Poly(dimethylsiloxane)-polyimide blends in the formation of thick polyimide films

Thick polyimide layers can be formed by using some unique properties of poly(dimethylsiloxane)-polyimide (PDMS/PMDA–ODA) blends followed by surface modification and deposition of a second layer of polyimide precursor chemicals. The method is based on the micro-phase separation characteristics of these blends to yield surfaces that have PDMS-like character. Upon modification with UV/ozone treatment, a surface that is essentially SiO _x and hydrophilic in nature is produced. This surface is amenable to reaction and deposition of a second polyimide layer from polyimide precursors. The thicker polyimide layer has enhanced adhesion between the original layer of the blend and the new polyimide layer and this approach finds extensive applications for products that require thick polymer layers. Changes in surface energy for various blend compositions were monitored by measurement of advancing contact angle with de-ionized water. Contact angle for unmodified polyimide films was on the order of 70° and it increased to about 104° after blending with PDMS and curing. UV/ozone treatment reduced the contact angle of the doped polyimide to less than 5°. X-ray photoelectron spectroscopy (XPS) and angle resolved XPS (ARXPS) measurements were used to monitor the chemical compositions of the various surfaces. High-resolution XPS spectra in the Si2p region confirm the transformation of O–Si–C bonds in PDMS to SiO _x , where x is about 2. Scanning electron microscopy (SEM) of some selected samples shows that the blends contain phase separation of the polymers at the surfaces of the samples. Atomic force microscopy (AFM) of siloxane-free polyimide, and PDMS/PMDA–ODA blends both prior to and after UV/ozone exposure, show that the films are essentially flat at short treatment times (less than 60 min). AFM also reveals the separation of PDMS into micro-domains at the cured film surface and throughout the layer below the surface of the blended films. Adhesion of a subsequently deposited polyimide layer to the modified polyimide surface was found to be greatly improved when compared to the adhesion obtained for deposition onto a pristine polyimide surface.     

Transformation of Poly(dimethylsiloxane) into thin surface films of SiO x by UV/Ozone treatment. Part I: Factors affecting modification

UV/ozone treatment of poly(dimethylsiloxane) (PDMS) was used to produce thin surface films of SiO _x . Films of PDMS were applied by spin-coating onto gold-coated silicon wafers having (100) orientation. Characterization of the UV/ozone system was performed to map the spatial distribution of intensities of UV radiation. This mapping was used to ensure reproducible modification of films and to aid in the understanding of modification as measured by advancing contact angle using deionized water and x-ray photoelectron spectroscopy (XPS). Rutherford backscattering spectroscopy (RBS) was used to measure thickness of the PDMS films. Treatment reduced the wetting angle, in some cases from a value greater than 100° to a value less than 5°. High resolution XPS spectra were used to study the nature of the modified PDMS film and its relationship to the characteristics of the unmodified PDMS. High resolution XPS spectra in the Si 2p region show that O–Si–C bonds in the siloxane, observed prior to treatment, are converted to SiO _x , where x is between 1.6 and 2. Modified films also contain some oxidized carbon components. The time required to reduce the contact angle to a minimum value was greater for the thicker PDMS film samples. The effects of ozone alone (without UV) and UV radiation at 184.9 and 253.7 nm (without ozone) were also investigated. The results of UV/ozone treatment are compared to results achieved by means of plasma surface oxidation.     

Effect of UV/ozone treatment on interactions between ink-jet printed Cu patterns and polyimide substrates

In this study, we apply UV/ozone treatment to modify the surface properties of polyimide substrate and investigate the effects of UV/ozone treatment on surface properties of polyimide and the morphologies of ink-jet printed Cu patterns. Wettability of polyimide surface is enhanced by UV/ozone treatment as confirmed by contact angle analysis and XPS results. The change in wettability affected droplet sizes and morphologies of ink-jet-printed lines. The average droplet size increased from 26.8 μm on untreated polyimide to 42.5 μm after UV/ozone treatment. Furthermore, irregular patterns of coexisting beads and short lines were observed in untreated polyimide film, despite minimal overlap of dots. In contrast, patterns that were ink-jet printed on polyimide film that was modified by UV/ozone for 1 h showed continuous lines with straight edges.     

