Chain pullout and mobility effects in friction and lubrication

The interfacial shear stress that occurs when a network of a polymer that is highly mobile at the segment level (an elastomer) is slid over a smooth surface of an immobile (glassy) polymer has been measured. The glassy material is covered by a thin layer of end-attached chains of the mobile material. The experiment was designed so that there were no free chains at the interface; the slip occurred between network chains on the one side and rigid material plus end-attached mobile chains on the other side. Two main results were obtained. (i) The interfacial shear stress is strongly affected by the segment mobility of the materials on both sides of the slip plane, and considerably lower stress is observed when the materials on both sides of the interface are highly mobile. (ii) Very thin layers of tethered chains can increase the interfacial friction. Both results are relevant to the understanding of a number of practical situations that range from the operation of thin layers of lubricants, such as those found in magnetic storage devices, to the problem of wall slip and melt fracture in polymer processing.     

The use of graft copolymers to bind immiscible blends

Computer simulations and experimental studies were combined to design copolymers that enhance the strength of polymer composites. These copolymers contain side chains that associate across the boundary between phase-separated regions to form a "molecular velcro" that effectively binds the regions together. This behavior significantly improves the structural integrity and mechanical properties of the material. Because the side chains can be fabricated from a large class of compounds, the technique greatly increases the variety of copolymers that can be used in forming high-strength polymer blends.     

Polymerization-induced epitaxy: scanning tunneling microscopy of a hydrogen-bonded sheet of polyamide on graphite

A molecularly thin film of a two-dimensional polymer network formed by hydrogen bonding was synthesized and investigated with scanning tunneling microscopy. Poly(in-caprolactam) (nylon 6) was epitaxially grown on the basal plane of graphite and an ultrathin film of the polymer was obtained after the bulk materials had been washed away with solvents. The polymer chain has a planar, all-trans conformation and adjacent chains run in the antiparallel direction. This produces complete pairing of hydrogen bonding groups, with each amide group lying on a straight line perpendicular to the polymer backbone. This hydrogen-bonded sheet is oriented so that each polymer backbone lies in the (1010) direction on the graphite hexagonal lattice, as opposed to the (1120) direction taken by other paraffinic molecules studied so far. This experiment shows that hydrogen bonding can be used to control the orientation of macromolecules in two dimensions.     

A tough, thermally conductive silicon carbide composite with high strength up to 1600 degreesC in Air

A sintered silicon carbide fiber-bonded ceramic, which consists of a highly ordered, close-packed structure of very fine hexagonal columnar fibers with a thin interfacial carbon layer between fibers, was synthesized by hot-pressing plied sheets of an amorphous silicon-aluminum-carbon-oxygen fiber prepared from an organosilicon polymer. The interior of the fiber element was composed of sintered beta-silicon carbide crystal without an obvious second phase at the grain boundary and triple points. This material showed high strength (over 600 megapascals in longitudinal direction), fibrous fracture behavior, excellent high-temperature properties (up to 1600 degreesC in air), and high thermal conductivity (even at temperatures over 1000 degreesC).     

Molecular basis of the shish-kebab morphology in polymer crystallization

In the rich and long-standing literature on the flow-induced formation of oriented precursors to polymer crystallization, it is often asserted that the longest, most extended chains are the dominant molecular species in the "shish" of the "shish-kebab" formation. We performed a critical examination of this widely held view, using deuterium labeling to distinguish different chain lengths within an overall distribution. Small-angle neutron-scattering patterns of the differently labeled materials showed that long chains are not overrepresented in the shish relative to their concentration in the material as a whole. We observed that the longest chains play a catalytic role, recruiting other chains adjacent to them into formation of the shish.     

Atomic structure of thymidylate synthase: target for rational drug design

The atomic structure of thymidylate synthase from Lactobacillus casei was determined at 3 angstrom resolution. The native enzyme is a dimer of identical subunits. The dimer interface is formed by an unusual association between five-stranded beta sheets present in each monomer. Comparison of known sequences with the Lactobacillus casei structure suggests that they all have a common core structure around which loops are inserted or deleted in different sequences. Residues from both subunits contribute to each active site. Two arginine side chains can contribute to binding phosphate on the substrate. The side chains of several conserved amino acids can account for other determinants of substrate binding.     

