Lamination of conductive polypyrrole films to poly(tetrafluoroethylene) films via interfacial graft copolymerization

A simple technique for the lamination of a conductive polymer film to an inert dielectric polymer film was demonstrated. The electrochemically synthesized and p‐toluenesulfonic acid‐doped polypyrrole (PPY) film was laminated simultaneously to the argon plasma‐pretreated PTFE film during the thermally induced graft copolymerization of the PTFE surface with a functional monomer. The graft copolymerization was carried out using glycidyl methacrylate (GMA) monomer containing 20% v/v hexamethyldiamine (HMDA) and in the absence of any polymerization initiator. Thermally induced graft copolymerization of the GMA monomer on the PPY surface was minimal. The lap shear and T‐peel adhesion strengths of the laminates were found to be dependent on the GMA graft concentration on the PTFE surface, which, in turn, was affected by the plasma pretreatment time of the film. To increase the GMA graft concentration for the enhancement of adhesion strength, the plasma‐pretreated PTFE surfaces were premodified via UV‐induced graft copolymerization with GMA prior to the simultaneous thermal graft copolymerization and lamination process. The modified surfaces and interfaces were characterized by X‐ray photoelectron spectroscopy (XPS). Through XPS measurements of the delaminated surfaces, it was found that the PPY/PTFE laminates failed predominantly by cohesive failure inside the PTFE substrate. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 716–727, 2001     

Surface structures and adhesion enhancement of poly(tetrafluoroethylene) films after modification by graft copolymerization with glycidyl methacrylate

Surface modifications of Ar plasma-pretreated poly(tetrafluoroethylene) (PTFE) film were carried out via near-UV light-induced graft copolymerization with glycidyl methacrylate (GMA). The structure and chemical composition of the copolymer surface and interface were studied by angle-resolved X-ray photoelectron spectroscopy (XPS). For PTFE substrate with a substantial amount of grafting, the grafted GMA polymer penetrates or becomes partially submerged beneath a thin surface layer of dense substrate chains to form a stratified surface microstructure. The concentration of the surface-grafted GMA polymer increases with the plasma pretreatment time, the near-UV light illumination time, and the monomer concentration. The GMA graft copolymerized PTFE surfaces adhere strongly to one another when brought into direct contact and cured (i) in the presence of a diamine alone or (ii) in the presence of an epoxy adhesive (epoxy resin plus diamine curing agent). In the presence of diamine alone, failure occurs in the interfacial region. For epoxy adhesive-promoted adhesion, the failure mode is cohesive, i.e. it takes place in the bulk of one of the delaminated PTFE films. The lap shear strengths in both cases increase with the amount of surface-grafted epoxide polymer. The development of the adhesion strength depends on the concentration of the surface graft, the microstructure of the graft copolymerized PTFE surface, the interfacial reactions, and the nature of the bonding agent.     

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     

Surface modification of polytetrafluoroethylene films by plasma pretreatment and graft copolymerization to improve their adhesion to bismaleimide

BACKGROUND: Polytetrafluoroethylene (PTFE) is utilized in many engineering applications, but its poor wettability and adhesion properties with other materials have limited its use. The study reported was aimed at achieving surface modification of PTFE films by radiofrequency NH₃ and N₂ plasma treatment, followed by graft copolymerization, in order to improve the interfacial adhesion of PTFE and bismaleimide. RESULTS: X‐ray photoelectron spectroscopy results showed that a short‐time plasma treatment had a distinct defluorination effect and led to nitrogen functional group formation. The nitrogen chemical bonding form was different for NH₃ and N₂ plasma treatments. Under the same experimental conditions, the NH₃ plasma exhibited a better etching effect than did the N₂ plasma. Contact angle measurement showed an improvement in both surface energy and wettabliity by short‐time plasma treatment. The concentration of the surface‐grafted bismaleimide on PTFE increased after the plasma pretreatment. The lap shear strength between PTFE and bismaleimide increased significantly after surface modification. CONCLUSION: This study found that plasma treatment caused changes in surface chemistry, thus leading to an increase of the wettability of PTFE surfaces. Hence, the adhesion properties of PTFE with bismaleimide were significantly improved. Copyright © 2008 Society of Chemical Industry     

Surface passivation of nylon‐6,6 films by graft copolymerization for reduction of moisture sorption