Surface modification of a flexible polyimide film using a reactive fluorinated polymer nanosheet

This paper describes an effective approach to surface modification of a flexible polyimide film using a reactive fluorinated polymer nanosheet. N-(1H,1H-pentadecafluorooctyl)methacrylamide copolymers containing carboxyl group as a reactive moiety form stable monolayer on the water surface and highly ordered reactive polymer nanosheets can be fabricated by the Langmuir-Blodgett technique. This reactive fluorinated polymer nanosheet was utilized to modify the surface properties of polyimide film through its immobilization using thermal treatment. The modification process was studied by X-ray photoelectron spectroscopy (XPS) and modified PI surface was characterized by contact angle measurements and atomic force microscopy (AFM).     

Adhesive properties of polypropylene (PP) and polyethylene terephthalate (PET) film surfaces treated by DC glow discharge plasma

In this study, the adhesive properties of the plasma modified polypropylene (PP) and polyethylene terephthalate (PET) film surfaces have been investigated. Hydrophilicity of these polymer film surfaces was studied by contact angle measurements. The surface energy of the polymer films was calculated from contact angle data using Fowkes method. The chemical composition of the polymer films was analyzed by X-ray photoelectron spectroscopy (XPS). Atomic force microscopy (AFM) was used to study the changes in surface feature of the polymer surfaces due to plasma treatment. The adhesion strength of the plasma modified film was studied by T-peel strength test. The results showed a considerable improvement in surface wettability even for short exposure times. The AFM and XPS analyses showed changes in surface topography and formation of polar groups on the plasma modified PP and PET surfaces. These changes enhanced the adhesive properties of polymer film surfaces.     

Poly(dimethylsiloxane) surface modification by plasma treatment for DNA hybridization applications

In this work, the surface modification of poly(dimethylsiloxane) (PDMS) was carried out by using a 2-step plasma modification with Ar followed by acrylic acid (AAc). The optimal conditions were found to be 0.5 min with Ar at 0.7 mbar; and 5 min with AAc at 0.2 mbar. The water contact angle (WCA) of the native PDMS decreased from 110 degrees to 30 degrees after modification, then stabilized to values between 50 degrees to 60 degrees after 1 day exposure to air. The stability of the modified PDMS was further improved by Soxhlet-extracting the PDMS with hexane prior to plasma treatment. Atomic force microscopy (AFM) showed significant changes in surface morphology after the 2-step plasma modification. X-ray photoelectron (XPS) spectroscopy further confirmed the successful modification of the PDMS surface with PAAc, by exhibiting C1s peaks at 285.9 eV, 287.4 eV and 289.9 eV, originating from C-O, C=O and O-C=O moieties, respectively. Fourier transform infrared-attenuated total reflection (FTIR-ATR) spectroscopy of the poly(acrylic acid) (PAAc) modified PDMS surface showed a distinctive peak at 1715 cm(-1), attributed to the presence of COOH groups from the PAAc. The carboxyl peak on the spectra of the PAAc modified PDMS was quite stable even after storage at room temperature in phosphate buffer saline (PBS) and N-2-hydroxyethylpiperazine-N'-2-ethanesulfonic acid (HEPES) buffer for 17 h. 5'-amino-terminated oligonucleotides were covalently attached to the PAAc modified PDMS surface via carbodiimide coupling. Subsequently, fluorescently tagged complementary oligonucleotides were successfully hybridized to this surface, as determined by fluorescence microscopy.     

硬沥青对聚丙烯抗光老化性能的改性研究

利用深度萃取脱油方法制备高软化点硬沥青材料,通过熔融共混的方法对聚丙烯进行添加改性,并通过人工加速紫外光老化试验,对改性后的聚丙烯进行抗老化性能的测试表征,相应的红外谱图以及力学性能的测试结果表明硬沥青的添加对聚丙烯材料的抗光老化性能有很好的改善作用.     

Facile surface modification of silicone rubber with zwitterionic polymers for improving blood compatibility

A facile approach to modify silicone rubber (SR) membrane for improving the blood compatibility was investigated. The hydrophobic SR surface was firstly activated by air plasma, after which an initiator was immobilized on the activated surface for atom transfer radical polymerization (ATRP). Three zwitterionic polymers were then grafted from SR membrane via surface-initiated atom transfer radical polymerization (SI-ATRP). The surface composition, wettability, and morphology of the membranes before and after modification were characterized by X-ray photoelectron spectroscopy (XPS), static water contact angle (WCA) measurement, and atomic force microscopy (AFM). Results showed that zwitterionic polymers were successfully grafted from SR surfaces, which remarkably improved the wettability of the SR surface. The blood compatibility of the membranes was evaluated by protein adsorption and platelet adhesion tests in vitro. As observed, all the zwitterionic polymer modified surfaces have improved resistance to nonspecific protein adsorption and have excellent resistance to platelet adhesion, showing significantly improved blood compatibility. This work should inspire many creative uses of SR based materials for biomedical applications such as vessel, catheter, and microfluidics.     

