Epoxy resin containing polyphenylsilsesquioxane: Preparation,morphology, and thermomechanical properties

Polyphenylsilsesquioxane (PPSQ) was incorporated into an epoxy resin to prepare organic–inorganic composites, and two strategies were adopted to afford composites with different morphologies. Phase separation induced by polymerization occurred in the physical blending system. However, nanostructured composites were obtained when a catalytic amount of aluminum triacetylacetonate was added to mediate the reaction between PPSQ and diglycidyl ether of bisphenol A (DGEBA). The intercomponent reaction significantly suppressed the phase separation on the micrometer scale. Organic–inorganic composites with different morphologies displayed quite different thermomechanical properties. Both differential scanning calorimetry and dynamic mechanical analysis showed that the nanostructured composites possessed higher glass‐transition temperatures than the phase‐separated composites with the same loading of PPSQ, although the intercomponent reaction between PPSQ and DGEBA reduced the crosslinking density of the epoxy matrix. This result was ascribed to the presence of nanosized PPSQ domains in the nanostructured composites, which acted as physical crosslinking sites and thus reinforced the epoxy networks. The nanoreinforcement of the PPSQ domains afforded the enhanced dynamic storage modulus for the nanostructured composites in comparison with the phase‐separated composites with a PPSQ concentration less than 15 wt %. In terms of thermogravimetric analysis, the organic–inorganic composites displayed improved thermal stability and flame retardancy. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1093–1105, 2006     

Synthesis of TiO2–SiO2/polymer core–shell microspheres with a microphase‐inversion method

A novel microphase‐inversion method was proposed for the preparation of TiO₂–SiO₂/poly(methyl methacrylate) core–shell nanocomposite particles. The inorganic–polymer nanocomposites were first synthesized via a free‐radical copolymerization in a tetrahydrofuran solution, and the poor solvent was added slowly to induce the microphase separation of the nanocomposite and result in the formation of nanoparticles. The average particle sizes of the microspheres ranged from 70 to 1000 nm, depending on the reaction conditions. Transmission electron microscopy and scanning electron microscopy indicated a core–shell morphology for the obtained microspheres. Thermogravimetric analysis and X‐ray photoelectron spectroscopy measurements confirmed that the surface of the nanocomposite microspheres was polymer‐rich, and this was consistent with the core–shell morphology. The influence of the synthetic conditions, such as the inorganic composition and the content of the crosslinking monomer, on the particle properties was studied in detail. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3911–3920, 2006     

Highly substituted poly(2,3‐diphenyl‐1,4‐phenylenevinylene) derivatives having bulky phenyl and fluorenyl pendant groups: Synthesis,characterization, and electro‐optical properties

Two series of poly(2,3‐diphenyl‐1,4‐phenylenevinylene) (DP‐PPV) derivatives containing multiple bulky substituents were synthesized. In the first series, two different groups were incorporated on C‐5,6 positions of the phenylene moiety to increase steric hindrance and to obtain blue‐shifted emissions. In the second series, bulky fluorenyl groups with two hexyl chains on the C‐9 position were introduced on two phenyl pendants to increase the solubility as well as steric hindrance to prevent close packing of the main chain. Polymers with high molecular weights and fine‐tuned electro‐optical properties were obtained by controlling the feed ratio of different monomers during polymerization. The maximum photoluminescent emissions of the thin films are located between 384 and 541 nm. Cyclic voltammetric analysis reveals that the band gaps of these light‐emitting materials are in the range from 2.4 to 3.3 eV. A double‐layer EL device with the configuration of ITO/PEDOT/P4/Ca/Al emitted pure green light with CIE′1931 at (0.24, 0.5). Using copolymer P6 as the emissive layer, the maximum luminescence and current efficiency were both improved when compared with the homopolymer P4. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6738–6749, 2006     

Surface characterization and barrier properties of plasma‐modified polyethersulfone/layered silicate nanocomposites

This study describes the preparation of polyethersulfone (PES)/layered silicate nanocomposites (PLSNs) by mixing PES polymer chain into organically‐modified layered silicate in 1‐methyl‐2‐pyrrolidinone (NMP) solution. Both X‐ray diffraction data and transmission electron microscopy images of PLSNs indicate that the silicate layers were almost exfoliated and randomly distributed into the PES matrix. The mechanical and barrier properties of PLSNs show remarkable enhancement in the storage modulus and water/oxygen permeability when compared with that of neat PES matrix. Surfaces modification of PES and PLSN films with various treated times, system pressures, and radio frequency (RF) powers were performed using a mixture of oxygen (O₂) and nitrogen (N₂) plasmas. The topographical and physical properties of plasma‐modified PES and PLSN surfaces were investigated using scanning probe microscopy (SPM), contact‐angle measurements, and X‐ray photoelectron spectroscopy (XPS). These results indicate that the surface roughness of PLSNs with the same condition of plasma modification is lower than that of neat PES matrix and is probably due to the increase of stiffness with the presence of inorganic layered silicates in PES matrix. The surface properties of the PES and PLSNs are also changed from hydrophobic to hydrophilic. The XPS spectra suggest that the exposure of the PES and PLSNs to the plasmas led to the combination of etching reactions of polymer surface initiated by plasma and the following addition reactions of new oxygen‐ and nitrogen‐containing functional groups onto polymer surfaces to change their surface properties. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3185–3194, 2006     

