Surface modification of poly(tetrafluoroethylene) films by plasma polymerization and UV-induced graft copolymerization for adhesion enhancement with electrolessly-deposited copper

Surface modification of H₂ plasma-pretreated poly(tetrafluoroethylene) (PTFE) films, either by plasma polymerization and deposition of GMA, or by UV-induced graft copolymerization with glycidyl methacrylate (GMA), was carried out for adhesion enhancement with the electrolesslydeposited copper. XPS and FTIR results revealed that the epoxide groups in the plasma-polymerized GMA (pp-GMA) layer had been preserved to various extents, depending on the glow discharge conditions. The T-peel adhesion test results showed that the adhesion strengths of the electrolesslydeposited copper on both the pp-GMA modified PTFE (pp-GMA-PTFE) film and the GMA graftcopolymerized PTFE (GMA-g-PTFE) film were much higher than that of the electrolessly-deposited copper on the pristine or the H₂ plasma-treated PTFE film. The high adhesion strength between the electrolessly-deposited copper and the surface-modified PTFE film was attributed to the fact that the plasma-polymerized and the UV graft-copolymerized GMA chains were covalently tethered on the H₂ plasma-pretreated PTFE surface, as well as the fact that these GMA chains were spatially and interactively distributed into the copper matrix.     

Grafting sulfobetaine monomer onto silicone surface to improve haemocompatibility

Silicone rubber has been used as a biomaterial for more than two decades and displays good mechanical and optical properties, but its chemical nature, poor antithrombogenicity, as well as its hydrophobicity, prevents its use in many demanding biomedical applications. In order to provide modified silicone with enhanced haemocompatibility, surface modification techniques were used. Ozonization was used to introduce active peroxide groups onto the silicone film surface and, subsequently, graft polymerization of N,N′‐dimethyl‐N‐methacryloyloxyethyl‐N‐(3‐sulfopropyl) ammonium (DMMSA), a zwitterionic sulfobetaine structure, onto the ozone activated silicone surface was conducted. Surface analysis was accomplished by means of attenuated total reflectance‐Fourier‐transform infrared (ATR‐FTIR), and X‐ray photoelectron spectra (XPS), and scanning electron microscopy (SEM) and contact angle measurement. ATR‐FTIR and XPS investigation confirmed the graft polymerization. The grafted film possessed a relatively hydrophilic surface as indicated by contact angle measurement. The blood compatibility of the grafted films was evaluated by platelet adhesion in platelet‐rich plasma (PRP) and protein adsorption in bovine fibrinogen using silicone film as the reference. No platelet adhesion was observed for the grafted films incubated in PRP for 120 min. The protein adsorption was reduced on the grafted films after incubated in bovine fibrinogen for 120 min. These results confirmed that the improved blood compatibility was obtained by grafting this new zwitterronic sulfobetaine structure onto silicone film. Copyright © 2003 Society of Chemical Industry     

Surface grafting polymerization of vinyl monomers on poly(tetrafluoroethylene) films by plasma treatment

Poly(tetrafluoroethylene) films were surface modified by argon plasma treatment followed by graft polymerization. Peroxidе groups were introduced on the surface of poly(tetrafluoroethylene) films after plasma treatment and the consequent contact with air when the films were taken out of the reactor. Grafting polymerization initiated by the surface peroxide (hydroxide) groups was performed on the poly(tetrafluoroethylene) film surface by using acrylic acid, 4-vinylpyridine and 1-vinylimidazole as monomers. Copolymers were obtained with grafting yield from 0.436 to 0.457 mg/cm² for poly(acrylic acid), from 0.299 to 0.390 mg/cm² for poly(4-vinylpyridine) and from 0.212 to 0.256 mg/cm² for poly(1-vinylimidazole), respectively. The free surface energies of the copolymers were determined. The chemical structures and the copolymer surfaces were characterized by IR, XPS and SEM analyses. High energy resolution X-ray photoelectron spectroscopy (XPS) confirmed the grafting of acrylic acid, 4-vinylpyridine and 1-vinylimidazole. The surface hydrophilicities of modified polytetrafluoroethylene films were significantly enhanced after plasma treatment and grafting modification. It is worth emphasizing that in this work acrylic acid, 4-vinylpyridine and 1-vinylimidazole were used as the reactive monomers for grafting on the poly(tetrafluoroethylene) film by plasma treatment. We believe that this vinyl monomers may be employable as functional groups, permitting a potentially wide range of applications: as ionomers, membranes, carriers for immobilization of biomolecules, for complex formation with heavy metals as catalysts.     

