General strategies for nanoparticle dispersion

Traditionally the dispersion of particles in polymeric materials has proven difficult and frequently results in phase separation and agglomeration. We show that thermodynamically stable dispersion of nanoparticles into a polymeric liquid is enhanced for systems where the radius of gyration of the linear polymer is greater than the radius of the nanoparticle. Dispersed nanoparticles swell the linear polymer chains, resulting in a polymer radius of gyration that grows with the nanoparticle volume fraction. It is proposed that this entropically unfavorable process is offset by an enthalpy gain due to an increase in molecular contacts at dispersed nanoparticle surfaces as compared with the surfaces of phase-separated nanoparticles. Even when the dispersed state is thermodynamically stable, it may be inaccessible unless the correct processing strategy is adopted, which is particularly important for the case of fullerene dispersion into linear polymers.     

Photoinduced plasticity in cross-linked polymers

Chemically cross-linked polymers are inherently limited by stresses that are introduced by post-gelation volume changes during polymerization. It is also difficult to change a cross-linked polymer's shape without a corresponding loss of material properties or substantial stress development. We demonstrate a cross-linked polymer that, upon exposure to light, exhibits stress and/or strain relaxation without any concomitant change in material properties. This result is achieved by introducing radicals via photocleavage of residual photoinitiator in the polymer matrix, which then diffuse via addition-fragmentation chain transfer of midchain functional groups. These processes lead to photoinduced plasticity, actuation, and equilibrium shape changes without residual stress. Such polymeric materials are critical to the development of microdevices, biomaterials, and polymeric coatings.     

Organic Glasses: A New Class of Photorefractive Materials

The performance of amorphous organic photorefractive (PR) materials in applications such as optical data storage is generally limited by the concentration of active molecules (chromophores) that can be incorporated into the host without forming a crystalline material with poor optical quality. In polymeric PR systems described previously, performance has been limited by the necessity of devoting a large fraction of the material to inert polymer and plasticizing components in order to ensure compositional stability. A new class of organic PR materials composed of multifunctional glass-forming organic chromophores is described that have long-term stability and greatly improved PR properties.     

Templating organic semiconductors via self-assembly of polymer colloids

A route for producing semiconducting polymer blends is demonstrated in which a doped pi-conjugated polymer is forced into a three-dimensionally continuous minor phase by the self-assembly of colloidal particles and block copolymers. The resulting cellular morphology can be viewed as a high-internal phase polymeric emulsion. Compared with traditional blending procedures, this process reduces the percolation threshold for electrical conductivity by a factor of 10, increases the conductivity by several orders of magnitude, and simultaneously improves thermal stability. Following this route, new applications can be envisaged for semiconducting polymer blends that require only minimal concentrations of doped pi-conjugated polymer.     

林业院校高分子材料科学与工程专业的特色发展

以高分子材料与工程专业为例,基于东北林业大学材料科学与工程学院的实际情况,探讨了林业院校高分子材料与工程专业的人才培养模式,认为主要措施是发掘自身优势,优化课程体系,在理论和实践教学中突出生物质材料及生物质复合材料方向,体现林业工程的特色。     

食品纳米包装材料的应用与安全性评价

纳米技术是当今科学界最具前景的科学技术之一,生物纳米复合材料的研究和开发将取得巨大突破。本文概述了纳米材料在食品包装领域的基本应用现状,并对相关的安全性评价问题进行了探讨。     

Design and application of electron-transporting organic materials

Operating lifetime is the main problem that complicates the use of polymeric light-emitting diodes (LEDs). A class of electron transport (ET) polymers [poly(aryl acrylate) and poly(aryl ether)s] is reported in which moieties with high electron affinities are covalently attached to stable polymer backbones. Devices based on poly(p-phenylenevinylene) (PPV) prepared with these materials exhibited a 30-fold improvement in stability and, in one case, dramatically lower (10 volts versus about 30 volts) operating voltage relative to those having conventional ET layers. The current-carrying capacity of indium tin oxide-PPV-polymeric ET layer-aluminum LEDs was also increased by a factor of 30. These improvements lead to an enhancement in power efficiency of nearly an order of magnitude. Choosing polymers with high glass transition temperatures increases device lifetime.     

Thin Films of n-Si/Poly-(CH3)3Si-Cyclooctatetraene: Conducting-Polymer Solar Cells and Layered Structures

The optical and electronic properties of thin films of the solution-processible polymer poly-(CH(3))(3)Si-cyclooctatetraene are presented. This conjugated polymer is based on a polyacetylene backbone with (CH(3))(3)Si side groups. Thin transparent films have been cast onto n-doped silicon (n-Si) substrates and doped with iodine to form surfacebarrier solar cells. The devices produce photovoltages that are at the theoretical limit and that are much greater than can be obtained from n-Si contacts with conventional metals. Two methods for forming layered polymeric materials, one involving the spincoating of preformed polymers and the other comprising the sequential polymerization of different monomers, are also described. An organic polymer analog of a metal/insulator/metal capacitor has been constructed with the latter method.     

