Surface modification and adhesion of wood-plastic composite (WPC) treated with UV/ozone

Because of the surfaces of wood-plastic composite (WPC) materials are enriched in polymers of low surface energy, they exhibit low adhesion properties. UV/ozone is proposed as surface treatment for increasing the surface energy and adhesion of WPC materials made with different polymers (polyethylene, polypropylene and polyvinyl chloride). UV lamp-WPC surface distance and time of UV exposure were varied for optimizing UV/ozone treatment of WPC, and UV dose used ranged between 2.02 × 10^?14 and 5.05 × 10^?12 J·s/m². UV/ozone treatment created new carbon-oxygen polar groups in WPC surfaces and increased their surface energy, mainly their polar component. Furthermore, ablation of the outermost WPC surface was produced, more noticeably by reducing the distance between WPC surface and UV lamp and by increasing the duration of the treatment. Noticeable increase in 180° peel adhesion was obtained in the joints made with UV/ozone treated WPC at 10–30 mm distance during 1–5 min (i.e., UV dose between 5.61 × 10^?14 and 2.53 × 10^?12 J·s/m²). Although 180° peel strength of joints made with acrylic adhesive tape and UV/ozone treated WPC for 10 min and 10 mm distance (UV dose: 5.05 × 10^?12 J·s/m²) was not increased because of dominant effect of ablation over creation of polar groups, the cross-hatch adhesion to different coatings was highly improved, irrespective of the polymer used and the wood content of WPC; however, the surface modifications and adhesion of UV/ozone treated WPC were more marked when its wood content was higher and by using UV dose between 0.10 × 10^?12 and 2.53 × 10^?12 J·s/m².     

Surface modification of poly(dimethylsiloxane) for microfluidic assay applications

The surface of a poly(dimethylsiloxane) (PDMS) film was imparted with patterned functionalities at the micron-scale level. Arrays of circles with diameters of 180 and 230 μm were functionalized using plasma oxidation coupled with aluminum deposition, followed by silanization with solutions of 3-aminopropyltrimethoxy silane (3-APTMS) and 3-mercaptopropyltrimethoxy silane (3-MPTMS), to obtain patterned amine and thiol functionalities, respectively. The modification of the samples was confirmed using X-ray photoelectron spectroscopy (XPS), gold nanoparticle adhesion coupled with optical microscopy, as well as by derivatization with fluorescent dyes. To further exploit the novel surface chemistry of the modified PDMS, samples with surface amine functionalities were used to develop a protein assay as well as an array capable of cellular capture and patterning. The modified substrate was shown to successfully selectively immobilize fluorescently labeled immunoglobulin G (IgG) by tethering Protein A to the surface, and, for the cellular arrays, C2C12 rat endothelial cells were captured. Finally, this novel method of patterning chemical functionalities onto PDMS has been incorporated into microfluidic channels. Finally, we demonstrate the in situ chemical modification of the protected PDMS oxidized surface within a microfluidic device. This emphasizes the potential of our method for applications involving micron-scale assays since the aluminum protective layer permits to functionalize the oxidized PDMS surface several weeks after plasma treatment simply after etching away the metallic thin film.     

Reactive sputtering TiO2 films for surface coating of poly(dimethylsiloxane)

Titanium dioxide (TiO₂) films were prepared on poly(dimethylsiloxane) (PDMS) substrate by direct current (DC) reactive sputtering to change surface physical properties of PDMS. The effects of the changes were investigated by using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) analysis, water contact angle measurements and protein adsorption tests. Improved wettability and reduced adsorption properties were observed on PDMS surface coated TiO₂ films.     

