Synthesis and optoelectronic properties of silole‐containing polyfluorenes with binary structures

2,5‐Bis(2‐bromofluorene‐7‐yl)silole was prepared by a modified one‐pot synthesis with a reverse addition procedure, from which novel silole‐containing polyfluorenes with binary random and alternating structures (silole contents between 4.5 and 25% and high M_w up to 509 kDa were successfully synthesized. The well‐defined repeating unit of the alternating copolymer comprises a terfluorene and a silole ring. Optoelectronic properties including UV absorption, electrochemistry, photoluminescence (PL), and electroluminescence (EL) of the copolymers were examined. The different excitation energy transfers from fluorene to silole of the copolymers in solution and in the solid state were compared. The films of the copolymers showed silole‐dominant green emissions with high absolute PL quantum yields up to 83%. EL devices of the copolymers with a configuration of ITO/PEDOT/copolymer/Ba/Al displayed exclusive silole emissions peaked at around 543 nm and the highest EL efficiency was achieved with the alternating copolymer. Using the alternating copolymer and poly(9,9‐dioctylfluorene) as the blend‐type emissive layer, a maximum external quantum efficiency of 1.99% (four times to that of the neat film) was realized, which was a high efficiency so far reported for silole‐containing polymers. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 756–767, 2007     

Metallothionein as a biomarker for mercury in tissues of rat fed orally with cinnabar

Cinnabar, as one of the most widely used mineral drugs in traditional Chinese medicines, has been proven to have prominent curative effects in clinical use for more than 2000 years. But the safety and toxicity of the drug has been under constant debate in clinic usage. Metallothionein (MT) contains about 30% of cysteine in the molecule, and plays an important detoxification role against heavy metals. In this study, it was used as a biomarker to assess mercurial accumulation in rats fed orally with cinnabar. After feeding rats with cinnabar by gastric gavage at different dosages and at different times, the distribution of heavy metals (including mercury, copper and zinc) and MT was investigated among rat tissues, including liver, kidney, heart, brain, testis and blood. Metals and MT determinations were carried out using inductively coupled plasma mass spectrometry (ICP‐MS) and a modified mercury saturation assay technique respectively. The results indicated that mercury was easily accumulated in the tissues of rats exposed to cinnabar, especially in kidney. For example: at a feeding dosage of 5 g kg^?1 (bw) for 4 weeks, the mercury concentrations in kidney were 13, 8.7, 21.6 and 26 times those in liver, testis, brain and heart respectively; and at 2.5 g kg^?1 (bw) for 2 weeks, the mercury concentrations in kidney were 21, 2.1, 3 and 21 times those in liver, testis, brain and heart respectively. In addition, mercury in kidney and liver of all cinnabar groups was significantly higher than that of the control group (P < 0.01). A high positive correlation observed between MT concentrations and mercury levels in both liver and kidney (R² = 0.9299, P < 0.02 for liver; R² = 0.9923, P < 0.0008 for kidney) indicated that MT could be used as a biomarker for mercury in tissues. Copyright © 2004 John Wiley & Sons, Ltd.     

A projection method for solving incompressible viscous flows on domains with moving boundaries

In this paper, a projection method is presented for solving the flow problems in domains with moving boundaries. In order to track the movement of the domain boundaries, arbitrary‐Lagrangian–Eulerian (ALE) co‐ordinates are used. The unsteady incompressible Navier–Stokes equations on the ALE co‐ordinates are solved by using a projection method developed in this paper. This projection method is based on the Bell's Godunov‐projection method. However, substantial changes are made so that this algorithm is capable of solving the ALE form of incompressible Navier–Stokes equations. Multi‐block structured grids are used to discretize the flow domains. The grid velocity is not explicitly computed; instead the volume change is used to account for the effect of grid movement. A new method is also proposed to compute the freestream capturing metrics so that the geometric conservation law (GCL) can be satisfied exactly in this algorithm. This projection method is also parallelized so that the state of the art high performance computers can be used to match the computation cost associated with the moving grid calculations. Several test cases are solved to verify the performance of this moving‐grid projection method. Copyright © 2004 John Wiley Sons, Ltd.     