Multipolymer systems

Different polymers can be combined to yield a wide variety of composite materials: layered sheets and films, homogeneous and heterogeneous blends, interpenetrating polymer networks, bicomponent fibers, and others. Some properties of a multipolymer material are roughly additive, but synergistic interactions can yield properties and performances superior to those of the individual constituents. Consequently, the use of polymers in combination is a rapidly growing component of polymer materials technology.     

Laser ablation and the production of polymer films

The formation of high-quality thin films of polytetrafluoroethylene (PTFE) is important in many applications ranging from material reinforcement to molecular electronics. Laser ablation, a technique widely used to deposit a variety of inorganic materials, can also be used as a simple and highly versatile method for forming thin polymer films. The data presented show that PTFE films can be produced on various supports by the evaporation of a solid PTFE target with a pulsed ultraviolet laser. The composition of the ablation plume suggests that PTFE ablation and subsequent film formation occur by way of a laser-induced pyrolitic decomposition with subsequent repolymerization. The polymer films produced by this method are composed of amorphous and highly crystalline regions, the latter being predominantly in a chain-folded configuration with the molecular axis aligned parallel to the substrate surface.     

Molecular confinement accelerates deformation of entangled polymers during squeeze flow

The squeezing of polymers in narrow gaps is important for the dynamics of nanostructure fabrication by nanoimprint embossing and the operation of polymer boundary lubricants. We measured stress versus strain behavior while squeezing entangled polystyrene films to large strains. In confined conditions where films were prepared to a thickness less than the size of the bulk macromolecule, resistance to deformation was markedly reduced for both solid-glass forging and liquid-melt molding. For melt flow, we further observed a complete inversion of conventional polymer viscosity scaling with molecular weight. Our results show that squeeze flow is accelerated at small scales by an unexpected influence of film thickness in polymer materials.     

Ultrastrong and stiff layered polymer nanocomposites

Nanoscale building blocks are individually exceptionally strong because they are close to ideal, defect-free materials. It is, however, difficult to retain the ideal properties in macroscale composites. Bottom-up assembly of a clay/polymer nanocomposite allowed for the preparation of a homogeneous, optically transparent material with planar orientation of the alumosilicate nanosheets. The stiffness and tensile strength of these multilayer composites are one order of magnitude greater than those of analogous nanocomposites at a processing temperature that is much lower than those of ceramic or polymer materials with similar characteristics. A high level of ordering of the nanoscale building blocks, combined with dense covalent and hydrogen bonding and stiffening of the polymer chains, leads to highly effective load transfer between nanosheets and the polymer.     

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.     

Negative linear compressibility and massive anisotropic thermal expansion in methanol monohydrate

The vast majority of materials shrink in all directions when hydrostatically compressed; exceptions include certain metallic or polymer foam structures, which may exhibit negative linear compressibility (NLC) (that is, they expand in one or more directions under hydrostatic compression). Materials that exhibit this property at the molecular level--crystalline solids with intrinsic NLC--are extremely uncommon. With the use of neutron powder diffraction, we have discovered and characterized both NLC and extremely anisotropic thermal expansion, including negative thermal expansion (NTE) along the NLC axis, in a simple molecular crystal (the deuterated 1:1 compound of methanol and water). Apically linked rhombuses, which are formed by the bridging of hydroxyl-water chains with methyl groups, extend along the axis of NLC/NTE and lead to the observed behavior.     

Control of energy transfer in oriented conjugated polymer-mesoporous silica composites

Nanoscale architecture was used to control energy transfer in semiconducting polymers embedded in the channels of oriented, hexagonal nanoporous silica. Polarized femtosecond spectroscopies show that excitations migrate unidirectionally from aggregated, randomly oriented polymer segments outside the pores to isolated, aligned polymer chains within the pores. Energy migration along the conjugated polymer backbone occurred more slowly than Forster energy transfer between polymer chains. The different intrachain and interchain energy transfer time scales explain the behavior of conjugated polymers in a range of solution environments. The results provide insights for optimizing nanostructured materials for use in optoelectronic devices.     