To improve the moisture sorption property of nylon‐6,6 film, ally pentafluorobenzene (APFB) was incorporated on the argon plasma‐pretreated nylon film by UV or thermally induced surface graft copolymerzation. The plasma pretreatment introduced peroxides that were degraded into radicals to initiate the graft copolymerization of APFB on the nylon surface. The modified surfaces were characterized by X‐ray photoelectron spectroscopy (XPS) and contact angle measurement. The moisture sorption was assessed by the coulometric test method. The efficiency of surface graft copolymerization was affected by plasma pretreatment time of the nylon substrate, as well as by the UV or thermal graft copolymerization time. The UV graft‐copolymerized nylon film exhibited a significantly lower extent of moisture sorption when compared to that of the pristine films, even at low graft concentration. However, the moisture sorption behavior for the thermally graft copolymerized films was similar to that of the pristine films. Contact angle and XPS measurements suggested that the reduction in moisture sorption for the UV graft‐copolymerized nylon‐6,6 film was attributable to the fact that the hydrophobic polymer layer was formed on the nylon surface, and the hydrophobic layer of an appropriate thickness could serve as an effective barrier to moisture. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1366–1373, 2000     

Surface Graft Copolymerization of Poly(vinylidene fluoride) Film with Simultaneous Lamination to Copper Foil

Surface thermal graft copolymerization with concurrent lamination was carried out between an Ar plasma pretreated poly(vinyh'dene fluoride) (PVDF) film and a copper foil in the presence of a small quantity of a N-containing monomer, such as 4-vinyl pyridine (4-VPN) and acryloyl morpholine (ACMO), under atmospheric conditions and in the complete absence of an added polymerization initiator and system degassing. The adhesion strength, as reported by T-peel strength, was dependent on the argon plasma pretreatment time of the PVDF film, the thermal lamination temperature and the type of monomer. An optimum T-peel adhesion of about 10 N/cm was readily achieved in the Cu/PVDF laminate for grafting and lamination carried out in the presence of 4-VPN. A lower adhesion strength was obtained using ACMO and other N-containing monomers. The chemical compositions of the graft copolymerized and delaminated sample surfaces were studied by X-ray photoelectron spectroscopy (XPS). The failure mode of the Cu/4-VPN/PVDF assembly was a combined adhesional and cohesive failure. The strong adhesion between the Cu foil and the PVDF film arises from the strong charge transfer interaction between Cu and the pyridine ring, as well as the fact that the graft chains are covalently tethered on the PVDF films surfaces as a result of surface graft copolymerization.     

Thermal imidization of poly(amic acid) precursors on surface-modified poly(tetrafluoroethylene) films via graft copolymerization with glycidyl methacrylate

A novel method for preparing composites of polyimides (PI) laminated to poly(tetrafluoroethylene) (PTFE) films is reported. PI/PTFE composites were developed through thermal imidization of poly(amic acid) (PAA) precursors on surface-modified PTFE films. Surface modification of PTFE films was carried out via Ar plasma pretreatment of the films, followed by UV-induced graft copolymerization with glycidyl methacrylate (GMA). The surface composition and topography of the graft copolymerized PTFE films and the delaminated PI and PTFE surfaces were characterized by X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM), respectively. The adhesion strengths of the PI (imidized PAA) on the GMA graft copolymerized PTFE films were evaluated as a function of various thermal imidization schedules. The adhesion reliability of the PI/PTFE composites was tested by a series of hydrothermal cycles. The development of strong Tpeel adhesion strengths of about 8 N/cm with excellent reliability for the PI/PTFE composites was attributable to the synergistic effect of coupling the curing of the epoxide functional groups of the grafted GMA chains with the imidization process of the PAA and the fact that the GMA chains were covalently tethered onto the PTFE surface. The PI/PTFE composites delaminated via cohesive failure inside the PTFE substrates. The delaminated PI film with a covalently adhered 'rough' PTFE surface layer exhibited a water contact angle as high as 140°.     

