Fundamentals and applications of polymers designed for laser ablation

The ablation characteristics of various polymers were studied at low and high fluences for an irradiation wavelength of 308 nm. The polymers can be divided into three groups, i.e. polymers containing triazene groups, designed ester groups, and reference polymers, such as polyimide. The polymers containing the photochemically most active group (triazene) exhibit the lowest thresholds of ablation (as low as 25 mJ cm^-2) and the highest etch rates (e.g. 250 nm/pulse at 100 mJ cm^-2), followed by the designed polyesters and then polyimide. Neither the linear nor the effective absorption coefficients have a clear influence on the ablation characteristics. The different behavior of polyimide might be explained by a pronounced thermal part in the ablation mechanism. The laser-induced decomposition of the designed polymers was studied by nanosecond interferometry and shadowgraphy. The etching of the triazene polymer starts and ends with the laser pulse, indicating photochemical ablation. Shadowgraphy reveals mainly gaseous products and a pronounced shockwave in air. The designed polymers were tested for an application as the polymer fuel in laser plasma thrusters. Received: 21 October 2002 / Accepted: 20 January 2003 / Published online: 28 May 2003 RID="*" ID="*"Corresponding author. Fax: +41-56/3104-412, E-mail: thomas.lippert@psi.ch     

Mechanisms of reversible thermal deformation of oriented polymers

Reversible thermal deformation coefficients (TDCs) of oriented samples of a flexible-chain polymer (polyethylene) and of a number of rigid-chain polymers were measured in the longitudinal and transverse directions near room temperature. The same samples were used to measure the TDCs of crystallites by x-ray diffraction. The magnitudes of the TDCs of macroscopic oriented samples and of constituting crystallites and the characteristics of the thermal deformation of flexible-chain and rigid-chain polymers are compared. A conclusion is made that the mechanisms that determine thermal deformation in the longitudinal and transverse directions for the flexible-chain and rigid-chain polymers are different.     

地西泮分子印迹聚合物的光谱学特性及其在传感测试中的应用

制备地西泮的分子印迹聚合物,应用紫外光谱(ultraviolet spectra,UV spectra)和红外光谱(infra-red spectra,IRspectra)分析该聚合物的识别特性及模板分子和功能单体的结合作用。在丝网印刷电极上原位制备地西泮的分子印迹膜,并在此基础上建立了检测地西泮的电导型传感方法。实验结果表明模板分子与功能单体可形成1:2型氢键配合物,印迹聚合物中存在可与模板分子通过协同氢键相互作用的官能团,该聚合物对地西泮有高度特异的识别力,电导型传感方法对地西泮的检测限达0.008mg.L-1,线性范围为0.039～0.62mg.L-1,可实现现场快速检测。     

聚合物材料的快重离子辐照效应

简要介绍了快重离子辐照损伤的特点,通过与低电离辐射粒子辐照在聚合物材料中产生的效应的类比论述了快重离子辐照在聚合物材料中产生的效应及其研究现状 ,并结合快重离子辐照效应的应用展望了该领域未来的发展.The irradiation effects in polymers induced by swift heavy ions were reviewed in comparison with that induced by low ionization particles based on the characteristics of swift heavy ion irradiations. It is shown that bond breaking and cross linking, gas releasing, amorphization and carbonization of polymers depend strongly on the electronic energy loss. Besides special effects such as alkynes production, can be induced under swift heavy ion irradiation. The perspectives...     

Calculation of the Band Intensities of the IR Spectra of Oriented Polymers

An attempt has been made to extend the theory of IR spectra of polymers to oriented polymers. Formulas for the absorption-band intensities in polarization IR spectra of oriented polymers reflecting the dependence of the polarized absorption-band intensity on the structural and orientation characteristics of polymers have been obtained. These formulas permit calculating the intensity of polarized absorption bands at different degrees of orientation of the polymer.     