Reduction of the contact resistance in copper phthalocyanine thin film transistor with UV/ozone treated Au electrodes

Bottom-contact (BC) copper phthalocyanine (CuPc) thin film transistor with UV/ozone treated Au as a source/drain electrode was fabricated and the contact resistance was estimated from the transmission line method (TLM). Comparing the properties of OTFT with untreated Au electrode, the performance of the BC CuPc-TFT with the UV/ozone treated Au electrodes was significantly improved: saturation mobility increased from 4.69 × 10⁻³ to 2.37 × 10⁻² cm²/V s, threshold voltage reduced from −29.1 to −6.4 V, and threshold swing varied from 5.08 to 2.25 V/decade. The contact resistance of the device with UV/ozone treated Au electrodes was nearly 20 times smaller than that of the device with untreated Au electrodes at the gate voltage of −20 V. This result indicated that using the UV/ozone treated Au electrode is an effective method to reduce the contact resistance. The present BC configuration with UV/ozone treated Au electrodes could be a significant step towards the commercialization of OTFT technology.     

Fabrication of optical devices in poly(dimethylsiloxane) by proton microbeam

Optical diffraction grating and micro Fresnel zone plate type structures were fabricated in relatively thin poly(dimethylsiloxane) (PDMS) layers using proton beam writing technique and the performance of these optical devices was tested. PDMS is a commonly used silicon-based organic polymer, optically clear, generally considered to be inert, non-toxic and biocompatible. PDMS has been used as a resist material for direct-write techniques only in very few cases. In this work, PDMS was used as a resist material; the structures were irradiated directly into the polymer. We were looking for a biocompatible, micropatternable polymer in which the chemical structure changes significantly due to proton beam exposure making the polymer capable of proton beam writing. We demonstrated that the change in the structure of the polymer is so significant that there is no need to perform any development processes. The proton irradiation causes refractive index change in the polymer, so diffraction gratings and other optical devices like Fresnel zone plates can be fabricated in this way. The observed high order diffraction patterns prove the high quality of the created optical devices.     

Preparation of poly(2-chloroaniline) membrane and plasma surface modification

P2ClAn membranes were obtained from chemically synthesized poly(2-chloroaniline) (P2ClAn) by casting method. These membranes were cast from dimethyl formamide (DMF) and were in the undoped state. P2ClAn membranes were characterized by Fourier infrared spectroscopy and scanning electron microscopy. Measurements of water content capacity, membrane thickness and ion-exchange capacity of the cast membranes were carried out. P2ClAn membranes were treated by electron cylotron resonance (ECR) plasma for surface modification. Plasma treatment has been successfully utilized for improving the surface properties of P2ClAn membranes such as increasing pore diameters and number of pores for better anion or molecule transportation.     

Asymmetric surface modification of poly(ethylene terephthalate) film by CF4 plasma immersion

Poly(ethylene terephthalate) (PET) films were treated with CF₄ plasma immersion. The samples were processed at different RF powers and treatment time. The surface modification of PET films was evaluated by water contact angle (CA), X-ray photoelectron spectroscopy (XPS) and atomic force microscope (AFM). Decrease in contact angle of both sides of PET films was observed under mild treatment conditions. However, as raising treatment power and/or time, the change in contact angle between the two sides of PET films was different. The relatively hydrophobic and hydrophilic surfaces were being in situ formed on the two sides of PET films, respectively. And the extreme values of water contact angle reached 108.63 and 7.56°, respectively. XPS analyses revealed that there was a substantial incorporation of fluorine and/or oxygen atoms in both side surfaces. The relative chemical composition of the C (ls) spectra's showed the incorporation of non-polar fluorine-based functionalities (i.e. CFCF_n, CF₂ or CF₃ groups) and polar oxygen-based functionalities (i.e. COOH or OH groups) in the surfaces. Correlation between the plasma parameters and the surface modification of PET films is also discussed.     

Studies on surface modification of poly(tetrafluoroethylene) film by remote and direct Ar plasma

Poly(tetrafluoroethylene) (PTFE) surfaces are modified with remote and direct Ar plasma, and the effects of the modification on the hydrophilicity of PTFE are investigated. The surface microstructures and compositions of the PTFE film were characterized with the goniometer, scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). Results show that the remote and direct plasma treatments modify the PTFE surface in morphology and composition, and both modifications cause surface oxidation of PTFE films, in the forming of some polar functional groups enhancing polymer wettability. When the remote and direct Ar plasma treats PTFE film, the contact angles decrease from the untreated 108-58° and 65.2°, respectively. The effect of the remote Ar plasma is more noticeable. The role of all kinds of active species, e.g. electrons, ions and free radicals involved in plasma surface modification is further evaluated. This shows that remote Ar plasma can restrain the ion and electron etching reaction and enhance radical reaction.     