Adhesion enhancement of thermally evaporated aluminum to surface graft copolymerized poly(tetrafluoroethylene) film

Surface modifications of Ar plasma-pretreated poly(tetrafluoroethylene) (PTFE) film via UV-induced graft copolymerization with glycidyl methacrylate (GMA) and 1-vinylimidazole (VIDz) were carried out to improve the adhesion with evaporated aluminum metal. The surface compositions of the graft copolymerized PTFE films were studied by X-ray photoelectron spectroscopy (XPS). The adhesion strength of the evaporated aluminum to the surface graft copolymerized PTFE film was affected by the type of monomer used for graft copolymerization, the graft concentration, the plasma post-treatment of the graft copolymerized PTFE surface prior to metallization, and the extent of thermal treatment after metallization. The optimum T-peel adhesion strengths of the Al/PTFE laminates were in excess of 10 and 5 N/cm, respectively, for the GMA and VIDz graft copolymerized PTFE films. These adhesion strengths are significantly higher than those obtained between the evaporated aluminum and the pristine or plasma-pretreated PTFE film. The mechanism of adhesion enhancement and the failure of the metal-polymer assembly were also investigated. It was observed that the failure occurred within the PTFE film. The strong adhesion between Al and PTFE arises from the charge-transfer interaction between the Al atom and the epoxide moiety of the grafted GMA polymer, as well as from the fact that the graft chains are covalently tethered on the PTFE film surface as a result of the grafting process.     

羧甲基甲壳素与丙烯酰胺接枝聚合反应研究

制备了羧甲基甲壳素接枝丙烯酰胺共聚物,讨论了反映温度、时间、引发剂用量、溶剂用量、单体用量对接枝反应的影响。最佳反应条件为：羧甲基甲壳素0．4g,溶济水50mL,引发剂60mg,单体1．6g,反应温度50℃,反应时间3．0h。     

Radiation induced graft copolymerization of vinyl monomers and their binary mixture onto rayon fibre

Ethyl acrylate (EA), Vinyl imidazole (VI), and their binary mixture have been copolymerized onto rayon in aqueous medium by mutual method using γ-radiation. The graft yield has been determined as a function of different reaction parameters such as total dose, concentration of vinyl monomers, and amount of water. Effect of surfactant (1-octane sulfonic acid, sodium salt) has been studied on the percentage of grafting of EA, VI, and (EA + VI). A plausible mechanism has been suggested to explain the observed behavior of the surfactant on grafting. Water retention and moisture regain of the grafted film was determined at appropriate relative humidity. The graft copolymers have been characterized by IR spectroscopy and scanning electron microscopic methods. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Surface Modification of Poly(Tetrafluoroethylene) Films by Graft Copolymerization for Adhesion Improvement with Sputtered In-Sn Oxides

Surface modification of Ar plasma-pretreated poly(tetrafluoroethylene) (PTFE) films was carried out via UV-induced graft Copolymerization with glycidyl methacrylate (GMA), acrylamide (AAm) and hydroxylethylacrylate (HEA) to improve the adhesion strength with sputtered indium-tin-oxide (ITO). The surface compositions of the graftcopolymerized PTFE films were studied by X-ray photoelectron spectroscopy (XPS). The graft yield increases with increasing monomer concentration and Ar plasma pre-treatment time of the PTFE films. The T-peel adhesion strength was affected by the type of monomer used for graft Copolymerization, the graft concentration, and the thermal post-treatment after ITO deposition. A double graft-copolymerization process, which involved initially the graft copolymeri/ation with AAm or HEA, followed by graft Copolymerization with GMA. was also employed to enhance the adhesion of sputtered ITO to PTFE. T-peel adhesion strengths in excess of 8 N cm were achieved in the ITO graft-modified PTFE laminates. The adhesion failure of the ITO/PTFE laminates in T-peel tests was found to occur inside the PTFE films. The electrical resistance of ITO on all graft-modified PTFE surfaces before and after thermal post-treatment remained conslant at about 30 Ω square, suggesting that the graft layer did not have any significant effect or. the electrical properties of the deposited ITO.     

