Preparation of conductive polypyrrole (PPy) composites under supercritical carbon dioxide conditions

Electrically conductive composites were prepared via the chemical oxidative polymerization of the pyrrole monomer in polystyrene (PS) and zinc neutralized sulfonated polystyrene (Zn-SPS) films under supercritical carbon dioxide (SC-CO₂) conditions. The strong swelling effect of SC-CO₂ made polypyrrole (PPy) particles not only form on the surface, but also become incorporated into the film, resulting in a homogeneous structure with a relatively higher conductivity. By comparison, the composite prepared in aqueous solutions shows a skin-core structure and a conductivity of 3 to 4 orders of magnitude lower than that of the former due to the diffusion-controlled process of the pyrrole monomer. The percolation thresholds of PS/PPy and Zn-SPS/PPy composites were 6.2% and 2.7% of the volume fraction of PPy, respectively, much lower than the theoretically predicted value of 16%. Moreover, the conductive composites prepared under SC-CO₂ conditions showed higher thermal stability, especially in the high-temperature region. Translated from Chemical Journal of Chinese Universities, 2006, 27(4): 771–774 (in Chinese)     

The mechanical properties and tribological behavior of epoxy resin composites modified by different shape nanofillers

Mechanical properties and tribological behavior of epoxy resin (EP) and EP nanocomposites containing different shape nanofillers, such as spherical silica (SiO₂), layered organo‐modified montmorillonite (oMMT) and oMMT‐SiO₂ composites, were investigated. The SiO₂‐oMMT composites were prepared by in situ deposition method and coupling agent modification, and transmission electron microscopy (TEM) analysis shows that spherical SiO₂ is self‐assembled on the surface of oMMT, which forms a novel layered‐spherical nanostructure. The mechanical properties test results show that oMMT obviously improves the strength of EP and SiO₂ enhances its toughness, but oMMT‐SiO₂ exhibits a synergistic effect on toughening and reinforcing EP simultaneously. A pin‐on‐disc rig was used to test friction and wear loss of pure EP and EP nanocomposites. The tribological test results prove that these nanofillers with different shapes play different roles for improving the wear resistance of EP nanocomposites. Morphologies of the worn surfaces were studied further by scanning electron microscopy (SEM) observations, and it was clarified that the EP and EP nanocomposites undergo similar wear mechanisms. Copyright © 2006 John Wiley & Sons, Ltd.     

Rigid nanoscopic containers for highly dispersed, stable metal and bimetal nanoparticles with both size and site control

We demonstrate a novel strategy for the preparation of mesoporous silica-supported, highly dispersed, stable metal and bimetal nanoparticles with both size and site control. The supporting mesoporous silica, functionalized by polyaminoamine (PAMAM) dendrimers, is prepared by repeated Michael addition with methyl acrylates (MA) and amidation reaction with ethylenediamine (EDA), by using aminopropyl-functionalized mesoporous silica as the starting material. The encapsulation of metal nanoparticles within the dendrimer-propagated mesoporous silica is achieved by the chemical reduction of metal-salt-impregnated dendrimer-mesoporous silica by using aqueous hydrazine. The site control of the metal or bimetal nanoparticles is accomplished by the localization of inter- or intradendrimeric nanoparticles within the mesoporous silica tunnels. The size of the encapsulated nanoparticles is controlled by their confinement to the nanocavity of the dendrimer and the mesopore. For Cu and Pd, particles locate at the lining of mesoporous tunnels, and have diameters of less than 2.0 nm. For Pd/Pt, particles locate at the middle of mesoporous tunnels and have diameters in the range of 2.0-4.2 nm. The Pd and Pd/Pt nanoparticles are very stable in air, whereas the Cu nanoparticles are stable only in an inert atmosphere.     

Studies on polymers and composites from lignin and fiber derived from sugar cane

Sugarcane fiber (i.e. bagasse) lignin has a larger fraction of aromatics unsubstitution in the ortho position than hardwood or softwood lignin and hence has the greater ability to be derivatized. Furthermore, organosolv lignin has a higher purity than sulfonated and kraft lignins. This work examines the purification of organosolv lignin derived from bagasse and the physico‐chemical properties of the lignin and lignin‐phenol formaldehyde (PF) resin coatings, and composites. The wetability tests have shown that lignin and lignin‐PF resin films are effective water barrier coatings, though the contact angles of lignin‐PF resin films were considerably less than the wax films. The overall mechanical properties (i.e. peak stress, peak strain and modulus) of the bagasse fiber composites were lower than the values obtained with the composites without the inclusion of bagasse fiber. Copyright © 2007 John Wiley & Sons, Ltd.     

Strategies for hydrogen storage in metal--organic frameworks

Increased attention is being focused on metal-organic frameworks as candidates for hydrogen storage materials. This is a result of their many favorable attributes, such as high porosity, reproducible and facile syntheses, amenability to scale-up, and chemical modification for targeting desired properties. A discussion of several strategies aimed at improving hydrogen uptake in these materials is presented. These strategies include the optimization of pore size and adsorption energy by linker modification, impregnation, catenation, and the inclusion of open metal sites and lighter metals.     

