Styrene polymerization catalyzed by metal porphyrin complex/MAO for in situ synthesizing polystyrene containing air stable pi cation radicals

A novel catalyst system based on nickel(II) tetraphenylporphyrin (Ni(II)TPP) and methylaluminoxane for styrene polymerization was developed. This catalyst system has a high thermal stability and show fairly good activity. The obtained polystyrene (PS) was isotactic-rich atactic polymer by C-13 NMR analysis, and its molecular weight distribution was rather narrow (M-w/M-n approximate to 1.6, by GPC analysis). ESR revealed that Ni(II)TPP pi cation radicals were formed in the polymerization and could remain in the resulting PS stably. The mechanism of the polymerization was discussed and a special coordination mechanism was proposed. The PS product containing Ni(II)TPP pi cation radicals can be used as a potential functional material.

Characterization of High Melt Strength Polypropylene Synthesized via Silane Grafting Initiated by In Situ Heat Induction Reaction

High melt strength polypropylene (HMSPP) was synthesized by in situ heat induction reaction, in which pure polypropylene (PP) powders without any additives were used as a basic resin and vinyl trimethoxysilane (VTMS) as a grafting and crosslinking agent. The grafting reaction of VTMS with PP was confirmed by FTIR. The structure and properties of HMSPP were characterized by means of various measurements. The content of grafted silane played a key role on the melt strength and melt flow rate (MFR) of HMSPP. With increasing the content of grafted silane, the melt strength of HMSPP increased, and the MFR reduced. In addition, due to the existence of cross-linking structure, the thermal stability and tensile strength of HMSPP were improved compared with PP.

Micelle-assisted synthesis of polyaniline/magnetite nanorods by in situ self-assembly process

Polyaniline/magnetite nanocomposites consisting of polyaniline (PANI) nanorods surrounded by magnetite nanoparticles were prepared via an in situ self-assembly process in the presence of PANI nanorods. The synthesis is based on the well-known chemical oxidative polymerization of aniline in an acidic environment, with ammonium persulfate (APS) as the oxidant. An organic acid (dodecylbenzenesulfonic acid, DBSA) was used to replace the conventional strong acidic (1 M HCl) environment. Here, dodecylbenzenesulfonic acid is used not only as dopant, but also as surfactant in our reaction system.

Effects of thermal annealing on polymer photovoltaic cells with buffer layers and in situ formation of interfacial layer for enhancing power conversion efficiency

We have investigated the effects of thermal annealing before and after cathode deposition on poly(3-hexylthiophene)(P3HT)/[6,6]-phenyl C61-butyric acid methyl ester (PCBM) blend photovoltaic cells with different cathode buffer layers. The introduction of cathode buffer layer such as lithium fluoride (LiF) and calcium oxide (CaO) in pre-annealing cells can increase the open-circuit voltage (V-oc) and the power conversion efficiency (PCE). Post thermal annealing after cathode deposition further enhanced the PCE of the cells with LiF/Al cathode.

In situ PEI and formic acid directed formation of Pt NPs/MWNTs hybrid material with excellent electrocatalytic activity

A hybrid material based on Pt nanoparticles (Pt NPs) and multi-walled carbon nanotubes (MWNTs) was fabricated with the assistance of PEI and formic acid. The cationic polyelectrolyte PEI not only favored the homogenous dispersion of carbon nanotubes (CNTs) in water, but also provided sites for the adsorption of anionic ions PtCl42- on the MWNTs' sidewalls. Deposition of Pt NPs on the MWNTs' sidewalls was realized by in situ chemical reduction of anionic ions PtCl42- with formic acid. The hybrid material was characterized with TEM, XRD and XPS. Its excellent electrocatalytic activity towards both oxygen reduction in acid media and dopamine redox was also discussed.

In Situ Observation of Tensile Deformation Processes of Soft Colloidal Crystalline Latex Fibers

The deformation mechanism or styrene/n-butyl acrylate copolymer latex films with fiber symmetric crystalline structure subjected to uniaxial stretching was studied using synchrotron small-angle X-ray scattering technique. The fibers were drawn at angles or 0, 35, and 55 degrees with respect to the Fiber axis. In all cases, the microscopic deformation within the crystallites was Found to deviate from affine deformation behavior with respect to the macroscopic deformation ratio. Moreover, the extent of this deviation is different in the three cases. This peculiar behavior can be attributed to the relative orientation of the (111) plane of the crystals, the plane of densest packing, with respect to the stretching direction in each case. When the stretching direction coincides with the crystallographic (111) plane, which is the case for stretching directions of 0 and 55 degrees with respect to the fiber axis, the microscopic deformation deviates less from affine behavior than when the stretching direction is arbitrarily oriented with respect to the crystallographic (111) plan.

In Situ Preparation and Luminescent Properties of CeF3 and CeF3:Tb3+ Nanoparticles and Transparent CeF3:Tb3+/PMMA Nanocomposites in the Visible Spectral Range

CeF3 and CeF3:Tb3+ nanoparticles were prepared by reverse microemulsion with a functional monomer, methyl methacrylate (MMA), as the oil phase, and CeF3:Tb3+/poly (methyl methacrylate) (PMMA) nanocomposites were obtained via polymerization of the MMA monomer. The nanoparticles and nanocomposites have been well characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), low- and high-resolution transmission electron microscope (TEM), selected-area electron diffraction (SAED), thermogravimetric analysis (TGA), UV/vis transmission spectra, photoluminescence excitation, and emission spectra and luminescence decays. The well-crystallized CeF3 and CeF3:Tb3+ nanoparticles are spherical with a mean diameter of 15 nm. They show the characteristic emission of Ce3+ 5d-4f (313 nm, D-2-F-2(5/2); 323 nm, D-2-F-2(7/2)) and Tb3+ D-5(4)-F-7(J) (J = 6-3, with D-5(4)-F-7(5) green emission at 541 nm as the strongest one) transitions, respectively.