Polymer-based metal adsorbents via graft copolymerization of polyvinyl alcohol with diaminomaleonitrile: A green chemistry approach

Synthesis, characterization, and amidoximation of diaminomaleonitrile-functionalized polyvinyl alcohol (PVA) grafts were studied. Ceric ammonium nitrate (CAN) was used as an initiator in an aqueous nitric acid medium under N₂ atmosphere. Optimum conditions for grafting were as follows: monomer concentration [DAMN] = 1.4M, [CAN] = 16 × 10⁻² mol/L, T = 50°C, and t = 2 h. Water uptake of the PVA graft films increased with the increase of grafting yield. The imparted cyano group of the grafted PVA polymer chains (with degree of grafting up to 136%) was converted into amidoxime group by the reaction with hydroxylamine hydrochloride. The grafted polymers were characterized by FTIR spectroscopy, differential scanning calorimetry, and thermal gravimetric analysis. The grafted PVA films are more thermally stable than the ungrafted PVA membrane, because the grafted membrane showed a single degradation pattern despite having two components. A decrease in T_g values is observed as the grafting yield of copolymers increases indicating the incorporation of polydiaminomaleonitrile chains in amorphous copolymers with higher thermal stability. The prepared amidoximated DAMN136-g-PVA was investigated for its properties in removing heavy toxic metals, such as Pb²⁺, Cd²⁺, Zn²⁺, Fe³⁺, Cu²⁺, Ni²⁺, and Co²⁺ from water. The amidoximated film is characterized by a considerably greater binding ability with respect to heavy metals. The nature of the metal ion also has great importance in the amount binding to the polymeric material. The kinetics of the sorption/desorption process for Co²⁺, Ni²⁺, and Zn²⁺ were investigated. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Role and relevance of polarity and hindrance of vinyl monomers in graft copolymerization onto potato starch

The graft copolymerization of the vinyl monomers that were prepared by reactions of methyl acrylate and 4‐aminoazobenzene derivatives, such as 4‐aminoazobenzene, 4‐amino‐4′‐methyl azobenzene, 4‐amino‐4′‐nitro azobenzene, and 4‐amino‐3′,5′‐dinitro azobenzene, onto potato starch were carried out by the initiation of potassium persulfate. The evidence of grafted copolymers was investigated by using FTIR spectroscopy and acid hydrolysis technique. The relationship between grafting efficiency and monomer structure as well as polarity was studied. The experimental results showed that the graft copolymerization is independent of the polarity of the vinyl monomers and that the structures of monomers exhibit a marked influence on the graft copolymerization, namely, the larger the substitute is, the lower the grafting efficiency will be. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 896–899, 2002     

Platelet adhesion on a polyurethane surface grafted with a zwitterionic monomer of sulfobetaine via a Jeffamine spacer

A possible approach to improve the blood compatibility of poly(ether urethane)s (PU) involves the covalent attachment of key molecules on its surface. The purpose of the present study was to design and synthesise a novel non‐thrombogenic biomaterial by modifying the surface of the PU with a zwitterionic monomer of sulfobetaine via a Jeffamine spacer. In this study, sulfobetaine was grafted onto a PU surface through the following reaction steps: (1) The PU surface was activated with hexamethylene diisocyanate (HDI) in toluene at 50 °C in the presence of di‐n‐butyltin dilaurate (DBTDL) as a catalyst. The extent of the reaction was measured by ATR‐FTIR spectra; a maximum number of free NCO groups was obtained after a reaction time of 90 min. (2) One cap of Jeffamine was reacted with isocyanate groups bound on the surface, so Jeffamine was introduced. (3) The PU surface terminated by Jeffamine was recoupled with isocyanate groups by HDI. (4) The hydroxyl groups of 4‐dimethylamino‐1‐butanol (DMAB) or 2‐dimethylaminoethanol (DMAE) were allowed to react with the isocyanate groups capped on Jeffamine. (5) Sulfobetaines were constructed on the surface through the ring‐opening reaction between tertiary amine and 1,3‐propanesultone (PS). It was confirmed by ATR‐FTIR and XPS that the grafted surfaces were composed of sulfobetaine. The results of the contact‐angle measurements and water absorption showed that they were strongly hydrophilic. The results of this platelet adhesion experiment as a preliminary test showed that PU grafted with sulfobetaine has good blood compatibility featured by the low platelet adhesion. Copyright © 2004 Society of Chemical Industry     

羧甲基甲壳素接枝丙烯酸丁酯共聚物的制备及水溶性

制备了羧甲基甲壳素接枝丙烯酸丁酯共聚物,讨论了反应温度、时间、引发剂用量、溶剂用量、单体用量对接枝反应的影响。最佳反应条件为:羧甲基甲壳素0.3g,溶剂水30mL,引发剂50mg,单体1.2g,反应温度60℃,反应时间3.5h。用红外光谱对接枝产物进行了表征,考察了不同接枝率的产物在10种常见溶剂中的溶解性,结果表明不同接枝率的接枝产物都有水溶性。     

