Three-dimensional photochemical microfabrication of conductive polymers in transparent polymer sheet

By focused illumination at the wavelength of 800 nm using a femtosecond laser, the tris(2,2′-bipyridyl)ruthenium complex displayed a two-photon excitation as observed by the quadratic dependence of the emission intensity on the incident laser power. Since the oxidation of pyrrole is induced by the oxidative quenching of the excited state, polypyrrole can be formed by a continuous illumination. The polymerization area showed a high spatial selectivity which can be scanned in the XYZ axis by a piezo device. In the present study, three-dimensional (3D) polypyrrole microstructures were formed in the transparent polymer sheet.     

Three-dimensional printing of conducting polymer microstructures into transparent polymer sheet: Relationship between process resolution and illumination conditions

Three-dimensional (3D) polypyrrole microstructures were successfully obtained in a transparent polymer sheet by 3D scanning of the laser focal point. The lateral process resolution of the microstructures was studied under different photofabrication conditions such as the repetition rate of the femtosecond pulse laser and the waiting time of the laser focal point scanning. As a result, a very small line width of the polypyrrole deposition of less than 500 nm was realized with good reproducibility.     

All-solid-state lithium-based polymer cells for high-temperature applications

A lithium salt doped siloxane/methacrylate copolymer membrane, prepared by a rapid UV curing process, has been characterised and tested as a fully solid electrolyte in rechargeable lithium test cells using low cost materials as electrodes. In addition, results of a laboratory-scale Li-ion polymer cell, assembled by contacting a LiFePO₄ cathode with a graphite anode and using the solid polymer as electrolyte, are presented. The polymer electrolyte production process is simple and versatile and the highly cross-linked membrane demonstrates mechanical integrity, low T _g and large thermal stability. It is an extra soft, non-crystalline, transparent solid and shows sufficient ionic conductivity (>10⁻⁴ S cm⁻¹ at 60 °C) along with a wide electrochemical stability window and improved interfacial stability with respect to lithium. The performances in Li-based cells have been determined by cycling tests carried out at 80 °C. Good rate capability, along with high charge/discharge efficiency even at 1C-rate, and a satisfactory cyclability have been obtained. These results outline the practical relevance of the use of this solid electrolyte membrane (which serves as the separator simultaneously) in Li-based cells conceived for high-temperature applications.     

Effect of cross-linkable polymer on the morphology and properties of transparent multi-walled carbon nanotube conductive films

In this study, we fabricated optically transparent and electrically conductive multi-walled carbon nanotube (MWCNT) thin films using a spray-coating technique. The transparency and the electrical resistance of thin film are dependent on the nanotube content deposited on the polyethylene terephthalate (PET) substrate. Poly(acrylic acid) (PAA) and poly(N-vinyl pyrrolidone) (PVP) were used as adhesion promoters to improve MWCNT coating more significantly. The cross-linked polymer resulted in a superior bond between the MWCNTs and the substrates. The surface electrical resistance was significantly lower than the original sheet after nitric acid (HNO₃) treatment because of the removed surfactant and the increased interconnecting networks of MWCNT bundles, thus improving the electrical and optical properties of the films. Stronger interaction between the MWCNTs and the substrates resulted in lower decomposition of the polymer chain and less amounts of MWCNTs separated into the HNO₃ solution. The lower sheet electrical resistance of PVP/PAA-g-MWCNT conductive films on the PET substrate was because of a more complete conductive path with the cross-linked polymer than that without. Such an improved sheet of electrical resistance varied from 8.83 × 10⁴ Ω/□ to 2.65 × 10³ Ω/□ with 5.0 wt.% PVP/PAA-g-MWCNT sprayed on the PET after acid treatment.     

Fabrication of microchip based on UV transparent polymer for DNA electrophoresis by F2 laser ablation

A microchip for DNA electrophoresis made of a new UV transparent polymer material (CYTOP) whose absorption edge is much shorter than 190 nm has been fabricated by F₂ laser ablation. F₂ laser ablation achieves high-quality microfabrication of CYTOP surface with little deterioration of the optical property and little debris deposition at etched area. The microchip in which the microchannel connected with two reservoirs was embedded was successfully fabricated by bonding the ablated sample to the virgin CYTOP sheet. The fabricated microchip was applied for DNA analysis by electrophoresis and succeeded in separating different base-pares (bp) of DNA from 50 to 766 bp with resolution of 100 bp. PACS 42.70.Jk; 52.38.Mf; 82.45.-h     

Anisotropic models of polymer ferroelectrics

The phase transitions to an ordered state in three-dimensional polymer systems that consist of flexible and rigid segments with intrachain and interchain orientational-deformational dipole interactions are considered. The statistic properties of the proposed models correspond to the Gaussian and spherical approximations that are used to describe the behavior of anisotropic Heisenberg ferroelectrics and ferromagnets. In the three-dimensional models under consideration, there exists a critical point T _c where a secondorder phase transition from an isotropic state to a state with long-range orientational order occurs. The laws of variation in the temperature T _c as a function of anisotropy of the interactions are established by analytical methods. The temperature dependences of the long-range dipole order parameter for a given chain bending are calculated and the results are compared with the experimental data obtained by the piezoelectric pressure step (PPS) method for thick ferroelectric PVDF and P(VDF-TrFE) polymer films.     