Chevron morphology in deformed semicrystalline polymers

Chevron morphology was observed using transmission electron microscopy in various semicrystalline polymers deformed in tensile experiments. The morphological and mechanical prerequisites for chevron structure formation in semicrystalline polymers were revealed. It was demonstrated that chevron folding is a common deformation mode which can appear in real, i.e. globally unoriented or partially oriented samples, in areas where the lamellar stacks are oriented perpendicular to the deformation direction. Similarities with the behaviour of other layered systems were found. The mechanism of chevron formation is discussed in the light of the fundamental statements of the folding theories and is related to the specific microstructure of the polymers. The effect of boundary conditions, deformation temperature and macroscopic strain on the characteristics of the chevron structure is described.     

On the Electronic Transport and Optical Properties of Some Poly(Azomethine Urethane) in Thin Films

Abstract

Newly synthesized poly(azomethine urethanes) in thin films were deposited onto glass substrates from dimethylformamide solutions. Temperature dependences of the electrical conductivity and thermoelectric power were studied. The investigated polymers have interesting semiconductor characteristics. The values of important parameters of these films (activation energy of electrical conduction, charge carrier concentrations, and ratio of carrier mobilities) were calculated. The nature of the electrical conduction mechanism in the respective polymers is discussed. Transmission and absorption spectra were studied in the spectral domain, 300–1250 nm.     

新型联苯胺基窄带隙共轭聚合物的光学及电化学性能研究

随着化石燃料的日益枯竭,人类社会对能源的需求在不断增长。为了平衡能量应用需求并提升能量使用效率,开发高效能量转换材料与电化学储能材料成为当前研究的重要课题。导电聚合物基电极材料面临着相应储能器件能量密度、功率密度、循环性能不高的挑战,需进行结构改性提高电导率、改善界面性质。鉴于共轭高分子的电子结构、光学及电化学性质由共轭链骨架结构决定,对导电共轭聚合物进行结构修饰以提升其电荷传输性能和载流子迁移率,进而设计合成新型高迁移率导电聚合物基共轭聚合物是提高相应器件特性的关键所在。已有研究大多借助复杂的结构设计来实现提升迁移率,设计合成了结构简单,有助提升电荷迁移的新型窄带隙聚联苯胺基共轭聚合物聚物。通过光谱学及电化学方法对材料结构与性能进行了表征分析。采用核磁共振氢谱、红外光谱,X射线粉末衍射对单体及聚合物进行了结构表征,通过紫外光谱、紫外可见漫反射、循环伏安、计时电位、交流阻抗对其进行了光学及电化学性能测试。结果表明,成功制得具有预期结构的共轭聚合物,所得聚合物结晶性较佳,光学带隙Eopt_g为1.85 eV,HOMO及LUMO能级分别为-5.44和-3.59 eV,前者高于,后者则低于大部分文献值,呈现可同时促进p-型和n-型掺杂的结构特性,具备增强材料容纳电荷能力的性能优势。聚合物储能特性受化学结构、晶体结构及微观形貌综合影响。改善材料微观结构特性有助于提升其电子电导率,但层状致密块体形貌特征又使其离子电导率受限。电化学性能测试结果显示,聚合物具有一定电化学活性,具有较小的电荷转移阻抗,具备基本满足使离子顺利扩散的条件,0.05 A·g-1时的放电比电容达256.6 F·g-1。研究结果表明,制得的联苯胺基窄带隙共轭聚合物在光电转换、储能及微型电子器件中有广阔的应用前景。     

Gamma ray photon-induced modifications in Triafol-TN and Triafol-BN polymeric track detectors

Photon induced modifications in Triafol-TN and Triafol-BN polymers have been studied in the dose range of 10¹–10⁶ Gy at room temperature using a ⁶⁰Co source. To monitor the chemical and structural changes induced by gamma rays, UV, IR, and ESR studies were carried out. Thermal studies were also conducted for understanding the effects of gamma irradiations on these polymers. Variation of track etching characteristics and activation energy for bulk etching have been studied at different gamma rays doses. The experimental results are presented and discussed.     