Grafting of Epoxy Resin on Surface-modified Poly(tetrafluoroethylene) Films

An epoxy/PTFE composite was prepared by curing the epoxy resin on the surface-modified PTFE film. Surface modification of PTFE films was carried out via argon plasma pretreatment, followed by UV-induced graft copolymerization with glycidyl methacrylate (GMA). The film composite achieved a 90°-peel adhesion strength above 15 N/cm. The strong adhesion of the epoxy resin to PTFE arose from the fact that the epoxide groups of the grafted GMA chains were cured into the epoxy resin matrix to give rise to a highly crosslinked interphase, as well as the fact that the GMA chains were covalently tethered on the PTFE film surface. Delamination of the composite resulted in cohesive failure inside the PTFE film and gave rise to an epoxy resin surface with a covalently-adhered fluoropolymer layer. The surface composition and microstructures of the GMA graft-copolymerized PTFE (GMA-g-PTFE) films and those of the delaminated epoxy resin and PTFE film surfaces were characterized by X-ray photoelectron spectroscopy (XPS), water contact angle and scanning electron microscope (SEM) measurements. The delaminated epoxy resin surfaces were highly hydrophobic, having water contact angles of about 140°C. The value is higher than that of the pristine PTFE film surface of about 110°. The epoxy resin samples obtained from delamination of the epoxy/GMA-g-PTFE composites showed a lower rate of moisture sorption. All the fluorinated epoxy resin surfaces exhibited rather good stability when subjected to the Level 1 hydrothermal reliability tests.     

Grafting of Epoxy Resin on Surface-modified Poly(tetrafluoroethylene) Films

An epoxy/PTFE composite was prepared by curing the epoxy resin on the surface-modified PTFE film. Surface modification of PTFE films was carried out via argon plasma pretreatment, followed by UV-induced graft copolymerization with glycidyl methacrylate (GMA). The film composite achieved a 90°-peel adhesion strength above 15 N/cm. The strong adhesion of the epoxy resin to PTFE arose from the fact that the epoxide groups of the grafted GMA chains were cured into the epoxy resin matrix to give rise to a highly crosslinked interphase, as well as the fact that the GMA chains were covalently tethered on the PTFE film surface. Delamination of the composite resulted in cohesive failure inside the PTFE film and gave rise to an epoxy resin surface with a covalently-adhered fluoropolymer layer. The surface composition and microstructures of the GMA graft-copolymerized PTFE (GMA-g-PTFE) films and those of the delaminated epoxy resin and PTFE film surfaces were characterized by X-ray photoelectron spectroscopy (XPS), water contact angle and scanning electron microscope (SEM) measurements. The delaminated epoxy resin surfaces were highly hydrophobic, having water contact angles of about 140°C. The value is higher than that of the pristine PTFE film surface of about 110°. The epoxy resin samples obtained from delamination of the epoxy/GMA-g-PTFE composites showed a lower rate of moisture sorption. All the fluorinated epoxy resin surfaces exhibited rather good stability when subjected to the Level 1 hydrothermal reliability tests.     

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°.     

Surface modification of poly(tetrafluoroethylene) film by plasma graft polymerization of sodium vinylsulfonate

Poly(tetrafluoroethylene) (PTFE) surface was modified by the graft polymerization of sodium vinylsulfonate, and the chemical composition of the graft-polymerized PTFE surface was analyzed by X-ray photoelectron spectroscopy. Peroxides were formed on the PTFE surface by a combination procedure of argon plasma irradiation and air exposure, and the graft polymerization of sodium vinylsulfonate was initiated by the peroxide groups at 65–80°C. The peroxide concentration is 3 × 10⁺¹³ to 5 × 10⁺¹³ numbers/cm². The average degree of polymerization of the graft polymers was 3.4 × 10³. The graft polymer is distributed over the PTFE surface, but part of the PTFE surface remains uncovered. The coverage with the graft polymer is 43%. The PTFE surface graft polymerized with sodium vinylsulfonate was somewhat hydrophilic, but the hydrophilicity was lower than that of the PTFE surface modified by plasma treatment. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 77–84, 1997     