In situ preparation and luminescent properties of LaPO4:Ce3+, Tb3+ nanoparticles and transparent LaPO4:Ce3+, Tb3+/PMMA nanocomposite

LaPO4:Ce3+, Tb3+ nanoparticles were prepared by the reverse microemulsion with functional monomer, methyl methacrylate (MMA) as oil phase, and LaPO4:Ce3+, Tb3+/poly(methyl methacrylate) (PMMA) nanocomposite was obtained via polymerization of MMA monomer. The nanoparticles and nanocomposite have been well characterized by XRD, SEM, TEM, UV/vis spectrum, photoluminescence excitation and emission spectra and luminescence decays. The obtained solid nanocomposite LaPO4:Ce3+, Tb3+/PMMA is highly transparent and exhibits strong green photoluminescence upon UV excitation, due to the integration of luminescent LaPO4:Ce3+, Tb3+ nanoparticles. The luminescent lifetime of Tb3+ is determined to be 1.25 ms in the nanocomposite. (C) 2009 Elsevier Inc. All rights reserved.

In situ chlorinating-graft copolymerization on isotactic polypropylene in gas-solid phase

A novel method in situ chlorinating-graft copolymerization (ISCGC) of grafting maleic anhydride (MAH) on isotactic polypropylene (iPP) in gas-solid phase was investigated in this paper. Chlorine (Cl-2) was used as initiator, chlorinating agent and termination agent at the same time during the reaction. The iPP was chlorinated as well as grafted with MAH in the reaction process. The product with chlorine and MAH in the same molecule was named as PP-cg-MAH. Existence of PP-cg-MAH was identified by Fourier transform infrared. Thermal behavior and crystallinity of PP-cg-MAH were analyzed by differential scanning calorimetry, X-ray diffraction and polarizing microscope. Influencing factors for the value of graft degree were also discussed. Compared with conventional peroxide initiated graft method, ISCGC revealed higher MAH graft efficiency (33%), and particularly alleviated degradation of iPP. iPP could be grafted successfully and without changing physical properties dramatically through this method.

Incorporation of Nanoparticles into Polyelectrolyte Multilayers via Counterion Exchange and in situ Reduction

We report a general method for incorporation of nanoparticles into polyelectrolyte multilayer (PEM) thin films by utilizing the excess charges and associated counterions present in the PEMs. Silver ions were introduced directly into multilayers assembled from poly(diallyldimethylammonium chloride) (PDDA) and poly(styrene sulfonate) (PSS), (PDDA/PSS)(n), by a rapid ion exchange process, which were then converted into silver nanoparticles via in situ reduction to create composite thin films. The size and the content of the nanoparticles in the film call be tuned by adjusting the ionic strength in the polyelectrolyte solutions used for the assembly. Spatial control over the distribution of the nanoparticles in the PEM was achieved via the use of multilayer heterostructure containing PDDA/PSS bilayer blocks assembled at different salt concentrations. Because excess charges and counterions are always present in any PEM, this approach can be applied to fabricate a wide variety of composite thin Films based on electrostatic self-assembly.

In Situ Scanning Tunneling Microscopy on the Dynamic Process of the Replacement of Coronene on Au (111) by 6-Mercapto-1-Hexanol

The replacement of coronene monolayer on Au (111) by 6-mercapto-1-hexanol (MHO) was studied by in situ scanning tunneling microscopy (STM) in solutions. It was found that the rate of replacement depends strongly on the concentration of MHO. The replacement finished within a second at a higher concentration of MHO. At a lower concentration, the slow replacement could be followed by in situ STM. The replacement occurred initially near the elbow position of reconstructed Au (111) with the formation of pits in a single or several missing molecules. With the proceeding of replacement, these small pits expanded, and the surrounding coronene molecules were gradually substituted by MHO, which developed into ordered domains within a spatial confined environment. Meanwhile, the reconstruction of Au (111) was lifted. The replacement expanded fast along the reconstruction lines in the domain. For the fast replacement, a (root 3 x root 3) R30 degrees adlattice was observed, while a c(4 x 2) superlattice was observed for the slow replacement.

Phase Behavior and dewetting for polymer blend films studied by in situ AFM and XPS: From thin to ultrathin films

In this work, the film thickness (l(0)) effect on the phase and dewetting behaviors of the blend film of poly(methyl methacrylate)/poly (styrene-ran-acrylonitrile) (PMMA/SAN) has been studied by in situ atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). The thinner film shows the more compatibility of the blend, and the phase separation of the film occurs at l(0) > 5R(g) (radius of gyration). An initially time-independent q*, the characteristic wavenumber of the phase image, which is in good agreement of Cahn's linearized theory for the early stage of spinodal decomposition, has been obtained in real space and discussed in detail. For 5R(g) > l(0) > 3R(g), a "pseudo-dewetting/(phase separation + wetting)" behavior occurs, where the pseudo-wetting is driven by the concentration fluctuation mechanism. For 10 < 3R(g), a "real dewetting/(phase separation + wetting)" behavior occurs.