the cross‐sectional view of the scanning electron micrograph. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1478–1489, 1999     

Structure and adhesion properties of acrylic acid grafted high‐density polyethylene powders synthesized by a novel photografting method

A novel photografting, nonvapor, and nonliquid phase living graft polymerization was developed to functionalize high‐density polyethylene (HDPE) powder. The structure and adhesion properties of HDPE powder grafted with acrylic acid (AA) were studied by Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), water contact angle, peel strength, and graft degree measurements. The result shows that HDPE powder can be grafted with AA via the method with a short reaction time and a high monomer conversion. The graft degree increases with the reaction time. Then, the hydrophilicity of the grafted HDPE powder increases also. The peel strength of HPDE/steel joint improved significantly when acrylic acid grafted HPDE powder was used as hot melt adhesive in place of ungrafted HDPE powder. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Surface modification by continuous graft copolymerization. II. Photoinitiated graft copolymerization onto polypropylene film surface

A method for photochemically induced graft copolymerization of acrylamide (AM) onto polypropylene (PP) film surface by a continuous presoaking process under nitrogen atmosphere has been developed. After removal of homopolymer formed, ESCA, UV spectroscopy, contact angle, and adhesion measurements confirmed a photografted layer on the surface of the PP film. The results from spectral analysis and surface properties measurements were consistent. The best grafting yield was obtained for 7–10 s irradiation time. Stabilizing additives in the PP film had no evident effect on the photografting. Benzophenone was an efficient photoinitiator for photografting of PP film with AM. An AM concentration of 0.5–1.3M in the presoaking solution was appropriate in the present case. Acetone was the best solvent among the three alifatic ketones tested (acetone, methylethylketone, and methylpropylketone).     

Surface modification of aromatic polyamide film by plasma graft copolymerization of glycidylmethacrylate for epoxy adhesion

The graft copolymerization of glycidyl methacrylate, GMA, onto poly(p-phenylene terephthalamide), PPTA, film surfaces was investigated to improve adhesion between the PPTA film and epoxy adhesives. The graft copolymerization of GMA was carried out in two steps; a peroxide formation by a combination of argon plasma irradiation and air exposure, and the polymerization reactions of GMA. XPS analyses showed the graft copolymerization of GMA on the PPTA film surface, and only 31–40% of the PPTA film surface was covered with the GMA graft polymers. The graft copolymerization of GMA improved the adhesion between the PPTA film and the epoxy adhesive. The adhesion strength was improved 2.7 times by the graft copolymerization. The failure from the adhesive joint occurred in the epoxy adhesive layer rather than at the interface between the PPTA film and the epoxy adhesive layer. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 1179–1185, 1998     

Surface grafting of polymer onto carbon thin film

The surface grafting of polymers onto carbon thin film deposited on a glass plate was achieved by two methods: the graft polymerization initiated by initiating groups introduced onto the surface; and the trapping of polymer radicals by surface aromatic rings of the thin film. It was found that the radical and cationic graft polymerization of vinyl monomers are initiated by azo and acylium perchlorate groups introduced onto the surface, respectively, and the corresponding polymers are grafted onto the surface: the surface grafting of polymers were confirmed by the contact angle of the surface with water. In addition, the anionic ring-opening alternating copolymerization of epoxides with cyclic acid anhydrides was found to be initiated by potassium carboxylate groups on the carbon thin film to give the corresponding polyester-grafted carbon thin film. On the other hand, polymer radicals formed by the decomposition of azo polymer, such as poly(polydimethylsiloxane-azobiscyanopentanoate) and poly(polyoxyethylene-azobiscyanopentanoate), were successfully trapped by the surface aromatic rings of carbon thin film and polydimethylsiloxane and polyoxyethylene were grafted onto the surface. © 1995 John Wiley & Sons, Inc.     

Surface immobilization of polymer brushes onto porous poly(vinylidene fluoride) membrane by electron beam to improve the hydrophilicity and fouling resistance

Poly(vinylidene fluoride) (PVDF) membrane was pre-irradiated by electron beam, and then poly(ethylene glycol) methyl ether methacrylate (PEGMA) was grafted onto the membrane surface in the aqueous solution. The degree of grafting was significantly influenced by the pH value of the reaction solution. The surface chemical changes were characterized by the Fourier transform infrared attenuated total reflection spectroscopy (FTIR-ATR) and X-ray photoelectron spectroscopy (XPS). Combining with the analysis of the nuclear magnetic resonance proton and carbon spectra (¹H NMR and ¹³C NMR), PEGMA was mainly grafted onto the membrane surface. Morphological changes were characterized by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The porosity and bulk mean pore size changes were determined by a mercury porosimeter. The surface and bulk hydrophilicity were evaluated on the basis of static water contact angle, dynamic water contact angle and the dynamic adsorption process. Furthermore, relative high permeation fluxes of pure water and protein solution were obtained. All these results demonstrate that both hydrophilicity and fouling resistance of the PVDF membrane can be improved by the immobilization of hydrophilic comb-like polymer brushes on the membrane surface.     

SURFACE MODIFICATION OF POLYETHER ETHER KETONE (PEEK) FILMS FOR FLEXIBLE PRINTED CIRCUIT BOARDS

The surface of polyether ether ketone (PEEK) films was modified using plasma treatment, corona, or surface etching to improve their adhesion with regard to glued copper foils and copper layers generated by physical vapor deposition. After the pretreatments, surface chemical analysis was performed by X-ray photoelectron spectroscopy (XPS). The wetting behavior was qualitatively investigated by contact angle measurements. Surface topography was monitored by laser scanning microscopy (LSM). After coating, the adhesion strength of the copper layer was measured by a peel force test. Plasma treatment, corona discharge, or etching lead to a significant increase in adhesion. This increase is caused by a change in surface topography as well as by the incorporation of polar groups into the surface.     

Glow-discharge-induced graft polymerization of acrylic acid onto poly[1-(trimethylsilyl)-1-propyne] film

Graft polymerization of acrylic acid onto poly[1-(trimethylsilyl)-1-propyne] [poly(TMSP)] film was examined. The water contact angle of poly(TMSP) film decreased remarkably from 90 to 15° by plasma treatment, which gradually increased up to 40° after several days. When the film exposed to a glow discharge was heated in an aqueous solution of acrylic acid at 80°C for 24 h, graft polymerization proceeded on the film surface, which was confirmed by ATR-IR and ESCA spectra. Graft polymerization effectively occurred above a threshold temperature (80°C). The water contact angle of the grafted film was about 30°, and did not change with time. In contrast, when a poly(TMSP) film exposed to UV irradiation was heated in an aqueous solution of acrylic acid, graft polymerization took place not only on the film surface but also inside the film.