Surface modification of low density polyethylene films by homogeneous catalytic ozonation

Low density polyethylene films were treated by ozone to generate peroxides on the surfaces. The peroxides generated are capable of initiating radical graft polymerization of hydrophilic vinyl monomers onto the polymers, resulting in hydrophilic surfaces. Results of ozonation revealed that molecular ozone instead of hydroxyl radicals was the main oxidant for peroxide generation. A novel approach, aqueous ozonation with the addition of a soluble transitional metal salt, FeCl₃, as a homogeneous catalyst, was proposed and proved to be successful in this study. The addition of FeCl₃ could increase peroxide generation by 22.7%, compared to its non-catalyzed counterpart. An optimum catalyst concentration, 0.04 g/L, was determined. Also, the effects of pH, ozonation time and applied ozone dose on peroxide generation were investigated. The loss in tensile strength of the films would be 15% or less if the applied ozone dose was not over 2 wt.%. The functional groups generated on the film surfaces were characterized by FTIR, the contact angle and surface roughness of the film were also examined before and after ozonation.     

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...     

Surface modification of poly(tetrafluoroethylene) films by graft copolymerization for adhesion enhancement with electrolessly deposited copper

The surface modification of Ar plasma-pretreated poly(tetrafluoroethylene) (PTFE) films via UV-induced graft copolymerization with either 3-(trimethoxysilyl)propyl methacrylate (TM-SPMA) or glycidyl methacrylate (GMA) was carried out to enhance their adhesion to electrolessly deposited copper. The surface compositions of the PTFE films at various stages of surface modification and electroless plating were studied by X-ray photoelectron spectroscopy (XPS). The adhesion strength of the graft-copolymerized PTFE film to the electrolessly deposited copper was affected by the type of monomer used for graft copolymerization, the graft concentration, the plasma post-treatment time after graft copolymerization, and the extent of thermal post-treatment after metallization. The maximum T-peel strength achieved between the electrolessly deposited copper and the GMA graft-copolymerized PTFE film was about 11 N/cm. This adhesion strength represented a more than 20-fold increase over what could be achieved when the PTFE film was treated by Ar plasma alone. The mechanisms of the adhesion strength enhancement and the failure mode in the metal-polymer laminates were also investigated. It was found that the failure was cohesive in nature within the PTFE film.     

Effects of surface modification by remote hydrogen plasma on adhesion in poly(tetrafluoroethylene)/copper composites

Poly(tetrafluoroethylene) (PTFE) sheet was modified with the remote hydrogen plasma, and the effect of the modification on adhesion between the PTFE sheet and copper metal was investigated. The remote hydrogen plasma was able to make PTFE surfaces hydrophilic without etching. In the modification process, defluorination and oxidation occurred on the PTFE surface. Reactivity of defluorination was 25% (estimated from the concentration of CF₂ component) −39% (estimated from the F/C atom ratio). Surface modification of PTFE surface by remote hydrogen plasma contributed to the adhesion between PTFE and copper metal. Peel strength was improved from 7.5 to 92 mN/5 mm by surface modification by a factor of 12. Failure of the PTFE/copper adhesive joint occurred at the interface between the PTFE and copper metal layers, rather than in the inner layer of the PTFE polymer or copper metal layers. Remote hydrogen plasma treatment is a preferable pretreatment of PTFE surface for the fabrication of PTFE and copper metal composites. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 2191–2200, 1999     

Modification of poly(tetrafluoroethylene) and copper foil surfaces by graft polymerization for adhesion improvement

Thermal graft polymerization-induced lamination of surface-modified copper foil to surface-modified poly(tetrafluoroethylene) (PTFE) film was achieved in the presence of an epoxy resin adhesive and glycidyl methacrylate (GMA) monomer, or in the presence of GMA and hexamethylenediamine (HEDA). The copper foil surfaces were pretreated with an organosilane coupling agent (SCA), such as (3-mercaptopropyl)trimethoxysiane, 3-(trimethoxysilyl)propyl methacrylate, or N¹-[3-(trimethoxysilyl)propyl]diethylene-triamine. The silanized copper foils were subjected to brief Ar plasma treatment and subsequently to UV-induced graft polymerization with GMA (the Cu-SCA-g-GMA surface). Surface modification of PTFE film included Ar plasma treatment alone, or Ar plasma pretreatment followed by UV-induced graft polymerization with GMA (the GMA-g-PTFE surface). The modified surfaces and interfaces were characterized by X-ray photoelectron spectroscopy (XPS) and water contact angle measurements. The Cu-SCA-g-GMA/epoxy resin-GMA/PTFE or Cu-SCA-g-GMA/GMA–HEDA/GMA-g-PTFE laminates exhibited T-peel adhesion strengths in excess of 9 N/cm and the joints delaminated by cohesive failure inside the bulk of the PTFE film. The strong adhesion in these Cu foil-PTFE laminates is attributable to the fact that the GMA chains are covalently tethered on both the PTFE and the silanized Cu surfaces, as well the fact that these grafted GMA chains are covalently incorporated into the highly crosslinked network structure of the adhesive at the interphase.     