Independence of the brittle–ductile transition from the rubber particle size for impact‐modified poly(vinyl chloride)

A series of acrylic impact modifiers (AIMs) with different particle sizes ranging from 55.2 to 927.0 nm were synthesized by seeded emulsion polymerization, and the effect of the particle size on the brittle–ductile transition of impact‐modified poly(vinyl chloride) (PVC) was investigated. For each AIM, a series of PVC/AIM blends with compositions of 6, 8, 10, 12, and 15 phr AIM in 100 phr PVC were prepared, and the Izod impact strengths of these blends were tested at 23 °C. For AIMs with particle sizes of 55.2, 59.8, 125.2, 243.2, and 341.1 nm, the blends fractured in the brittle mode when the concentration of AIM was lower than 10 phr, whereas the blends showed ductile fracture when the AIM concentration reached 10 phr. It was concluded that the brittle–ductile transition of the PVC/AIM blends was independent of the particle size in the range of 55.2–341.1 nm. When the particle size was greater than 341.1 nm, however, the brittle–ductile transition shifted to a higher AIM concentration with an increase in the particle size. Furthermore, the critical interparticle distance was found not to be the criterion of the brittle–ductile transition for the PVC/AIM blends. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 696–702, 2006     

Reinforcement effect of MAA on nano‐CaCo3‐filled EPDM vulcanizates and possible mechanism

Methacrylic acid (MAA) was used as in situ surface modifier to improve the interface interaction between nano‐CaCO₃ particle and ethylene–propylene–diene monomer (EPDM) matrix, and hence the mechanical properties of nano‐CaCO₃‐filled EPDM vulcanizates. The results showed that the incorporation of MAA improved the filler–matrix interaction, which was proved by Fourier transformation infrared spectrometer (FTIR), Kraus equation, crosslink density determination, and scanning electron microscope (SEM). The formation of carboxylate and the participation of MAA in the crosslinking of EPDM indicated the strong filler–matrix interaction from the aspect of chemical reaction. The results of Kraus equation showed that the presence of MAA enhanced the reinforcement extent of nano‐CaCO₃ on EPDM vulcanizates. Crosslink density determination proved the formation of the ionic crosslinks in EPDM vulcanizates with the existence of MAA. The filler particles on tensile fracture were embedded in the matrix and could not be observed obviously, indicating that a strong interfacial interaction between the filler and the matrix had been achieved with the incorporation of MAA. Meanwhile, the presence of MAA remarkably increased the modulus and tensile strength of the vulcanizates, without negative effect on the high elongation at break. Furthermore, the ionic bond was thought to be formed only on filler surface because of the absolute deficiency of MAA, which resulted in the possible structure where filler particles were considered as crosslink points. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1226–1236, 2006     

Chiral separation of synthetic vicinal diol compounds by capillary zone electrophoresis with borate buffer and beta-cyclodextrin as buffer additive.

The investigation on capillary electrophoretic enantioseparation of six synthetic compounds containing vicinal diol groups has been undertaken to acquire the optimum conditions using native beta-cyclodextrin (beta-CD) as chiral selector and borate as a background electrolyte. The separation was carried out in an uncoated capillary (58.5 cm x 75 microm i.d., effective length 48.5 cm) and the effects of several important factors were investigated in detail. The results showed that beta-CD as a chiral selector exhibited good enantioselectivity and that the enantioseparation was greatly influenced by the structure of the diols, the borate concentration and the buffer pH. The optimum performance was obtained for the chiral vicinal diols under the conditions of 200 mM borate buffer of pH 9.8 containing 1.7% beta-CD at an applied voltage of 15 kV and a capillary temperature of 20 degrees C. Under the conditions, four diols were baseline separated with fast analysis time and the good theoretical plate numbers (above 10 x 10(4)) and favorable migration-time reproducibilities (RSDs below 3.0%) were obtained. The separation results were satisfactory.     

韧性金属裂纹尖端损伤区内应变场测量——数字散斑相关法应用

本文用数字散斑相关方法测量了五种不同幂硬化指数韧性金属材料(铝和铜),双边裂纹尖端细观区域内应变场.对所得结果用韧性损伤模型进行了分析.在此法中以金属自然表面结构为散斑场,不同加载状态的散斑场进行比较,得到相对变形与应变.图象之间相关性 C 是变形参数或是位移及其导数的泛函.使其相关性 C 取最大值的试凑变形即为其真实变形场.这一方法在细观测量中应用得到满意的结果.     

Essay on gravitation: Present-time variation of Newton's gravitational constant in superstring theories

Superstring theories provide an appropriate framework for studying the time variation of fundamental coupling constants. The present time variation of coupling constants in Superstring theories with currently favorable internal backgrounds critically depends on the shape of the potential for the size of internal space. If the potential is almost flat, as in perturbation theory to all orders, the present value of ¦/G¦ for Newton's gravitational constant is calculable and estimated to be 1×10^–11±1yr^–1, which is just at the edge of the present observational bound for/G. If the potential has a minimum with finite curvature due to unknown nonperturbative effects,/G will become unobservably small. The improvement of the measurement of/G of 1 or 2 orders of magnitude would discriminate between the two situations. Problems with the time variation of other coupling constants are also discussed.This essay received the fourth award from the Gravity Research Foundation for the year 1987-Ed.