The Effects of High Contact Pressures and Temperatures on the Adhesion of Amorphous Polystyrene to Borosilicate (Pyrex) Glass

The effects on adhesive joint strength of four pressure-temperature histories, each over the range of pressures from 1 to 1500 bars and temperatures from 25 to 200°C, has been investigated with polystyrene-Pyrex glass butt joint specimens. The various pressure-temperature histories were designed to show the separate effects of permanent stresses, transient stresses and interfacial contact on joint strength. This strength increased as the number of stress concentration loci were reduced through application of high contact pressures on the melt. However, isobaric solidification of the polymer led to a maximum in fracture stress as a function of applied molding pressure because of the existence of a critical pressure at which permanent thermal stresses were minimized. A series of isothermal compression-decompression molding operations showed fracture stress to increase with interfacial contact area until maximum contact was achieved. A 100 per cent gain in bond strength was realized when interfacial contact was maximized concurrent with minimizing both the permanent and transient stresses which normally develop when the adhesive joint is formed. Microscopic observations of interfaces in both non-fractured and fractured butt joints established a qualitative relationship between debonding, the mechanism of fracture, and joint strength.     

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     

Low-temperature graft copolymerization of 1-vinyl imidazole on low-density polyethylene films with simultaneous lamination of copper foils

Surface modification of argon plasma-pretreated low-density polyethylene (LDPE) films by graft copolymerization with 1-vinyl imidazole (VIDz) and with concurrent lamination of copper foils at room temperature and at an elevated temperature were carried out. The adhesion strengths were reported as lap shear adhesion strengths and T-peel strengths. The surfaces of the graft copolymerized films and the mechanically delaminated LDPE and Cu surfaces were characterized by X-ray photoelectron spectroscopy (XPS). It was found that plasma pretreatment of LDPE alone, and in the absence of VIDz, could give rise to strong lap shear adhesion between the polymer and copper. Significant T-peel strengths, however, were obtained only for LDPE/Cu laminates obtained from the simultaneous graft copolymerization and lamination technique. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 1977–1983, 1998     

Chemically induced graft copolymerization of vinyl monomers onto cotton fibers

We investigated the chemically induced graft copolymerizations of acrylic acid (AA), acrylamide, crotonic acid, and itaconic acid (IA) onto cotton fibers. Benzoyl peroxide was used as an initiator. The effects of grafting temperature, grafting time, and monomer and initiator concentrations on the grafting yields were studied, and optimum grafting conditions were determined for the sample material. The maximum grafting yield value obtained was 23.8% for AA. Swelling tests, Fourier transform infrared spectroscopy, and scanning electron microscopy analyses of grafted and ungrafted fibers were also performed to characterize fiber properties. IA‐grafted fibers were measured as the most swollen fibers, with a swelling value of 510%. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2343–2347, 2006     

Cation exchange membranes by radiation‐induced graft copolymerization of styrene onto PFA copolymer films. IV. Morphological investigations using X‐ray photoelectron spectroscopy

Morphological investigations of poly(tetrafluoroethylene‐co‐perfluorovinyl ether) (PFA)‐g‐polystyrene sulfonic acid membranes prepared by radiation‐induced graft copolymerization of styrene onto PFA films followed by sulfonation were performed by X‐ray photoelectron spectroscopy. The analyzed materials included grafted film and sulfonated membrane samples having various degrees of grafting. Original PFA film was used as a reference material. The results of the X‐ray photoelectron spectral analysis show that PFA film undergoes changes in terms of chemical compositions and binding energies of its basic elemental components under the influence of membrane preparation procedure, i.e., grafting and sulfonation. The chemical compositions of the surfaces of the membranes were found to be dependent on the degree of grafting unlike the binding energies of their elemental components (C, F, O, and S), which were found to be independent of the degree of grafting. The atomic ratio of F/C was found to decrease drastically with the increase in the degree of grafting and the membranes were found to have almost pure hydrocarbon structure at the layers close to their surfaces where degradation is suggested to be concentrated. The results of these investigations suggest that the morphology of the membranes plays an important role in the chemical degradation of the membranes. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2455–2463, 2000