聚四氟乙烯膜的表面改性研究

利用氩等离子体对聚四氟乙烯膜进行预处理,经与空气接触后接枝丙烯酸。用碘化钠法测定了膜表面过氧基团的浓度,探讨了等离子体处理时间、放电功率对膜表面过氧基团浓度的影响;过氧基团的浓度对接枝率的影响。利用红外光谱和X射线光电子能谱图鉴定了接枝产物,对改性后薄膜的表面亲水性进行了测试。     

Hydrophilicity Enhancement of High‐Density Polyethylene Film by Ozonation

High‐density polyethylene (HDPE) films were ozonated in the gas phase and in distilled water, respectively, to improve their surface hydrophilicity. The efficiency of ozonation conducted in the gaseous and aqueous phases was compared. The results indicated that the aqueous ozonation was more effective than its gaseous counterpart in terms of peroxide generation. The results also showed that the concentration of peroxides generated on the film surfaces increased with the applied ozone dose and ozonation time in both phases. It was found that the peroxides generated by aqueous ozonation were accessible to monomers for graft polymerization. The hydrophilicity of the HDPE films was significantly improved by graft polymerization of acrylamide (AAm) initiated by the peroxides. The contact angle reduction from 74.9° to 38.6° indicated the successful graft polymerization. The successful graft polymerization of AAm was further confirmed by the formation of new peaks corresponding to amide groups in FTIR spectra and by scanning electron microscope images.     

Photochemical modification of DLC films with oxygen functionalities and their chemical structure control

The photoreaction of diamond-like carbon (DLC) films in the presence of hydrogen peroxide leads to the covalent modification of their surface through the introduction of oxygen-containing functional groups, as confirmed by X-ray photoelectron, infrared and Raman spectroscopies. The DLC films modified with oxygen moieties showed high hydrophilicity, evaluated by their contact angle with water, compared with a pristine DLC film, and good tribological properties from the initial stage in water. The chemical structure of oxygen-terminated DLC films was also controlled by reduction of the oxygen moieties using hydride agents.     

Planarizing CVD diamond films by using hydrogen plasma etching enhanced carbon diffusion process

Polycrystalline diamond films, deposited by microwave plasma chemical vapor deposition (MPCVD), were planarized in hydrogen plasma under the graphitization of iron film obtained by reduction of iron chloride under hydrogen plasma ambient. For this process, the free-standing diamond films were dipped in a saturated iron chloride solution and dried horizontally in atmospheric ambient. Then the diamond samples were heated by hydrogen plasma in the same MPCVD reactor. Under the effect of hydrogen reduction, iron thin film was formed on the surface of diamond films. Under ca. 800 °C, the carbon diffusion process was carried out under the graphitization effect of iron thin film. Since the iron film used in this process is very thin, the diffused carbon will diffuse from the diamond side to the hydrogen plasma side and then etched away by the plasma. Therefore, the etching rate of diamond film can be kept consistent. After etching the growth surface of a free-standing diamond film, we investigated the surface morphologies and the carbon phases on the etched surfaces of diamond films. Finally, compared with the result of mechanical lapping experiments, we suggest that the hydrogen plasma etching enhanced carbon diffusion process can serve as a new planarization method for rough diamond film surface. A mechanism for this enhanced etching effect is also presented and discussed.     