Ultraviolet-induced surface modification of polyurethane films in the presence of oxygen or acrylic acid vapours

An efficient surface functionalization of polyurethane (PU) films has been obtained by ultraviolet (UV)-assisted modification in the presence of oxygen or acrylic acid (AA) vapours. Film analyses were carried out by water contact angle measurements, X-ray photoelectron spectroscopy (XPS) and Near-edge X-ray absorption fine structure (NEXAFS). Film hydrophilicity increased with photolysis time in the presence of oxygen or AA vapours. Incorporation of COO and CO functional groups at the polymer surface after the UV-assisted treatments was observed. In addition, High resolution XPS and NEXAFS results showed that a thin film of poly (acrylic acid) (PAA) is formed over the PU films during the UV irradiation with AA vapours. The obtained results are compared with previous published oxygen and AA low-power plasma treatments. Similarity between both treatment methodologies is shown. UV surface functionalization and polymerization of PAA can be used instead of a traditional plasma treatment with the advantage of set-up simplicity and lower costs.     

低温空气等离子体改性PDMS的研究

为了改善聚二甲基硅氧烷（PDMS）的亲水性和稳定其电渗性能,采用空气微波等离子体在低温条件下对其表面进行改性。利用原子力显微镜（AFM）、X射线光电子能谱（XPS）及静态接触角对处理前后的PDMS进行分析。经空气微波等离子体处理3min后,PDMS的亲水性得到极大的改善,水在其表面的接触角接近零度。XPS结果表明：处理后PDMS表面形成SiOx薄层;AFM显示空气等离子体处理对PDMS的表面没有损伤。与文献报道的高、中真空氧等离子体处理方法相比,亲水效果基本一致,却大幅度降低了对设备真空系统的要求,并缩短了操作时间,节约了成本。最佳处理条件为：微波为100W,腔体内气压为1.0kPa,空气的流量为20sccm（1sccm=1cm3·min^-1）,时间3min。     

Contact angle analysis of low-temperature cyclonic atmospheric pressure plasma modified polyethylene terephthalate

Polyethylene terephthalate (PET) films are modified by cyclonic atmospheric pressure plasma. The experimentally measured gas phase temperature was around 30 °C to 90 °C, indicating that this cyclonic atmospheric pressure plasma can treat polymers without unfavorable thermal effects. The surface properties of cyclonic atmospheric pressure plasma-treated PET films were examined by the static contact angle measurements. The influences of plasma conditions such as treatment time, plasma power, nozzle distance, and gas flow rate on the PET surface properties were studied. It was found that such cyclonic atmospheric pressure plasma is very effective in PET surface modification, the reduced water contact angle was observed from 74° to less than 37° with only 10 s plasma treatment. The chemical composition of the PET films was analyzed by X-ray photoelectron spectroscopy (XPS). Atomic force microscopy (AFM) was used to study the changes in PET surface feature of the polymer surfaces due to plasma treatment. The photoemission plasma species in the continuous cyclone atmospheric pressure plasma was identified by optical emission spectroscopy (OES). From OES analysis, the plasma modification efficiency can be attributed to the interaction of oxygen-based plasma species in the plasma with PET surface. In this study, it shows a novel way for large scale polymeric surface modification by continuous cyclone atmospheric pressure plasma processing.     

Ethanol-mediated metal transfer printing on organic films

Ethanol-mediated metal transfer printing (mTP) is a soft method, which allows to efficiently deposit metals onto various organic surfaces for applications in organic electronics. This simple approach in based on the stronger adhesion of the metals to the organic materials in the presence of thin ethanol layer between the metallized PDMS and the substrate due to the capillary action. Patterns with a resolution of at least 20 μm have been obtained on organic polymeric materials and photoresists without heating or applied pressure. Compared to other methods ethanol mediated mTP is considerably faster and has smaller limitations on the stamp depth. Residual silicone layer detected on the metal surface after the transfer by XPS studies has been mostly removed by UV/ozone treatment. Organic field-effect transistors (OTFTs) based on the metal electrodes deposited by mTP have been successfully fabricated and tested.     