Air plasma or UV-irradiation applied to surface modification of pectin/poly(vinyl alcohol) blends

Poly(vinyl alcohol), pectin and their blends with different components ratio were exposed to low-temperature air plasma or high energy UV-irradiation (λ = 254 nm) for the purpose of surface modification. The physico-chemical changes in surface properties have been studied by attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) and contact angle measurements. Surface free energy of polymeric films, its polar and dispersive components have been calculated by Owens-Wendt method. Moreover, the work of adhesion was estimated and the recovery of hydrophobic properties of modified films after storage have been also studied.The few seconds air-plasma treatment caused more effective surface modification than 5-6 h UV-irradiation. The observed changes were partially reversible, contrary to these caused by photo-modification.It was found that pectin/PVA (50:50) blend was characterised by larger susceptibility to plasma modification compared to pure pectin and pure PVA, whereas the photosensitivity to radiation of 254 nm wavelength was the lowest for this specimen in comparison to other studied samples.     

Investigation of structural relaxation and surface modification of ultrathin films of poly(ethylene terephthalate)

We studied dynamic properties of ultrathin films of poly(ethylene terephthalate) spincoated on different substrates, by means of dielectric spectroscopy and surface patterning experiments. We did not observe any variations of structural dielectric relaxation dynamics for films spincoated on aluminium substrate having thicknesses down to 40 nm. On the same substrate, 13 nm thick films are instead characterized by a reduction of the chains mobility. Surprisingly the chains dynamics as probed by a surface nanopatterning experiment evidenced a strong dependence on the substrate interaction even for 50 nm thick films, where dielectric relaxation dynamics is unaffected. It can be deduced that different length scales characterise dielectric relaxation dynamics and the processes related to the surface patterning, even if both are related to the chain mobility. Further experiments are wished to better understand this intriguing scenario.     

Structural modification of poly(methyl methacrylate) by proton irradiation

A general survey is presented on the structural modification of poly(methyl methacrylate) (PMMA) by proton implantation. The implanted PMMA films were characterized by FT-IR attenuated total reflection (FT-IR ATR), Raman, Rutherford backscattering spectroscopy (RBS), gel permeation chromatography (GPC) and surface profiling. The ion fluence of 350 keV protons ranged from 2×10¹⁴ to 1×10¹⁵ ions/cm². The IR and Raman spectra showed the reduction of peaks from the pendant group of PMMA. The change of absorption and composition was observed by UV–VIS and RBS, respectively. These results showed that the pendant group is readily decomposed and eliminated by proton irradiation. The change of molecular weight distribution was also measured by GPC and G-value of scission was estimated to be 0.67.     

Nano-SiC implantation into the structure of carbon/graphite materials made by pyrolysis (carbonization) of the precursor system coal tar pitch/poly(dimethylsiloxane)

Conversion of the air-cured poly(dimethylsiloxane) {–O–Si(CH₃)₂–}_n to SiC during co-pyrolysis with a coal tar pitch is studied with reference to the related SiO₂/pitch system. Each binary mixture is first homogenized at 160 °C followed by carbonization at 500 °C under argon to afford initial carbonizates. In both cases, one part of the initial carbonizate is further pyrolyzed at 1300 °C and another part at 1650 °C under an argon flow resulting in composite products. All products are studied with FT-IR, XRD, and XPS spectroscopic methods supplemented with SEM and ‘wet’ Si-analyses, when applicable. Carbothermally assisted conversion of both silicon precursors to nanocrystalline SiC embedded in the evolving C-matrix, i.e. nano-SiC/C composites, is evident only after the 1650 °C carbonization stage.     