远程等离子体处理对聚四氟乙烯表面的功能化改性

采用远程氩等离子体对聚四氟乙烯(PTFE)膜进行了表面改性研究,通过接触角测定仪、扫描电子显微镜(SEM)和X射线光电子能谱仪(XPS)等手段,分析研究了改性后材料表面结构、性能的变化。结果表明:PTFE表面经远程氩等离子体处理后,表面微观形态和表面化学成分均发生了变化,且处理效果优于常规氩等离子体。远程氩等离子体可以在一定程度上抑制电子、离子的刻蚀作用,强化自由基反应,使材料表面获得更好的改性效果。经远程氩等离子体短时间(100s)处理后,PTFE表面的F/C比例从1.97降至1.44,O/C比例从0.015增至0.086;表面的水接触角从108°减小到53°;表面自由能从22.4×10-5N·cm-1增加至52.3×10-5N·cm-1。     

Dry Processes for Surface Modification of a Biopolymer: Chitosan

Standard dry surface modification reactions have been applied to partially deacetylated chitosan without affecting its bulk properties. Chitin, extracted from shells of Penaeus vannamei, yielded chitosan with a degree of acetylation of 70% and molecular weight of 250 000 D. The copolymer consists of (β‐(1‐4)‐2‐2‐acetamido‐D ‐glucose) units linked to (β‐(1‐4)‐2‐amino‐D ‐glucose) units. Since the main interest of this work was to study the surface properties of films on substrates, a method to cast this material onto Al‐coated silicon wafers had to be developed. X ray photoelectron spectroscopy (XPS) has been used to determine the surface composition of the unmodified films and to follow modification changes. The films were treated in either an oxygen plasma environment or under UV/ozone irradiation. Water advancing contact angle measurements and infrared spectroscopy (FTIR) were used to complement XPS measurements. The films appeared to orient on the silicon wafer surface in the type II chitin structure. The rates of oxidation are faster for the plasma process but they result in similar changes to those induced by UV/ozone treatment. Atomic force microscopy (AFM) clearly shows the advantage of the milder modification reaction without much change in surface morphology. The oxidation processes, as detected by XPS, proceed without much alteration of the amine nitrogen atoms but carbonyl containing moieties are formed as a function of treatment time. Specific reactions with a fluorosilane to measure the activity of hydroxyl groups indicate that at short treatment times, these groups are essentially inactive. The resulting surfaces can also serve as a potential way to induce silica‐like domains that can function as diffusion barriers. Irradiation of chitosan solutions shows that UV/ozone induces depolymerization. In both cases, i.e., plasma and UV/ozone reactions, the main active component to surface modification appears to be UV irradiation with a wavelength below 360 nm.

AFM surface profile for oxygen plasma treated film in barrel etcher for 1 min.     

Surface modification of coil coatings with thin plasma polymer films structure and stability

Plasma deposition of a thin top layer with tailored properties is an effective strategy of modification of the organic coating surface. Thin plasma polymer layers are candidates and can provide superior hardness, scratch resistance, modified surface hydrophobicity and easy to clean properties.The present work studies the stability of thin plasma polymer films deposited as top layer on polyurethane coil coating systems. Microwave, hollow cathode and radio frequency plasma polymerization reactors were employed in order to deposit a thin SiO_x based plasma polymer layer.The plasma film stability was studied using surface analysis techniques, ex situ and in situ atomic force microscopy and scanning electron microscopy. Energy dispersive spectroscopy, FTIR spectroscopy and optical measurements confirm the composition and plasma layer properties. The structure of the plasma layers was investigated by means of transmission electron microscopy.The surface morphology together with composition evolution allows the study of the stability of the different coatings. The structure examination of the formed plasma polymer film offers good clarification for coating failure. Decrease of the operating pressure during plasma polymerization and oxygen concentration in precursor mixture lead to formation of compacter layer with higher stability. Introduction of fluorine-containing precursor also increases the anti-weathering performance of the plasma polymer films.     

The initiation of in situ polymerization of vinyl monomers in polyester by glow discharge

Glow discharge initiation of in situ polymerization of acrylic acid and other vinyl monomers incorporated in PET films was investigatigated. The influence of glow discharge conditions such as the gas used, plasma power, discharge current, and plasma treatment time on polymerization yield was determined. Though glow discharge effects are limited to the film surface, in situ polymerization of the vinyl monomers took place and the vinyl polymer could be found all through the film cross section. At short plasma treatment time only surface modification took place, while at longer treatment time bulk modification occurred, too. Good polymerization yields were obtained. Gel effect behavior was observed. Mechanical properties of the modified PET film were not changed, while the contact angle with water improved when polar vinyl monomers were used.