Surface modification of starch based blends using potassium permanganate-nitric acid system and its effect on the adhesion and proliferation of osteoblast-like cells

The surface modification of three starch based polymeric biomaterials, using a KMnO₄/NHO₃ oxidizing system, and the effect of that modification on the osteoblastic cell adhesion has been investigated. The rationale of this work is as follows—starch based polymers have been proposed for use as tissue engineering scaffolds in several publications. It is known that in biodegradable systems it is quite difficult to have both cell adhesion and proliferation. Starch based polymers have shown to perform better than poly-lactic acid based materials but there is still room for improvement. This particular work is aimed at enhancing cell adhesion and proliferation on the surface of several starch based polymer blends that are being proposed as tissue engineering scaffolds.The surface of the polymeric biomaterials was chemically modified using a KMnO₄/HNO₃ system. This treatment resulted in more hydrophilic surfaces, which was confirmed by contact angle measurements. The effect of the treatment on the bioactivity of the surface modified biomaterials was also studied. The bioactivity tests, performed in simulated body fluid after biomimetic coating, showed that a dense film of calcium phosphate was formed after 30 days. Finally, human osteoblast-like cells were cultured on unmodified (control) and modified materials in order to observe the effect of the presence of higher numbers of polar groups on the adhesion and proliferation of those cells. Two of the modified polymers presented changes in the adhesion behavior and a significant increase in the proliferation rate kinetics when compared to the unmodified controls.     

硅橡胶的等离子体表面亲水改性

利用甲醇等离子体对硅橡胶进行表面亲水改性,并利用光电子能谱和接触角测量研究了表面亲水改性效果和表面动力学性质。结果表明,甲醇等离子体通过等离子体聚合在硅橡胶表面形成覆盖层,可以使硅橡胶良好的亲水性,并能使这一性质较好地保持。     

Solventless adhesive bonding using reactive polymer coatings

A novel solventless adhesive bonding (SAB) process is reported, which is applicable to a wide range of materials including, but not limited to, poly(dimethylsiloxane) (PDMS). The bonding is achieved through reactions between two complementary polymer coatings, poly(4-aminomethyl-p-xylylene-co-p-xylylene) and poly(4-formyl-p-xylylene-co-p-xylylene), which are prepared by chemical vapor deposition (CVD) polymerization of the corresponding [2.2]paracyclophanes and can be deposited on complementary microfluidic units to be bonded. These CVD-based polymer films form well-adherent coatings on a range of different substrate materials including polymers, glass, silicon, metals, or paper and can be stored for extended periods prior to bonding without losing their bonding capability. Tensile stress data are measured on PDMS with various substrates and compared favorably to current methods such as oxygen plasma and UV/ozone. Sum frequency generation (SFG) has been used to probe the presence of amine and aldehyde groups on the surface after CVD polymerization and their conversion during bonding. In addition to bonding, unreacted functional groups present on the luminal surface of microfluidic channels provide free chemical groups for further surface modification. Fluorescently labeled molecules including rhodamine-conjugated streptavidin and atto-655 NHS ester were used to verify the presence of active functional groups on the luminal surfaces after bonding.     

Grafting of gold nanoparticles and nanorods on plasma-treated polymers by thiols

Grafting of gold nanoparticles and nanorods on the surface of polymers, modified by plasma discharge, is studied with the aim to create structures with potential applications in electronics or tissue engineering. Surfaces of polyethyleneterephthalate and polytetrafluoroethylene were modified by plasma discharge and subsequently, grafted with 2-mercaptoethanol, 4,4′-biphenyldithiol, and cysteamine. The thiols are expected to be fixed via one of –OH, –SH or –NH₂ groups to reactive places on the polymer surface created by the plasma treatment. “Free” –SH groups are allowed to interact (graft) with gold nanoparticles and nanorods. Gold nano-objects were characterized before grafting by transmission electron microscopy and UV–Vis spectroscopy. X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), and electrokinetic analysis (zeta potential determination) were used for the characterization of polymer surface at different modification phases. It was proved by FTIR and XPS measurements that the thiols were chemically bonded on the surface of the plasma-treated polymers, and they mediate subsequent grafting of the gold nano-objects. On the surfaces, modified polymers were indicated some objects by AFM, size of which was dramatically larger in comparison with that of original nanoparticles and nanorods. This result and the other results of UV–Vis spectroscopy indicate an aggregation of deposited gold nano-objects.     

