Conductive thin film formation onto radiation grafted polymeric surfaces using electroless plating technique

Surface modification of polypropylene films (PP) was carried out via radiation induced graft copolymerization of 4‐vinyl pyridine (4VP) and acrylamide (AAm) to enhance the adhesion ability of the PP surface for electroless deposition of copper. Factors affecting the grafting process such as suitable solvent, comonomer composition and concentration and irradiation dose were optimized. The grafted films produced were characterized by studying their Fourier‐transform infrared (FTIR) spectra and thermal stability. The grafted films were copper‐plated by electroless deposition using Pd as the catalyst to initiate the redox reaction. The influence of catalytic activation method parameters on the plating rate were studied. Scanning electron microscopy revealed a dense and void‐free copper deposited film. The adhesion of the deposited copper film to the modified PP films was determined by measuring the tensile strength of the copper plated films. The electrical characteristics of the copper plated films in comparison with grafted films were studied. The results showed the high adhesion of the deposited copper film to the grafted PP film as well as the high electrical conductivity. Copyright © 2008 John Wiley & Sons, Ltd.     

An atomic-force microscopy study of the formation of vinyl and acryl graft polymers on a polypropylene film surface

Changes in the surface structure of oriented polypropylene (PP) films in conditions of graft copolymerization of acrylamide, vinylpyridine, and styrene on a PP surface preliminary subjected to plasmochemical activation in oxygen plasma or in a plasma-electrolyte solution system are investigated by atomic-force microscopy. It is shown that the latter soft conditions of activation are superior to the hard conditions with oxygen plasma in retaining original lamellar structure of oriented PP films. It is established that the subsequent graft copolymerization of the vinyl and acryl monomers on the PP surface yields amorphous phases of respective polymers.     

Adhesion Enhancement and Characterization of Plasma Polymerized 1,2-Dichloroethane on Polypropylene Surface

Polypropylene (PP) films were modified in 1,2-dichloroethane (DCE) plasma. Surface energy measurement and rate of deposition showed two-step surface modification. First, incorporation of chloride ions on PP surface followed by deposition of cross-linked layer. DCE plasma modified PP films were subsequently compared with earlier reported work on carbontetrachloride (CCl₄) and chloroform (CHCl₃) plasma modification. Modified films were characterized using ATR-FTIR technique by monitoring the relative changes in intensities of C–H stretch vibrations. The nature of deposition on PP film was characterized using FTIR technique and solubility test. Peel strength measurements of DCE, CCl₄, and CHCl₃ plasma modified films showed improvement in bonding strength. Durability of plasma modified PP film was studied by calculating surface energy and peel strength of samples aged for two months.     

基板界面对PS/PMMA溶液共混物溶剂挥发成膜相结构的影响

研究了PS PMMA的共混物溶液溶剂蒸发成膜时的基板界面效应 .利用扫描电子显微镜 (SEM)研究了PS PMMA(5 5 ) (W W) THF高分子共混物溶液在不同基板上通过溶剂挥发成膜的相形态结构 .通过FTIR及ATR FTIR检测了共混物薄膜及其表面的共混组成 .研究结果表明 ,成膜基板对高分子共混物溶液成膜后的相形态有很重要的影响 .控制共混物溶液体系成膜过程中的动力学因素 ,可以调控出所设想的各种复杂的相结构形态     

The gas barrier coating of 3-aminopropyltriethoxysilane on polypropylene film

Nonporous films were formed on polypropylene (PP) films using 3-aminopropyltriethoxysilane (APTEOS) as the only precursor. The PP film was modified by corona-plasma treatment to provide appropriate adhesion between coating layer and substrate. Gas permeation properties of coating films were evaluated, and the influences of water ratio and film storing time on the gas permeability were investigated. Structural and surface properties of coating layers were characterized by ²⁹Si-NMR, FT-IR, and contact angle analyzer. The APTEOS coating films exhibit much higher barrier properties than PP film. The permeability coefficient of APTEOS coating film with water ratio of 3 is 0.011Barrer for nitrogen, 0.044Barrer for oxygen, and 0.002Barrer for carbon dioxide, while each permeability coefficient of PP bare film is 0.233, 0.858, and 2.886Barrer, respectively. The gas permeability coefficient is increased slowly along with storage time. Although additionally formed siloxane network may lead to a higher inorganic network density, the enhancement of gas permeability during storing period is largely attributed to film-swelling effect by the water vapor from atmosphere.     

