Experimental design and the optimization of a polymer supported palladium complex for use in the Heck reaction

Optimization of the Heck reaction of 4-bromoacetophenone with styrene by a polymer supported, sulfur-containing palladacycle, varying 6 factors at a total of 28 different levels, corresponding to 5760 different possibilities was undertaken. Conversion improved from 34%, with large observable leaching to 88% with no leaching. This was accomplished using a Design of Experiments approach facilitated by the Statistical Design Package, MODDE 7.0^TM.     

Laser printing of nanocomposite solid-state electrolyte membranes for Li micro-batteries

The electrochemical and mechanical properties of nanocomposite solid-state electrolyte membranes deposited using a laser direct-write technique from a suspended solution comprised of an ionic liquid (1,2-dimethyl-3-n-butylimidazolium-bis-trifluoromethanesulfonylimide)-polymer (poly(vinylidene fluoride-co-hexafluoropropylene)) matrix with dispersed nano-particles (TiO₂) are reported and discussed. These laser printed nanocomposite solid-state membranes are shown to exhibit the proper electrochemical behavior for ionic liquids while maintaining the strength and flexibility of the polymer matrix. This combination of physical properties and deposition technique makes these deposited nanocomposite membranes ideally suited for use as an electrolyte/separator in Li micro-batteries. Sample Li micro-batteries using these laser printed nanocomposite membranes have been fabricated and their charge/discharge behavior tested, demonstrating the feasibility of using these nanocomposite membranes in Li micro-battery applications.     

Preparation and electrical characterization of (PVC + KBrO3) polymer electrolytes for solid state battery applications

This paper presents results of studies on dc electrical conductivity and transference number measurements on potassium bromate (KBrO₃) complexed polyvinyl chloride (PVC) films prepared by solution cast technique. Temperature dependence of dc electrical conductivity and transference number data indicated the dominance of ion type charge transport in these specimens. The magnitude of conductivity increased with increase in concentration of the salt and temperature. Using this (PVC + KBrO₃) electrolyte, solid-state electrochemical cells were fabricated, and their discharge profiles were studied under a constant load of 100 kΩ. Several cell profiles such as open circuit voltage, short circuit current, power density, and energy density associated with these cells were evaluated and were reported. The features of complexation of the electrolytes were studied by X-ray diffraction and Fourier transform infrared spectroscopy. Paper presented at the Third International Conference on Ionic Devices (ICID 2006), Chennai, Tamilnadu, India, Dec. 7–9, 2006     

SSIMS analysis of organics, polymer blends and interfaces

This paper gives a critical review on the applications of ToF SIMS in the areas of polymer additive characterization and in the study of polymer blends and interfaces. Polymer additives can readily be identified by ToF SIMS using their parent molecular ions or characteristic fragments. This analytical capability has been successfully applied to monitor the migration or segregation of additives during polymer processing. ToF SIMS is an ideal analytical tool for the study of polymer blends and interfaces because it is able to provide information on both surface composition and morphology. In combination with other analytical techniques such as AFM and XPS, ToF SIMS chemical imaging capability has opened up new horizons in the investigation of complex polymer blend systems. Finally the main advantages and limitations of ToF SIMS in these application areas are also discussed.     

Rugged distal tips for CO2 laser medicine

Low-loss and rugged distal tips for CO₂ laser have been proposed and fabricated based on a commercially available stainless steel (St) pipe. A method of smoothening the inner surface of the St pipe with a rough inner surface is put forward. Fabrication parameters, transmission properties, and mechanical strength of the cyclic olefin polymer-coated silver hollow St distal tip are experimentally discussed.     

Physico-Chemical Characterization of Yu Guo Beads(1100-771 B. C. ) in China

When was the earliest glass produced in China? This has still been a question so far. Some archaeologists have thought that Yu Guo beads are real glass, the earliest glass(1100-771 B. C. ) in China. However, more details of scientific investigations in this paper show that Yu Guo beads are mainly made of clastic quartz (>95%) with a small amount of clay and sintered under the low temperature(500-600℃). It is not a glassy body, but a kind of polycrystal ornaments.     

ToF-SIMS analysis of a fluorocarbon-grafted PET with a gold cluster ion source

Cluster ions have been recognized as a superb primary species in time of flight secondary ion mass spectroscopy (ToF-SIMS) compared with monatomic primary ions, as they significantly enhance the secondary ion yields from bulk samples. Self-assembled monolayers provide an important system for studying the fundamental mechanism involved in the yield enhancement.We used a gold cluster ion source to analyze a new type of self-assembled monolayer: a fluorocarbon-grafted polyethylene terephthalate. In addition to the structure details, which helped to understand the grafting mechanism, ToF-SIMS analysis revealed that fluorocarbon secondary ion yield enhancements by cluster ions were due to the enhanced sputter efficiency. A larger information depth may also be expected from the enhancement. Both mathematical definitions of damage cross-section and disappearance cross-section were revisited under a new context. Another cross-section parameter, sputter cross-section, was introduced to differentiate the beam induced sputter process from damage process.     

Ab initio modelling of crosslinking in polymers. A case of chains with furan rings

A quantum chemical model (Abinitio HF-MO and DFT-B3LYP) of polyfurfuryl alcohol crosslinking is shown. Two pathways were considered: (a) a Diels–Alder (D–A) reaction between a dihydrofuran moiety and a furan ring; (b) the addition reaction of electrophilic specimens on conjugated double bonds. The ability for the formation of D–A adducts (dienes and dienophiles) was investigated by the frontier molecular orbital (FMO) theory. Energy gaps between the FMO's of diene and dienophile structures suggest that the occurrence of the D–A reaction is possible. The results suggest that the carbons of the exo double bonds attached to dihydrofuran rings are the sites most likely to be attacked by electrophilic species, while the C₃ and C₄ atoms display the opposite tendency due to their low HOMO electron densities. Results of a thermochemical approach to these reactions at the MP2 level was in agreement with reactivity modelled by MO predictions.     

Controlled structure and density of “living” polystyrene brushes on flat silica surfaces

Thin layers of polystyrene were grown from surface-grafted nitroxide initiators via controlled “living” free radical polymerization. The “reactive” Langmuir-Blodgett deposition method allowed an effective control of the initiator layer density leading to PS brushes with different and high grafting density and stretching. The influence of the grafting density on the layer structure was studied. Comparison with theoretical predictions for monodispersed brushes in bad solvent was discussed. The thickness was found to vary linearly with molecular weight and the density dependence was shown using wetting measurements. Special features of controlled radical nitroxide polymerization from a surface were discussed. A direct comparison of the molecular weight and polydispersity between surface and bulk polymers was made by de-grafting the brushes into a toluene/HF solution. Finally, some evidence of a “surface Fischer” effect was shown from re-initiated layers. Received 20 December 2001