电化学诱导表面引发原子转移自由基聚合构筑离子型聚醚砜膜功能表面

采用电化学诱导表面引发原子转移自由基聚合(SI-eATRP)技术,在涂覆聚多巴胺的聚醚砜膜基底上接枝离子型聚合物分子刷聚对苯乙烯磺酸钠,并通过单体浓度对聚合物分子刷进行调控。采用SEM、AFM、XPS、水接触角等表征方法对改性聚醚砜膜的结构和性能进行表征;采用水通量对其进行滤过性能测定。结果表明:成功地在改性聚醚砜膜表面接枝离子型聚合物分子刷聚对苯乙烯磺酸钠;聚合物刷相互缠结形成了球状颗粒;随着电化学诱导体系中单体浓度的增大,聚合物分子刷的接枝量增加,同时水接触角显著降低;聚合物膜表面离子型分子刷的构筑改善了亲水性,因此其纯水通量明显增加,牛血清白蛋白(BSA)截留率和通量恢复率都得到了提高。SI-eATRP用于聚合物膜材料的表面改性和调控,在生物相容性膜等领域具有潜在的应用前景。     

Covalent micropatterning of poly(dimethylsiloxane) by photografting through a mask

A new photografting method to micropattern a covalent surface modification on poly(dimethylsiloxane) (PDMS) provides advantages in simplicity and efficiency. To accomplish the entire process on the benchtop, the PDMS was initially treated with benzophenone dissolved in a water/acetone mixture. This process permitted limited diffusion of the photoinitiator into the PDMS surface. Polymerization of acrylic acid was initiated by exposure of the benzophenone-implanted PDMS to UV radiation through a photomask with a thin aqueous layer of acrylic acid sandwiched between the PDMS and photomask. This procedure resulted in patterned poly(acrylic acid) (PAA) on the PDMS surface. In the modified regions, PAA and PDMS formed an interpenetrating polymer network extending 50 microm into the PDMS with an X-Y spatial resolution of 5 microm. The carboxyl groups of the PAA graft could be derivatized to covalently bond other molecules to the patterned PAA. Two bioanalytical applications of this micropatterned surface were demonstrated: (1) a guide for cell attachment and growth and (2) a substrate for immunoassays. 3T3 cells were shown to selectively localize to modified surface regions where they could be cultured for up to 7 days. Additionally, the micropatterned surface was used to immobilize either protein A or antibody for heterogeneous immunoassays.     

Comparison of biocompatibility and adsorption properties of different plastics for advanced microfluidic cell and tissue culture models

Microfluidic technology is providing new routes toward advanced cell and tissue culture models to better understand human biology and disease. Many advanced devices have been made from poly(dimethylsiloxane) (PDMS) to enable experiments, for example, to study drug metabolism by use of precision-cut liver slices, that are not possible with conventional systems. However, PDMS, a silicone rubber material, is very hydrophobic and tends to exhibit significant adsorption and absorption of hydrophobic drugs and their metabolites. Although glass could be used as an alternative, thermoplastics are better from a cost and fabrication perspective. Thermoplastic polymers (plastics) allow easy surface treatment and are generally transparent and biocompatible. This study focuses on the fabrication of biocompatible microfluidic devices with low adsorption properties from the thermoplastics poly(methyl methacrylate) (PMMA), polystyrene (PS), polycarbonate (PC), and cyclic olefin copolymer (COC) as alternatives for PDMS devices. Thermoplastic surfaces were oxidized using UV-generated ozone or oxygen plasma to reduce adsorption of hydrophobic compounds. Surface hydrophilicity was assessed over 4 weeks by measuring the contact angle of water on the surface. The adsorption of 7-ethoxycoumarin, testosterone, and their metabolites was also determined after UV-ozone treatment. Biocompatibility was assessed by culturing human hepatoma (HepG2) cells on treated surfaces. Comparison of the adsorption properties and biocompatibility of devices in different plastics revealed that only UV-ozone-treated PC and COC devices satisfied both criteria. This paper lays an important foundation that will help researchers make informed decisions with respect to the materials they select for microfluidic cell-based culture experiments.     

MAH等离子体改性PVDF薄膜表面的亲水性研究

以马来酸酐(MAH)低温等离子体接枝聚合的方法对聚偏氟乙烯(PVDF)薄膜表面进行亲水改性.分析了袁面的MAH化学结构;考察了等离子体功率与表面聚合量和表面水接触角的关系;讨论了改性薄膜在热浓硫酸中长期作用的结果.结果表明:等离子体使MAH在表面双键打开并接枝聚合;聚合量随处理功率的增加呈先上升后下降的趋势,30W时最大;经过等离子体处理后,水接触角由97°下降至45°～70°,水解后降低至40°～55°,30W的改性膜表面水接触角最小;改性薄膜在热浓硫酸中作用1000h后,MAH聚合物没有被腐蚀掉,与未浸泡硫酸试样相比,水接触角变化不大.