Comparison of the surface characteristics of polypropylene films treated by Ar and mixed gas (Ar/O2) atmospheric pressure plasma

In an attempt to modify the hydrophobic surface properties of polypropylene (PP) films, this study examined the optimum process parameters of atmospheric pressure plasma (APP) using Ar gas. Under optimized conditions, the effects of a mixed gas (Ar/O2) plasma treatment on the surface-free energy of a PP film were investigated as a function of the O2 content. The polar contribution of the surface-free energy of the PP film increased with increasing O2 content in the gas mixture. However, slightly more oxygen-containing polar functional groups such as CO, CO, and COO were introduced on the PP film surface by the Ar gas only rather than by the Ar/O2 gas mixture. In addition, AFM analysis showed that the Ar plasma treatment of the PP film produced the smoothest surface as a result of the relatively homogeneous etching process.     

XPS analysis of the poly(ethylene terephthalate) film grafted with acrylamide

Graft polymerization of acrylamide (AAm) was performed onto the surface of a poly(ethylene terephthalate) (PET) film with the simultaneous UV irradiation method but using no photosensitizer and without degassing. To examine whether polyacrylamide (PAAm) was introduced into the bulk place of PET film by the surface graft polymerization, an x-ray photoelectron spectroscopic (XPS) study was performed on the PAAm-grafted PET films. The distribution of grafted PAAm chains on and in the PET films was estimated from the PAAm/PET ratio calculated from the XPS spectra of PET films with different amounts of grafted PAAm. The results clearly demonstrate that graft polymerization has actually occurred not merely on the outermost surface but also within the thin surface region of the PET film. In addition, the XPS analysis revealed that the PET component was always present in the grafted surface region by a mole fraction of 0.1 to 0.05 even when the amount of PAAm grafted was larger than 10 μg/cm².     

低介电常数聚喹啉衍生物薄膜的合成与表征

采用等离子体聚合技术合成了一种新型的低介电常数聚喹啉衍生物薄膜: 聚3-氰基喹啉(PP3QCN)薄膜. 借助于傅里叶变换红外光谱(FT-IR)、紫外-可见(UV-Vis)吸收光谱、X光电子能谱(XPS)和原子力显微镜(AFM)对薄膜结构进行了系统表征. 结果表明, 等离子体聚合条件对沉积膜的化学结构、表面组成、膜形态以及介电性能均有影响. 在较低的等离子体放电功率(10 W)条件下, 可得到具有较高芳环保留率和较大π-共轭体系的高质量聚3-氰基喹啉薄膜材料; 而在较高功率(25 W)条件下, 聚合过程中会出现比较严重的单体分子破碎, 形成较多非π-共轭体系的聚合物, 从而导致聚3-氰基喹啉的共轭度降低. 聚3-氰基喹啉薄膜的介电性能测试结果表明, 低放电功率(10 W)条件下制得的聚3-氰基喹啉薄膜具有比较低的介电常数值, 仅为2.45.     

Surface modification of polyolefins by photografting of acrylic monomers

High-speed surface modification of polypropylene (PP) and polyethylene (PE) films has been achieved by liquid phase photograft polymerisation of acrylic acid (AA) and hydroxypropyl acrylate (HPA). Benzophenone was used as photoinitiator to generate polymer radicals at the surface of the polyolefin film. The grafting reaction was carried out in aqueous solution or with the neat monomer, which was laminated between two PP films, in the presence of air. Under the intense illumination of a UV-curing line, acrylic acid was grafted within seconds to polypropylene films or fabrics, which were thus made hydrophilic. Direct evidence of surface grafting was obtained through infrared spectroscopy analysis and surface energy measurements. This continuous photografting process proved to be very efficient to improve the adhesion of UV-cured acrylate coatings on polyolefin-made materials.     

聚丙烯表面接枝PNIPAAm膜Ⅰ.光接枝反应和表面形态结构研究

以氧杂蒽酮或二苯甲酮为引发剂 ,通过紫外光引发表面接枝聚合的方法在聚丙烯薄膜表面引入了具有温度敏感特性的聚异丙基丙烯酰胺 (PNIPAAm)接枝聚合物层 .提高紫外光强度和接枝反应温度均有利于接枝率增大 ,而单体浓度对接枝率的影响存在最佳值 ,为 0 1 8mol L .在引发剂预浸渍引发接枝和休眠基引发接枝这两种方式中 ,后者能够实现更高的接枝率 .红外光谱 (FTIR)、X射线光电子能谱化学分析 (ESCA)和扫描电子显微镜 (SEM)等对接枝层组成的表征结果证实了接枝层的存在 .在不同温度下 ,接枝膜的FTIR谱图中酰胺I带和酰胺II带特征吸收峰发生位移 ,表明它具有温度敏感特性 .同时 ,SEM研究发现由于接枝膜的温度敏感特性而导致的球状表面形态结构     