Description of the photorefractive response in polymers

We employ a phenomenological approach to minimizing the assumptions underlying light-induced charge transport in polymers and expressing the steady-state photorefractive response of polymers through measurable medium characteristics. The relations obtained are shown to be useful for analysis of experimental data and theoretical predictions. The status of the phenomenological approach and its relationship with the known microscopic models are discussed.     

New polymer-containing piezoelectric materials

A review is presented of the data on the design of polymer-containing piezoelectric materials: electrets exhibiting a piezoelectric effect, ferroelectric polymers, piezoelectric composites (piezoelectric ceramic + polymer), and new piezoelectric polymer materials, such as piezoelectrics based on porous polymers and elastic active dielectrics, whose piezoelectric properties considerably surpass the characteristics of conventional piezoelectric materials, as well as the characteristics of electromechanical and mechanoelectrical transducers operating in receiving, generating, and deformation-inducing modes.     

Novel Multicolor Schiff Base Polymers Prepared via Oxidative Polycondensation

A series of diimine Schiff bases and their polymers were synthesized via the oxidative polycondensation reaction. The structures of the compounds were confirmed by ¹H-NMR, ¹³C-NMR, FT-IR and UV–vis spectral measurements. Electrochemical and optical band gap values of synthesized compounds were determined by cyclic voltammetry (CV) and UV–vis measurements, respectively. Fluorescence measurements of the compounds were conducted in various solvents. The effects of solution concentration on the fluorescence spectra were investigated and quantum yield was calculated for the polymer of 5-(diethylamino)-2-(biphenylmethylene) hydrazonomethylphenol (PDEAHP). According to fluorescence measurements, the quantum yield of PDEAHP was found as 16 % in DMF solution. Thermal characteristics of polymers were studied by TG-DTA and DSC analyses.     

Synthesis and spectral-luminescent properties of poly(N-isopropylacrylamide)

The spectral-luminescent characteristics of water and methanol solutions of polymers containing tetraphenylporphyrin substituents were investigated. The water-soluble polymer was obtained by the interaction of poly(N-isopropylamide) containing N-oxysuccinimide substituents with 5-(4-aminophenyl)-10,15,20-triphenylporphyrin. From the synthesized polymer its analog with Zn-porphyrin substituents was obtained. This phenomenon is attributed to the specific features of the conformational behavior of polymeric chains in water solutions. Water solutions of polymers experience a thermally reversible phase transition upon heating, which is accompanied by a considerable enhancement of light scattering. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 67, No. 4, pp. 483–487, July–August, 2000.     

Novel properties of nanoscale organic–inorganic systems and photonic crystals — conducting polymers in nanoscale periodic structures,microcavities and photonic crystals

Conducting polymer/C₆₀and C₆₀doped conducting polymer/C₆₀heterojunctions have been fabricated and found to exhibit remarkably enhanced photoresponse due to the highly effective photoinduced charge transfer at the interface. In conducting polymer/C₆₀alkali metal nanoscale composite systems, multiphase superconductivity has been clarified and explained by taking the coupling of nanoscale grains by Josephson junctions into consideration. As examples of intramolecular organic-inorganic combined systems, unique electrical and optical characteristics have been revealed in oligosilanylene oligophenylene polymers. Electroluminescence has been demonstrated in organic-inorganic junction devices such as conducting polymer/porous Si and conducting polymer/diamond junctions. Conducting, polymer-based nanoscale multilayer systems have been studied utilizing molecular self-assembly method and novel photosensitive characteristics have been revealed. \indent Novel optical and electrical properties of conducting polymers infiltrated in a photonic crystal, synthetic opal made of SiO₂spheres of several hundred nm in diameter, and also a conducting polymer replica have been revealed. A clear diffraction pattern was observed in a photonic crystal infiltrated with conducting polymers, and transmission spectra are dependent on various ambient conditions. Their photoluminescence (PL) spectra, spectral narrowing of PL and lasing characteristics at relatively low optical excitation have also been clarified. Novel conducting characteristics of conducting polymers in a photonic crystal that was prepared by pyrolysis of a polymer replica of opal have also been observed.     