Surface modification of poly(propylene carbonate) by oxygen ion implantation

Poly(propylene carbonate) (PPC) was implanted by oxygen ion with energy of 40 keV. The influence of experimental parameters was investigated by varying ion fluence from 1 × 10¹² to 1 × 10¹⁵ ions/cm². XPS, SEM, surface roughness, wettability, hardness, and modulus were employed to investigate structure and properties of the as-implanted PPC samples. Eight chemical groups, i.e., carbon, CH, COC, CO, OCO, CO, , and groups were observed on surfaces of the as-implanted samples. The species and relative intensities of the chemical groups changed with increasing ion fluence. SEM images displayed that irradiation damage was related strongly with ion fluence. Both surface-recovering and shrunken behavior were observed on surface of the PPC sample implanted with fluence of 1 × 10¹⁵ ions/cm². As increasing ion fluence, the surface roughness of the as-implanted PPC samples increased firstly, reached the maximum value of 159 nm, and finally decreased down the minimum value. The water droplet contact angle of the as-implanted PPC samples changed gradually with fluence, and reached the minimum value of 70° with fluence of 1 × 10¹⁵ ions/cm². The hardness and modulus of the as-implanted PPC samples increased with increasing ion fluence, and reached their corresponding maximum values with fluence of 1 × 10¹⁵ ions/cm². The experimental results revealed that oxygen ion fluence closely affected surface chemical group, morphology, surface roughness, wettability, and mechanical properties of the as-implanted PPC samples.     

Local chemical transformations in poly(dimethylsiloxane) by irradiation with 248 and 266 nm

Poly(dimethylsiloxane) (PDMS) has been irradiated with a frequency quadrupled Nd:YAG laser and a KrF^*-excimer laser at a repetition rate of 1 Hz. The analysis of ablation depth versus pulse number data reveals a pronounced incubation behavior. The thresholds of ablation (266 nm: 210 mJ cm⁻², 248 nm: 940 mJ cm⁻²) and the corresponding effective absorption coefficients α_eff (266 nm: 48900 cm⁻¹, 248 nm: 32700 cm⁻¹, α_lin = 2 cm⁻¹) were determined. The significant differences in the ablation thresholds for both irradiation wavelengths are probably due to the different pulse lengths of both lasers. Since the shorter pulse length yields a lower ablation threshold, the observed incubation can be due to a thermally induced and/or a multi-photon absorption processes of the material or impurities in the polymer.Incubation of polymers is normally related to changes of the chemical structure of the polymer. In the case of PDMS, incubation is associated with local chemical transformations up to several hundred micrometers below the polymer surface. It is possible to study these local chemical transformations by confocal Raman microscopy, because PDMS is transparent in the visible. The domains of transformation consist of carbon and silicon, as indicated by the appearance of the carbon D- and G-bands between 1310 and 1610 cm⁻¹, a band appearing between 502 and 520 cm⁻¹ can be assigned to mono- and/or polycrystalline silicon.The ablation products, which are detected in the surroundings of the ablation crater consist of carbon and amorphous SiO_x (x ≈ 1.5) as detected by infrared spectroscopy.     

Characteristics of ZnO MSM UV photodetector with Ni contact electrodes on poly propylene carbonate (PPC) plastic substrate

In this study, we report the fabrication of ZnO metal-semiconductor-metal UV photodetector (MSM UV PD) by deposition ZnO thin film on poly propylene carbonate (PPC) plastic substrate using direct current (DC) sputtering technique, and Nickel (Ni) contact as electrodes. The structural, optical and electrical properties of the ZnO thin film were investigated by using atomic force microscopy (AFM), X-Ray diffraction (XRD) measurement, and photoluminescence (PL). The electrical characteristics of the detector were investigated using the current–voltage (I–V) measurements, the dark- and photo-currents were found to be 1.04 and 93.80 μA, respectively. Using forward dark conditions at 5 volt; the barrier height Φ_B was calculated to be 0.675 eV. Under incident wavelength of 385 nm, it was found that the maximum responsivity (R) of the Ni/ZnO/Ni MSM PD was found to be 1.59 A/W.     