改性稻草/高密度聚乙烯复合材料的工艺性能

以改性稻草和高密度聚乙烯(HDPE)为原料,研究了改性稻草/HDPE复合材料的热压工艺,分析了稻草改性用NaOH溶液质量分数、热压时间、HDPE加入比例等因素对复合板材性能的影响.结果表明,热压最佳工艺参数为:密度0.75g/cm~3,施胶量4%,热压温度160℃,热压时间6min,HDPE加入比例30%,NaOH溶液质量分数2.5%.在此条件下制作的改性稻草/HDPE复合材料力学性能达到刨花板国家标准GB/T 4897-2003要求.     

Stepwise formation of multilayered nanostructural films from macromolecular precursors

Sequential adsorption of a cationic polyelectrolyte and individual sheets of the silicate mineral hectorite has allowed controlled, stepwise formation of multilayered films on silicon wafers. Each component adsorbs rapidly by an ion-exchange mechanism, and x-ray diffractometry indicates structural order even in films with thicknesses greater than 0.2 micrometer. The large lateral extent of the silicate sheets (about 25 to 35 nanometers) allows each layer to cover any packing defects in the underlying layer, thus preserving structural order in the growing film. With careful choice of component materials, this method should allow for the preparation of multilayered films with a variety of technologically important properties.     

Polymers with cavities tuned for fast selective transport of small molecules and ions

Within a polymer film, free-volume elements such as pores and channels typically have a wide range of sizes and topologies. This broad range of free-volume element sizes compromises a polymer's ability to perform molecular separations. We demonstrated free-volume structures in dense vitreous polymers that enable outstanding molecular and ionic transport and separation performance that surpasses the limits of conventional polymers. The unusual microstructure in these materials can be systematically tailored by thermally driven segment rearrangement. Free-volume topologies can be tailored by controlling the degree of rearrangement, flexibility of the original chain, and judicious inclusion of small templating molecules. This rational tailoring of free-volume element architecture provides a route for preparing high-performance polymers for molecular-scale separations.     

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.     

Three-dimensionally ordered array of air bubbles in a polymer film

We report the formation of a three-dimensionally ordered array of air bubbles of monodisperse pore size in a polymer film through a templating mechanism based on thermocapillary convection. Dilute solutions of a simple, coil-like polymer in a volatile solvent are cast on a glass slide in the presence of moist air flowing across the surface. Evaporative cooling and the generation of an ordered array of breath figures leads to the formation of multilayers of hexagonally packed water droplets that are preserved in the final, solid polymer film as spherical air bubbles. The dimensions of these bubbles can be controlled simply by changing the velocity of the airflow across the surface. When these three-dimensionally ordered macroporous materials have pore dimensions comparable to the wavelength of visible light, they are of interest as photonic band gaps and optical stop-bands.     

聚合物分子尺寸大小及其与岩石孔喉尺寸配伍关系的试验研究

为了探索和验证聚合物分子尺寸与岩石孔喉尺寸的配伍关系,以河南油田东部老油区稀油油田为例,应用数学方法、微孔滤膜过滤方法和动态光散射方法,对开展聚合物驱条件下拟使用的聚合物的分子尺寸进行试验测定,得到了双河油田不同渗透率岩石能够匹配的聚合物分子量。     

Multicomponent polymeric engineering materials

The great advances made in polymeric structural materials over the past decade have led to their replacement of conventional materials in a wide range of uses including high-performance aerospace applications. This shift in choice of materials is based on economic advantages, simplified fabrication, freedom from corrosion, and lower weight. The trend toward use of polymeric materials will grow as the materials science of this new technology is developed. Better insight into such fundamental problems as the mechanisms by which forces are transferred to the polymer molecule, the surface interactions between polymer phases or polymer and fiber, and the molecular processes by which energy is absorbed during fracture will greatly stimulate the development of this field.