Designing polymers for nuclear track detection

This article describes our attempts since 1996 to systematically design and synthesize monomers and corresponding polymers for nuclear track detection. So far more than 15 homopolymers/copolymers have been prepared and tested by us for this purpose. Some of these polymers show better track detection characteristics vis-á-vis commercially available poly allyl diglycol carbonate (PADC) track detectors.      

Emission of negative and positive ions at rupture of polymers

The emission of negative and positive ions at rupture of polymers has been recorded under high vacuum. The time characteristics of the emission have been investigated with a time resolution up to 1 μs by varying the sizes and the tension rate of poly(ethylene terephthalate), poly(caprolactam), poly(vinylidene fluoride), polyimide, and poly(tetrafluoroethylene) specimens. The kinetics of emission at the last stages of the tension is associated with the specific features of the intergrowth of the main crack in polymers of different types. Possible mechanisms of ion emission have been discussed.     

The effect of aging temperature on structure characteristics of ordered mesoporous silicas

A series of mesoporous silica materials were synthesized by applying Pluronic type polymers as pore creating agents. In order to differentiate the characteristics of porous structure of the obtained sorbents the temperature of aging process was changed in the synthesis. The parameters characterizing the pore structure were estimated from nitrogen adsorption/desorption isotherms. The changes of pore arrangement of the obtained materials being a result of different synthesis conditions were investigated by using a small angle X-ray scattering method. Correlations between the values of structure parameters and aging temperature were found.     

Structure of the Absorption and Fluorescence Spectra of Solutions of Silico-Organic Polymers

The spectroscopic characteristics of new -linked polymers, whose main chain contains tetracoordinated silicon, acetylene groups, and 1,4-biphenyl or 2,7-fluorene, in chloroform have been investigated. It has been established that the spectral features of the absorption, fluorescence, fluorescence excitation, and fluorescence polarization spectra of these polymers are due to the inhomogeneous broadening of the electronic states of the centers of two types formed in the disordered polymer chain.     

Spectroscopic and nonlinear characteristics of anthracene-containing silicon-organic polymers in solution

Spectroscopic characteristics, i.e. absorption, fluorescence, fluorescence excitation spectra, fluorescence decay time, fluorescence polarization degree of novel silicon-containing organic polymers including main chain anthracene groups were investigated. Three kinds of emission spectra were revealed and assigned to polaron–exciton, anthracene and anthracene dimer. The measured fluorescence polarization spectra gave evidence of directed excitation energy migration along the disordered polymeric chain. Strong quenching of anthracene fluorescence during the polaron–exciton lifetime was interpreted as a result of the interaction between two excitations that causes anthracene anion-radical formation. The third-order nonlinear susceptibility of the polymers in solution measured by the Z-scan technique at 1054 nm is 190×10⁻¹⁴ cm² W⁻¹.     

Spectroscopic studies on conjugated polymers in mesoporous channels: influence of polymer side-chain length

The influence of mesoporous environment on the conjugated polymers was studied by UV-Vis absorption and Photoluminescence spectroscopy. The applied polymers were three novel poly(p-phenylenevinylene) derivatives (DDMA-PPV). These polymers have dibenzothiophen-5,5-dioxide units in their backbones, but are different from each other in the length of alkoxy side-chains. The polymers were incorporated into the mesoporous channels of SBA-15 by sorption from their dilute solutions. The confined polymers exhibited different trends in the shifts of the absorption onsets and the emission peaks depending on the length of the side-chains. The polymer with shorter side-chain showed red-shifts in both the absorption and emission spectra, whereas the polymer with longer side-chain showed blue-shifts. These phenomena were caused by the combined influences from the electronic confinement and the conformation distortion. Moreover, these trends were enhanced when the polymers were loaded in amine-modified SBA-15.