Polypropylene surface modification by entrapment of polypropylene-graft-poly(butyl methacrylate)

Surface modification of polypropylene was carried out by entraping a copolymer of polypropylene grafted poly(butyl methacrylate) into polypropylene. The effects of structure of copolymers, contact die and content of modifiers on their surface enrichment were studied by attenuated total reflection infrared spectroscopy (ATR-FTIR), contact angle measurements and scanning electron microscopy (SEM). The results indicated that PPw-g-PBMA could diffuse preferably onto the surface and effectively increase the hydrophilicity of PP. Lower content and higher surface energy die were in favor of the copolymer to enrich on the PP surface. PPw-g-PBMA with low PBMA contents, short length of PBMA distributed in PP with smaller phase domains and favored its selective enrichment on the surface of PP, especially at lower loadings in blends. The modified material exhibited excellent solvent-resistance.     

A sensor for adenosine triphosphate fabricated by laser-induced forward transfer of luciferase onto a poly(dimethylsiloxane) microchip

Laser-induced forward transfer (LIFT) of the enzyme luciferase was explored as a potential technique to be used in the fabrication of a microchip adenosine triphosphate (ATP) sensor. Poly(dimethylsiloxane) (PDMS) was selected as the substrate for deposition of the luciferase. In comparison with other solid substrates, such as glass and polystyrene, it was found that the flexibility of PDMS made it a superior substrate for the immobilization of micro-spots of luciferase. LIFT of luciferase onto a PDMS substrate using a 355 nm laser was successfully carried out, while the bioactivity of the enzyme was maintained. Yellow luminescence ascribed to luciferase was observed from a transferred spot on the PDMS chip from the enzymatic reaction between luciferin and ATP. A microchip ATP sensor was also fabricated by attaching a small photodiode to the PDMS chip. On the basis of the fabricated microchip, the Michaelis-Menten relation between the luminescence intensity from the spot, and the ATP concentration was confirmed. The potential for fabricating biosensors using a combination of the LIFT technique with a PDMS substrate was shown to be very good.     

利用微悬臂梁表面应力研究聚N-异丙基丙烯酰胺分子的构象转变

提出了一种基于微悬臂梁传感技术研究大分子折叠/构象转变的新方法.通过分子自组装的方法将热敏性的聚N-异丙基丙烯酰胺(PNIPAM)分子链修饰到微悬臂梁的单侧表面，用光杠杆技术检测温度在20—40℃之间变化时由于微悬臂梁上的PNIPAM分子在水中的构象转变所引起的微悬臂梁变形.实验结果显示：在升温过程中，微悬臂梁的表面应力发生了变化并且导致微悬臂梁产生了弯曲变形，这个过程对应着微悬臂梁上的PNIPAM分子从无规线团构象到塌缩小球构象的构象转变.在降温过程中，微悬臂梁发生了反方向的弯曲变形，这对应着PNIPA 关键词： 构象转变 聚N-异丙基丙烯酰胺分子链 表面应力 微悬臂梁     

Surface analysis of oxygen plasma treated poly(p-phenylene benzobisoxazole) fibers

The influence of oxygen plasma treatment on surface properties of poly(p-phenylene benzobisoxazole) (PBO) fibers and aging effect of the oxygen plasma modified PBO fiber surfaces were investigated by X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM) and dynamic contact angle analysis (DCAA), respectively. The results indicated that the oxygen plasma treatment introduced some polar groups to PBO fiber surfaces, enhanced surface roughness and changed surface morphologies of PBO fibers by plasma etching and oxidative reactions. Surface wettability of PBO fibers may be significantly improved by increasing surface free energy of the fibers via oxygen plasma treatment. Aging effect of the oxygen plasma treated PBO fibers showed that the fiber surface wettability degraded in the first several days after the plasma treatment, and it was found to be changeless as the aging time continued as long as 30 days.