Surface roughness and hydrophilicity enhancement of polyolefin‐based membranes by three kinds of plasma methods

The introduction of antibacterial property, conductivity, wettability and antithrombogenicity into polyolefin‐based membranes has evoked much attention, which can be achieved by coating hydrophilic polymers. Therefore, it is necessary to modify the roughness and hydrophilicity of polyolefin‐based membranes to enhance the coating ability. In this paper, three kinds of plasma methods, including inductively coupled (ICP) plasma, radio frequency low pressure (RFP) plasma and atmospheric dielectric barrier discharge (DBD) plasma, were used to modify the surface of the polyethylene (PE), polypropylene (PP) and polyester‐polypropylene (PET–PP) membranes. The surface roughness of the plasma‐modified PE, PP and PET–PP films was investigated by scanning electron microscopy (SEM) and atomic force microscope (AFM). The polar functional groups of films were observed by energy dispersive spectrometer (EDX) and X‐ray photoelectron spectroscopy (XPS). Besides, the hydrophilicity of the plasma‐modified PE, PP and PET–PP films was evaluated by water contact angle measurement. It was found that the surface roughness and hydrophilicity of plasma‐modified PE, PP and PET–PP films increased with the generation of oxygen‐containing functional groups (i.e. C―O, and C?O). The PET–PP membranes were treated by RFP plasma at different processing powers and times. These results indicated that plasma is an effective way to modify films, and the treatment time and power of plasma had a certain accumulation effect on the membranes' hydrophilicity. As for the roughness and hydrophilicity, the DBD plasma modifies the PE film, which is the optimum way to get the ideal roughness and hydrophilicity. Copyright © 2015 John Wiley & Sons, Ltd.     

Increasing the Hydrophobicity of a PP Film Using a Helium/CF<Subscript>4</Subscript> DBD Treatment at Atmospheric Pressure

Plasma surface modification is widely used to tailor the surface properties of polymeric materials. Most treatments are performed using low pressure plasma systems, but recently, atmospheric dielectric barrier discharges (DBDs) have appeared as interesting alternatives. Therefore, in this paper, an atmospheric He + CF₄ DBD is used to increase the hydrophobicity of a polypropylene (PP) film. The surface characterization of the PP film is performed using contact angle measurements, X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). Results show that the hydrophobic properties of the polymer films are greatly enhanced after plasma treatment as evidenced by an increased contact angle. The incorporation of fluorine on the surface is significant (45 at%), demonstrating the ability of the used DBD set-up to generate fluorine-containing functional groups on the PP surface.     

聚丙烯表面接枝改性络合金的研究

探索了一种通过聚丙烯(PP)改性来络合金金属的新途径.首先在PP膜上经紫外光引发实施丙烯酸的接枝聚合反应,得到表面带—COOH基团的改性PP膜;再用负离子开环聚合的方法在改性后的PP膜上接枝尼龙6.上述处理后的膜表面含有大量O、N的功能基团,故可将此膜用于对溶液中金的络合.利用ATR、SEM、XPS等技术对改性及络合进行了表征.实验结果表明,此方法制备的PP膜对金的络合效果明显.     

A Polymer Composite Film with Reversible Responsive Behaviors

Summary: A responsive polymer composite film was generated by the use of reversibly switchable surface morphology of polystyrene‐block‐poly(methyl methacrylate) (PS‐b‐PMMA) films in response to different block selective solvents on the rough isotactic poly(propylene) (i‐PP) substrate. The maximum difference of the water contact angle of the composite films increased from 22.6° of PS‐b‐PMMA films on the smooth substrate to 42.6° when they were treated by PS and PMMA selective solvents, respectively. The mechanisms of the responsive extent enhanced and the superhydrophobicity of the composite films were discussed in detail.

Schematic illustration of how to fabricate a wettability‐responsive composite film: (a) on the flat Si substrate, (b) on the rough PP substrate.     

Adsorption behavior of urokinase by polypropylene film modified with amino acids as affinity groups

In order to prepare a new-type adsorbent with an affinity ligand, polypropylene films modified with amino acid groups such as -phenylalanine (Phe), , -Phe, -cysteine (Cys), and , -tryptophane (Try), were prepared by radiation-induced grafting of glycidyl methacrylate (GMA) onto polypropylene (PP) films and subsequent amination of poly-GMA graft chains. The physical and chemical properties of the GMA-grafted PP film and the PP film modified with amino acid groups were investigated by IR and XPS. The adsorption of urokinase for the PP films modified with four kinds of amino acid groups were examined under various conditions, such as the contents of the amino acid group and pH value. The adsorption of urokinase increased with the increasing content of the amino acid group. The adsorption of the PP film modified with four kinds of amino acid groups was in the following order: -Phe> , -Phe> , -Try> -Cys. The adsorption amounts of urokinase by the PP film modified with four kinds of amino acid groups at pH 7.4 was higher than that at pH 9.0.     