Synthesis and nuclear magnetic resonance analysis of starch‐g‐poly(1,4‐dioxan‐2‐one) copolymers

A new biodegradable starch graft copolymer, starch‐g‐poly(1,4‐dioxan‐2‐one), was synthesized through the ring‐opening graft polymerization of 1,4‐dioxan‐2‐one onto a starch backbone. The grafting reactions were conducted with various 1,4‐dioxan‐2‐one/starch feed ratios to obtain starch‐g‐poly(1,4‐dioxan‐2‐one) copolymers with various poly(1,4‐dioxan‐2‐one) graft structures. The microstructure of starch‐g‐poly(1,4‐dioxan‐2‐one) was characterized in detail with one‐ and two‐dimensional NMR spectroscopy. The effect of the feed composition on the resulting microstructure of starch‐g‐poly(1,4‐dioxan‐2‐one) was investigated. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3417–3422, 2004     

WAXS studies on block copolymers of ethylene and propylene

Wide-angle X-ray scattering from presumed block copolymers of polypropylene (PP) and ethylene-propylene copolymer (EPR), i.e., PP-EPR and PP-EPR-PP, synthesized by sequential polymerization with δ-TiCl₃? Et₂AlCl, was examined and compared with WAXS of mechanical blends and chain-transfer mixtures of PP and EPR with comparable compositions. The peak at 2θ = 20° for both the copolymers and the mixtures was attributed to the γ modification of PP in EPR. A strong variation in the ratio of diffraction intensities I₀₄₀/I₁₁₀ of PP in block copolymers and mixtures was explained in terms of crystallite growth in different directions. Analysis of the patterns and calculation of crystallinity, crystallite size, and lattice parameters led to the conclusion that block structure existed in the prepared copolymers.     

In‐line monitoring of UV photopolymerization with a quartz crystal resonator

An in‐line monitoring device using a quartz crystal resonator for thin film polymerization was proposed, and its performance has been evaluated by implementing in the UV polymerization of 2‐hydroxyethyl methacrylate with a photoinitiator of 1‐chloroanthraquinone. Because the variation of resonant resistance of the resonator is proportional to the square root of viscosity change that is closely related to the polymerization degree, the resistance can be used as a measure of the polymerization degree. The resistance measurements were compared with the outcome of instrumental analyses of polymerization degree using an FTIR spectrometer and a gel permeation chromatograph. The experimental results showed that the resistance measurements were consistent with the experimental outcome of the instrumental analyses, and this indicates the effectiveness of the proposed device. Owing to the simplicity and availability of the resonator system, its wide utilization in the monitoring of a variety of film polymerization processes, including photoresistor application, is expected. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2428–2439, 2006     

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     

Measurement and prediction of solubilities and diffusion coefficients of carbon dioxide in starch–water mixtures at elevated pressures

The solubility and diffusion coefficient of carbon dioxide in intermediate‐moisture starch–water mixtures were determined both experimentally and theoretically at elevated pressures up to 16 MPa at 50 °C. A high‐pressure decay sorption system was assembled to measure the equilibrium CO₂ mass uptake by the starch–water system. The experimentally measured solubilities accounted for the estimated swollen volume by Sanchez–Lacombe equation of state (S‐L EOS) were found to increase almost linearly with pressure, yielding 4.0 g CO₂/g starch–water system at 16 MPa. Moreover, CO₂ solubilities above 5 MPa displayed a solubility increase, which was not contributed by the water fraction in the starch–water mixture. The solubilities, however, showed no dependence on the degree of gelatinization (DG) of starch. The diffusion coefficient of CO₂ was found to increase with concentration of dissolved CO₂, which is pressure‐dependent, and decrease with increasing DG in the range of 50–100%. A free‐volume‐based diffusion model proposed by Areerat was employed to predict the CO₂ diffusivity in terms of pressure, temperature, and the concentration of dissolved CO₂. S‐L EOS was once more used to determine the specific free volume of the mixture system. The predicted diffusion coefficients showed to correlate well with the measured values for all starch–water mixtures. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 607–621, 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