Selective cell culture on UV transparent polymer by F2 laser surface modification

A microchip made of UV transparent polymer (CYTOP) that can perform selective cell culture has been fabricated by F₂ laser surface modification. The refractive index of CYTOP is almost the same as that of culture medium, which is essential for three-dimensional (3D) observation of cells. The F₂ laser modification of CYTOP achieves hydrophilicity only on the laser irradiated area with little deterioration of the optical properties and surface smoothness. After the laser modification, HeLa cells were successfully cultured and strongly adhered only on the modified area of CYTOP. The cells patterned on CYTOP were applied for clear 3D observation using an optical microscope in phase contrast mode.     

In situ production of CuS particles in polymer electrolyte matrix for mixed ion+electron conduction

Composites of polymer electrolyte polyethylene oxide (PEO) complexed with NH₄ClO_4, (PEO:NH₄ClO₄), having different weight ratios of dispersed semiconductor CuS (0–5 wt.%) have been prepared and characterized. The dispersal of CuS was achieved by its in situ formation in the viscous solution of polymer electrolyte (PEO:NH₄ClO₄) by sulfuration of CuSO₄ using H₂S. The band gap of CuS dispersed in the composites was found to be ~2.4 eV, which is higher than that of the bulk CuS for which it is 2.2 eV. Scanning electron microscopy studies show that the particle size varies from ~200 nm to several hundreds of nanometers. Polarization studies show that the semiconductor dispersed polymer composite so obtained has mixed ionic and electronic conduction. Detailed I–V studies show that the dispersoid is a p-type semiconductor.     

Characterization of pTMCnLiPF6 solid polymer electrolytes

In this study the results of our characterization of a solid polymer electrolyte based on poly(trimethylene carbonate), henceforth designated as p(TMC), and lithium hexafluorophosphate (LiPF₆) are described. Samples of solvent-free electrolytes were prepared with a range of concentration of guest salt using solvent casting from tetrahydrofuran and characterized by conductivity measurements, thermal analysis and electrochemical stability. Electrolytes based on this host polymer, with LiPF₆, were obtained as mechanically robust, flexible, transparent and completely amorphous films.     

Measurement of optical constants of thin polymer films using spectrally resolved white light interferometry

Using the spectrally resolved white light interferometry we present our experimental results on the measurement of the optical constants of thin polymer films coated on a transparent substrate. As an extension to our previous work (J. Opt. Soc. Am. B12, 1559 (1995)) on thick glass plates, we have shown here that this technique can be effectively applied to very thin polymer films also. We have improved the accuracy of our results by using the Sellmeier dispersion formula for fitting the data. From the width and position of the zero-order fringe and the frequency of modulations in the white light spectrum, the refractive indexn(λ) and thicknesst of the thin polymer films are calculated. To study the accuracies involved in the technique, PVA, PMMA and PS films of varied thicknesses are coated on glass plates and the measured values are compared with ellipsometer studies.     

打结高分子链穿孔行为的研究

以三叶草型结(即3₁结)为例,采用分子动力学(MD)方法,研究打结高分子链在外场力作用下穿越微孔的动力学过程.模拟发现,在拉动打结高分子链的过程中,结的大小呈涨落变化,直至最后散结.定性讨论了结的存在对高分子链穿孔速率的影响.在外场力作用下,打结高分子链平均穿孔时间(τ)与链长(N)满足标度关系τ～N ^α,其中标度系数α随外场力f增大而增大.对于短链,外场力越大,平均穿孔时间越短     

An analysis of absorption-desorption of volatile organic compounds by molecularly imprinted polymer films

A theoretical analysis of the experimental data on absorption (desorption) of volatile organic compounds by (from) molecularly imprinted polymer films was performed. The theoretical time dependences of the amount of absorbed analyte in a film were calculated using a system of equations with four kinetic parameters (Γ, K, K _sur , and C _eq ), which were determined by theoretically approximating the experimental data. The special features of the absorption-desorption process in a polymer film were suggested to be described using a parameter called the specificity coefficient. Specificity coefficients were determined for all the polymers and analytes studied. The specificity coefficients obtained from the chromatographing data were compared with the imprinting factors of chromatograms calculated from the experimental retention time values. An empirical linear dependence of specificity coefficients on imprinting factor values was obtained.     