Surface graft polymerization of acrylamide onto poly(ethylene terephthalate) film by UV irradiation

To improve the low water wettability of poly(ethylene terephthalate) (PET), graft polymerization of acrylamide (AAm) by UV irradiation was performed onto the surface of a PET film with the simultaneous irradiation method without using a photo sensitizer. The PET film immersed in a 10 wt % deaerated aqueous solution of AAm was found to become highly hydrophilic upon UV irradiation. Optical microscopy on cross sections of grafted films showed that localization of the graft polymerization was restricted to a thin surface region of the film. Both the low concentration of polymer radicals formed by UV irradiation and the monomer penetration limited to the film surface would be responsible for localization of the grafted layer to the film surface region. Pretreatment of the PET film with benzyl alcohol was effective for enhancement of the graft polymerization. Retention of high hydrophilicity of the surface even after rigorous extraction of homopolymer and a comparative study of polymerization without UV irradiation strongly suggested that UV irradiation of the PET film under immersion in the deaerated AAm aqueous solution would lead to formation of the true graft copolymer.     

5,10,15,20-四-(4-N,N,N-二甲基十六烷基氨基苯基)卟啉LB膜结构的研究

研究了两亲性卟啉5,10,15,20-四-(4-N,N,N-二甲基十六烷基氨基苯基)卟啉(TDMC₁₆PP)在气/液界面上的成膜性能,制备了其多层LB膜。用UV-Vis吸收光谱、荧光光谱、偏振UV-Vis吸收光谱和小角X射线衍射对LB膜进行了测试表征。结果表明:两亲性卟啉TDMC₁₆PP具有良好的成膜性能,其LB膜性质稳定,有较好的结构均匀性和周期性。在LB膜内,脂肪链并不是直立的,卟啉大环平面与基片平面成42.5°排列。     

预氧化聚烯烃膜的表面光接枝聚合

将经表面热氧化的聚丙烯和聚乙烯膜在不加敏化剂的情况下,通过紫外光照射与光稳定剂甲基丙烯酸(2,2,6,6-四甲基哌啶)酯进行接枝聚合,以改善膜的光稳定性。研究了各种因素,包括热氧化时间,光照射时间、单体浓度及溶剂等对表面预氧化膜的光接枝含量的影响。实验结果表明,常用的有机溶剂除酮类外均不能使膜接枝;接枝以后膜的光稳定性有很大的提高。     

Water vapour barrier performance of corn-zein coated polypropylene (PP) packaging films

The novel film structure of corn-zein coated on polypropylene (PP) synthetic film for packaging industry was developed to examine the feasibility of resulting coated films as an alternative water barrier performance for food packaging. The effects of coating formulation (solvent, corn-zein, plasticizer concentration and plasticizer type) on final properties of films were observed. Corn-zein is the most important protein of corn and has good film forming property. Composites structures of PP films coated with corn-zein were obtained through a simple solvent casting method. Polyethylene glycol (PEG) and glycerol (GLY) were used as plasticizer to increase film flexibility. Statistical analysis based on full factorial design was performed to observe coating formulation effects. The high water vapour barriers were obtained for films coated with coating formulation consisting of higher amounts of corn-zein plasticized by GLY. The lower glass transition temperatures (T _g) of films were obtained by plasticization of films and T _g decreased by increasing plasticizer content. The statistical analysis defined the key parameters of coating formulation that had major effects on the final properties of coated PP films as corn-zein, plasticizer concentration and plasticizer type. In conclusion, corn-zein coatings could have potential as an alternative to conventional synthetic polymers used in composite multilayer structures for food packaging applications.     

A Comparative Study of Properties of Acrylic Based Water-Borne Polymers Using Various Surfactants for Adhesive Applications

Emulsion polymerization of styrene/vinyl acetate/methyl methacrylate with butyl acrylate, acrylic acid and acrylamide is investigated using conventional and polymerizable surfactants. The effect of different surfactants on the water resistance, adhesion and surface properties of the polymer films was studied. The performance of films obtained from latexes using conventional surfactants is compared with that of latexes using polymerizable surfactants. The study showed that polymerizable surfactants are bound to the polymer backbone in such a way that their migration to film surfaces during drying is inhibited which helps in achieving better water resistivity with good adhesive performance.