Rheology and microscopic topology of entangled polymeric liquids

The viscoelastic properties of high molecular weight polymeric liquids are dominated by topological constraints on a molecular scale. In a manner similar to that of entangled ropes, polymer chains can slide past but not through each other. Tube models of polymer dynamics and rheology are based on the idea that entanglements confine a chain to small fluctuations around a primitive path that follows the coarse-grained chain contour. Here we provide a microscopic foundation for these highly successful phenomenological models. We analyze the topological state of polymeric liquids in terms of primitive paths and obtain parameter-free, quantitative predictions for the plateau modulus, which agree with experiment for all major classes of synthetic polymers.     

Polymer brushes

Polymers attached by one end to an interface at relatively high coverage stretch away from the interface to avoid overlapping, forming a polymer "brush." This simple picture may serve as the basis for models in diverse interfacial systems in polymer science, such as polymeric surfactants, stabilized suspensions of colloidal particles, and structures formed by block copolymers. The structure and dynamics of polymer brushes have been the subject of considerable theoretical and experimental activity in recent years. An account is given of recent advances in theoretical understanding of stretched polymers at interfaces, and the diverse experimental probes of systems modeled by brushes are briefly reviewed.     

Trends in polymer development

Polymer science and technology has flourished as polymers with many new compositions have been, synthesized. The range of properties attainable has been continually extended, providing materials with higher strength, better reinforcing capabilities, and greater resistance to extreme thermal and corrosive environments. Examples of evolutionary developments in the polyamides, the fluorocarbon resins, and the aromatic engineering plastics are used to illustrate the trends. It is expected that this process will continue in order to meet changing needs and that emphasis will be put on selective polymer design for specific applications.     

Direct measurement of the reaction front in chemically amplified photoresists

The continuing drive by the semiconductor industry to fabricate smaller structures using photolithography will soon require dimensional control at length scales comparable to the size of the polymeric molecules in the materials used to pattern them. The current technology, chemically amplified photoresists, uses a complex reaction-diffusion process to delineate patterned areas with high spatial resolution. However, nanometer-level control of this critical process is limited by the lack of direct measurements of the reaction front. We demonstrate the use of x-ray and neutron reflectometry as a general method to measure the spatial evolution of the reaction-diffusion process with nanometer resolution. Measuring compositional profiles, provided by deuterium-labeled reactant groups for neutron scattering contrast, we show that the reaction front within the material is broad rather than sharply defined and the compositional profile is altered during development. Measuring the density profile, we directly correlate the developed film structure with that of the reaction front.     

Low (Sub-1-volt) halfwave voltage polymeric electro-optic modulators achieved by controlling chromophore shape

Electro-optic (EO) modulators encode electrical signals onto fiber optic transmissions. High drive voltages limit gain and noise levels. Typical polymeric and lithium niobate modulators operate with halfwave voltages of 5 volts. Sterically modified organic chromophores have been used to reduce the attenuation of electric field poling-induced electro-optic activity caused by strong intermolecular electrostatic interactions. Such modified chromophores, incorporated into polymer hosts, were used to fabricate EO modulators with halfwave voltages of 0.8 volts (at a telecommunications wavelength of 1318 nanometers) and to achieve a halfwave voltage-interaction length product of 2.2 volt-centimeters. Optical push-pull poling and driving were also used to reduce halfwave voltage. This study, together with recent demonstrations of exceptional bandwidths (more than 110 gigahertz) and ease of integration (with very large scale integration semiconductor circuitry and ultra-low-loss passive optical circuitry) demonstrates the potential of polymeric materials for next generation telecommunications, information processing, and radio frequency distribution.     

Electrically conductive metallomacrocyclic assemblies

The design, synthesis, and study of electrically conductive molecular and polymeric substances constitute a new scientific endeavor involving the interaction of chemists, physicists, and materials scientists. The strategies, developments, and challenges in these two closely related fields are analyzed via a class of materials that bridges both: assemblies of electrically conductive metallomacrocycles. It is seen that efforts to rationally synthesize tailored, "metal-like" molecular arrays lead logically to structure-enforced polymeric assemblies of linked molecular subunits such as metallophthalocyanines. The properties of these assemblies and fragments thereof provide information on the relationship between atomic-level local architecture, electronic structure, and macroscopic transport properties. Electrcally conductive, processable polymeric materals also follow from these results.     