全湿法制备聚合物电致发光器件

利用全溶液方法制备了聚合物电致发光器件并研究了器件的性能。器件的所有膜层,包括发光层和上电极层均采用溶液湿法获得,完全摒弃了真空蒸镀工艺。利用二次溶剂掺杂获得的PEDOT∶PSS聚合物薄膜的电导率达到608.7 S/cm。在240 nm的厚度时,聚合物电极膜层的面电阻约为68 Ω/□; 当膜层厚度为1 μm时,薄膜的面电阻可低于16 Ω/□。采用溶液滴涂方法制备的高电导PEDOT∶PSS聚合物薄膜作为上电极替代通常所用的铝电极,所制备的聚合物发光器件的开启电压约为4 V。     

Reaction kinetics in polymer melts

We study the reaction kinetics of end-functionalized polymer chains dispersed in an unreactive polymer melt. Starting from an infinite hierarchy of coupled equations for many-chain correlation functions, a closed equation is derived for the 2nd order rate constant k after postulating simple physical bounds. Our results generalize previous 2-chain treatments (valid in dilute reactants limit) by Doi [#!doi:inter2!#], de Gennes [#!gennes:polreactionsiandii!#], and Friedman and O'Shaughnessy [#!ben:interdil_all_aip!#], to arbitrary initial reactive group density n₀ and local chemical reactivity Q. Simple mean field (MF) kinetics apply at short times, .For high Q, a transition occurs to diffusion-controlled (DC) kinetics with (where x_t is rms monomer displacement in time t) leading to a density decay . If n₀ exceeds the chain overlap threshold, this behavior is followed by a regime where during which k has the same power law dependence in time, , but possibly different numerical coefficient. For unentangled melts this gives while for entangled cases one or more of the successive regimes ,t ^-3/8 and t ^-3/4 may be realized depending on the magnitudes of Q and n₀. Kinetics at times longer than the longest polymer relaxation time are always MF. If a DC regime has developed before then the long time rate constant is where R is the coil radius. We propose measuring the above kinetics in a model experiment where radical end groups are generated by photolysis. Received: 2 June 1998 / Revised: 9 July 1998 / Accepted: 10 July 1998     

Transparent lithium-6 based polymer scintillation films containing a polymerizable fluor for neutron detection

A novel transparent polymer neutron scintillation material poly[styrene-co-lithium maleate-co-2-phenyl-5-(4-vinylphenyl)oxazole] has been synthesized and characterized for thermal neutron detection and neutron/gamma-ray discrimination. The terpolymer was synthesized using solution-based free radical polymerization and had a composition by mass of 60.64% styrene, 31.64% maleic anhydride, and 7.72% 2-phenyl-5-(4-vinylphenyl)oxazole. The maleic anhydride groups were hydrolyzed and titrated with ⁶LiOH to form the lithiated terpolymer, resulting in a ⁶Li content of 2.96% by mass. Monomer and polymer synthesis, film fabrication protocols, photoluminescence, and scintillation responses of this new scintillation material are reported. This approach demonstrates a novel method by which mechanically robust and transparent ⁶Li-based polymer films can be produced.     

Supercritical fluid-assisted synthesis of a carbon nanotubes-grafted biocompatible polymer composite

A nanocomposite consisting of multi-wall nanotubes (MWNTs) grafted with a biocompatible polymer poly(2-hydroxyethyl methacrylate) was prepared by in situ polymerization in supercritical carbon dioxide. The surface of the MWNTs was first surface modified with hydroxyl groups in the solution of KMnO₄ and a phase-transfer catalyst. MWNT-OH was then functionalized with vinyl groups using a silane coupling agent, γ-methacryloxypropyltrimethoxysilane. The silane groups can improve the dipersion of MWNTs in supercritical carbon dioxide, while the terminal vinyl groups help fabricate polymer chains on the MWNT surface. The as-synthesized products were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and thermo-gravimetric analysis. The SEM and TEM images showed that the nanotubes were well coated with the polymer shell. The composite had higher thermal stability than the pure polymer and dispersed well in methanol. This biocompatible polymer composite was prepared using a green method and is expected to be useful as a biomaterial composite with potential applications in the biological field.     

Non-newtonian flow for concentrated polymer systems

The modified Graessley theory with the three-dimensional Maxwell model can well explain some of the nonlinear viscoelastic behavior of concentrated polymer systems at least qualitatively with the assumption of a box-type relaxation spectrum for the equilibrium state.

The relaxation spectrum of concentrated polymer systems in shear flow is obtained by means of Graessley's theory. It is assumed that the characteristic time for the entanglement formation is the same order as that for its breakage and that the spectral density of the relaxation spectrum in the flow system is proportional to the number of entanglements between two molecules. The spectral density decreases approximately proportionally to 1/γ for relaxation times larger than 1/γ The non-Newtonian viscosity and other viscoelastic properties, such as the so-called stress overshoot and the stress relaxation, are calculated by using the obtained relaxation spectrum. Our theory explains very well the experimental results in many cases. Good agreement with experimental results is found if we assume that the so-called box-type relaxation spectrum in the equilibrium state has a finite gradient of the order of ?0.5 in the edge region of larger relaxation time on log-log plots.     

Spectral Line HeII 6560 Å as a Sensor of the Electron Concentration in a Dense Plasma of a Current Sheet

Stark broadening of the spectral line HeII 6560 Å by plasma was studied. The profiles of the line HeII 6560 Å were calculated for different values of the electron concentration N_e. We used the quasi‐static approximation to account for the perturbing ions and the impact approximation to describe the perturbing electrons. The electron concentration N_e in the central region of a current sheet plasma was deduced by comparing the experimentally obtained profiles of the line HeII 6560 Å with the set of the theoretically calculated profiles of this line.