Continuous,single-component,crystalline networks in polymer matrix and their vapor doping

It is shown, for the first time, that single-component continuous networks of a low molecular weight electron acceptor additive can be grown in a polymer matrix. Such networks can be doped using, e.g., iodine vapor and converted into conductive CT complexes without losing continuity, thereby making the polymer film conductive. Polyethylene films with tetrathiotetracene networks are obtained, and their doping with iodine vapor in air is investigated by means of conductivity and spectrophotometry in the visible range. It is concluded that doping of the surface layer of the microcrystallites is sufficient to observe a significant increase in the film conductivity, which makes possible the use of such systems as sensors.     

聚苯胺／聚乙烯醇导电复合膜的制备及性质研究

用较简单的化学氧化现场吸附聚合法（ｉｎ－ｓｉｔｕｐｏｌｙｍｅｒｉｚａｔｉｏｎ）制得了聚苯胺（ＰＡｎ）／聚乙烯醇（ＰＶＡ）导电复合膜．该膜具有较好的导电性和机械性能；其电导率可达５．８ｓ／ｃｍ，拉伸强度达１３ＭＰａ，断裂伸长率为１１０％左右．本文讨论了制备的各种条件对复合膜导电性能及力学性能的影响、稳定性及电化学活性；并采用循环伏安曲线、扫描电镜（ＳＥＭ）、ＦＴＩＲ谱及元素分析对该复合膜的结构和性能进行了表征．     

Mechanical and thermal properties of poly-ether ether ketone reinforced with CaCO3

CaCO₃/PEEK (poly-ether ether ketone) composites were prepared on a twin-screw extruder with different mass ratio of CaCO₃/PEEK from 0% to 30%. Four types of particles were used as filler in PEEK matrix. The influence of surface treatment with sulfonated PEEK (SPEEK) of the particles on the mechanical and thermal properties of the composites was studied. The experiments included tensile tests, flexural tests, notched Izod impact tests, TGA, DSC and SEM. The modulus and yield stress of the composites increased with CaCO₃ particles loadings. This increase was attributed to the bonding between the particles and the PEEK matrix, as can be proved by the SEM pictures of tensile fracture surface of the composites. The impact strength of the composites was modified by the SPEEK coated on the CaCO₃ particle surface. DSC experiments showed that the particle content and surface properties influenced the glass transition temperature (T_g) and melting temperature (T_m) of the composites. The T_g increased with the content of fillers while T_m decreased. In this study the fillers treated were found to give better combination properties, which indicated that SPEEK played a constructive role in the CaCO₃/PEEK composites.     

Percolation behaviour of ultrahigh molecular weight polyethylene/multi-walled carbon nanotubes composites

The electrical conductivity of polymer/multi-walled carbon nanotubes (MWCNTs) composites in a powder and in a hot-pressed compacted state, prepared by mechanical mixing, was studied. The semicrystalline ultrahigh molecular weight polyethylene (UHMWPE) was used as a polymer matrix. The data clearly evidence the presence of a percolation threshold φ_c at a very small volume fraction of the MWCNTs φ in a polymer matrix, φ_c ≈ 0.0004-0.0007. The ultralow percolation threshold in UHMWPE/MWCNTs thermoplastic composites was explained by high aspect ratio of the nanotubes and their segregated distribution inside the polymer matrix. The method of composite preparation effects the values of percolation threshold concentration φ_c and critical exponent t. A noticeable positive temperature coefficient of resistivity (PTC effect) was observed in the region of temperatures higher than melting point. It was explained by influence of thermal expansion of the polymer matrix and independence from the melting process that is a result of specific structure of conductive phase.     

Reversible anion exchanges between the layered organic-inorganic hybridized architectures: syntheses and structures of manganese(II) and copper(II) complexes containing novel tripodal ligands

Six noninterpenetrating organic-inorganic hybridized coordination complexes, [Mn(3)(2)(H(2)O)(2)](ClO(4))(2).2 H(2)O (5), [Mn(3)(2)(H(2)O)(2)](NO(3))(2) (6), [Mn(3)(2)(N(3))(2)].2 H(2)O (7), [Cu(3)(2)(H(2)O)(2)](ClO(4))(2) (8), [Mn(4)(2)(H(2)O)(SO(4))].CH(3)OH.5 H(2)O (9) and [Mn(4)(2)](ClO(4))(2) (10) were obtained through self-assembly of novel tripodal ligands, 1,3,5-tris(1-imidazolyl)benzene (3) and 1,3-bis(1-imidazolyl)-5-(imidazol-1-ylmethyl)benzene (4) with the corresponding metal salts, respectively. Their structures were determined by X-ray crystallography. The results of structural analysis of complexes 5, 6, 7, and 8 with rigid ligand 3 indicate that their structures are mainly dependant on the nature of the organic ligand and geometric need of the metal ions, but not influenced greatly by the anions and metal ions. While in complexes 9 and 10, which contain the flexible ligand 4, the counteranion plays an important role in the formation of the frameworks. Entirely different structures of complexes 5 and 10 indicate that the organic ligands greatly affect the structures of assemblies. Furthermore, in complexes 5 and 6, the counteranions located between the cationic layers can be exchanged by other anions. Reversible anion exchanges between complexes 5 and 6 without destruction of the frameworks demonstrate that 5 and 6 can act as cationic layered materials for anion exchange, as determined by IR spectroscopy, elemental analyses, and X-ray powder diffraction.