Replamineform: a new process for preparing porous ceramic, metal, and polymer prosthetic materials

The replamineform process (meaning replicated life forms) is a technique for duplicating the microstructure of carbonate skeletal components in ceramic, metal, or polymer materials. The special pore structures of marine invertebrate skeletal materials such as echinoid spines and corals, which are difficult or impossible to create artificially, can thus be copied in useful materials. Of immediate interest is the possibility of using these replicated microstructures in the fabrication of orthopedic prosthetic devices. By means of this technique, prosthetic materials having a controlled pore microstructure for optimum strength and tissue ingrowth may be obtained.     

Ultrapermeable, reverse-selective nanocomposite membranes

Polymer nanocomposites continue to receive tremendous attention for application in areas such as microelectronics, organic batteries, optics, and catalysis. We have discovered that physical dispersion of nonporous, nanoscale, fumed silica particles in glassy amorphous poly(4-methyl-2-pentyne) simultaneously and surprisingly enhances both membrane permeability and selectivity for large organic molecules over small permanent gases. These highly unusual property enhancements, in contrast to results obtained in conventional filled polymer systems, reflect fumed silica-induced disruption of polymer chain packing and an accompanying subtle increase in the size of free volume elements through which molecular transport occurs, as discerned by positron annihilation lifetime spectroscopy. Such nanoscale hybridization represents an innovative means to tune the separation properties of glassy polymeric media through systematic manipulation of molecular packing.     

A lost-wax approach to monodisperse colloids and their crystals

We report a nanoscale "lost-wax" method for forming colloids with size distributions around 5% and their corresponding colloidal crystals. Macroporous polymer templates are first prepared from a silica colloidal crystal. We then use the uniform and interconnected voids of the porous polymer to generate a wide variety of highly monodisperse inorganic, polymeric, and metallic solid and core-shell colloids, as well as hollow colloids with controllable shell thickness, as colloidal crystals. We can also uniformly deform the polymer template to alter colloidal shape and demonstrate the formation of elliptical particles with precisely controlled aspect ratios.     

乙基纤维素／多效唑微胶囊的制备与表征

农药缓释微胶囊剂是当前农药新剂型中技术含量最高、最具开发前景的一种剂型,能很好地满足日益严格的环境保护需要。作为胶囊材料,天然高分子材料如明胶、壳聚糖、纤维素等因其价廉、易降解而具有一定的优势,本文选择乙基纤维素作为囊皮材料,采用有机溶剂蒸发法对植物生长调节剂多效唑进行复合,合成了具有缓释功能的多效唑微胶囊,考察了反应温度和搅拌速度等对微胶囊形成的影响,并用光学显微镜对其进行了表征。     

Polymer gate dielectric surface viscoelasticity modulates pentacene transistor performance

Nanoscopically confined polymer films are known to exhibit substantially depressed glass transition temperatures (Lg's) as compared to the corresponding bulk materials. We report here that pentacene thin films grown on polymer gate dielectrics at temperatures well below their bulk Tg's exhibit distinctive and abrupt morphological and microstructural transitions and thin-film transistor (TFT) performance discontinuities at well-defined growth temperatures. The changes reflect the higher chain mobility of the dielectric in its rubbery state and are independent of dielectric film thickness. Optimization of organic TFT performance must recognize this fundamental buried interface viscoelasticity effect, which is detectable in the current-voltage response.     

三种环境材料及其复合施用对盐碱化土壤的改良效果研究

为了研发新型有机无机复合材料改良盐碱土壤,采用土柱淋溶模拟实验方法,研究了脱硫石膏、改性腐植酸、高分子材料及其复合材料对盐碱土壤理化性能的改良效果,并探讨了相关材料对盐碱土壤的改良机制。结果表明:与不加任何材料的对照处理(CK)相比,脱硫石膏的作用主要是降低盐碱土壤的pH值和土壤钠吸附比(SAR),淋溶后盐碱土壤pH和SAR分别下降了7.46%和37.7%;改性腐植酸的作用是降低盐碱土壤中水溶性盐含量,淋溶后水溶性盐含量较CK降低了64.61%;高分子材料主要作用是增强土壤的保水效果,土壤淋溶液总体积较CK降低了33.1%;三种材料复合处理的淋溶盐碱土壤中大于0.25 mm的土壤团聚体含量增加了20.41%,pH、SAR分别降低0.81%、26.23%。综合评价认为,三种材料复合处理能够在改善盐碱土壤理化性质的同时改良土壤结构,具有较好的综合改良效果。