Control of polymerization processes of 10,12-pentacosadiynoic acid LB films

Studies have been carried out on KrF excimer laser light (EX), X-ray or electron beam (EB) induced polymerization of 10,12-pentacosadiynoic acid (PDA) Langmuir-Blodgett (LB) films in relation to molecular density or molecular arrangement of the films using X-ray diffraction analysis, infrared (IR) spectroscopy and Raman spectroscopy. The molecular arrangement or density of the PDA LB films was controlled by subphase conditions when the films were built up, such as pH, temperature of a subphase or salt concentration in the subphase. Polymerization sensitivity of the PDA LB film was affected by the arrangement or molecular density. On low density (A type) films the polymerization occurred by irradiation with EX, X-ray or EB, but on high density (B type) films the polymerization occurred only when the irradiation was carried out by high energy beams such as X-ray or EB. Decomposition of polymerized films was observed further by excessive irradiation of EX or X-ray, but not on the B type films. It was revealed by X-ray diffraction analysis that in the A type film, the PDA molecules bent to a larger extent than those in the B type film and the polymerization proceeded topochemically, that is, the thickness decreased little after EB irradiation in a helium atmosphere. On the other hand, in the B type film, the thickness decreased by about 10% as a result of EB irradiation. By IR reflection-absorption (RA) and Raman measurements, it was confirmed that conjugated diacetylenic bonds disappeared and conjugated double and new conjugated triple bonds appeared after high energy beam irradiations. These results support the supposition that 1,4-polymerization, i.e. polydiacetylene type polymerization, occurs easily in the A type film and 1,2- or 3,4-polymerization, i.e. polyacetylene type polymerization, occurs in the B type film, and that the polymerized A type film was decomposed at the polydiacetylenic bond when the irradiation continued further. It was also shown that the polyacetylene type polymer was obtained only when the B type film was irradiated with the high energy beam.     

Development of an anisotropic conductive adhesive film (ACAF) from epoxy resins

A thermoset type anisotropic conductive adhesive film (ACAF), which electrically connects an ITO glass and a flex circuit both having conducting pattersn of less than 100 μm in pitch, has been developed. In this development, bisphenol A and bisphenol F epoxy resins were tested to formulate an ACAF with easy-to-handle tackiness, flexibility, and strenght. A curing agent that gives fast cure and long shelf-life properties to the epoxy resin was also selected. The tensile stress–strain responses of obtained adhesive films were successfully used for determining the formulation. Good aftercure physical properties (electrical and mechanical) were obtained. Durability against high temperature and high humidity were also tested to confirm long-term stability of the conduction of this ACAF. © 1995 John Wiley & Sons, Inc.     

Surface-initiated atom transfer radical polymerization of methyl methacrylate on magnetite nanoparticles

The synthesis of magnetite nanoparticles coated with a well-defined graft polymer is reported. The magnetite nanoparticles with an initiator group for copper-mediated atom transfer radical polymerization (ATRP), 2-(4-chlorosulfonylphenyl) ethyltrichlorosilane (CTCS) chemically bound on their surfaces were prepared by the self-assembled monolayer-deposition method. The surface-initiated ATRP of methyl methacrylate (MMA) was carried out with the CTCS-coated magnetite nanoparticles in the presence of free (sacrificing) initiator, p-toluenesulfonyl chloride. Polymerization proceeded in a living fashion, exhibiting first-order kinetics of monomer consumption and a proportional relationship between molecular weight of the graft polymer and monomer conversion, thus providing well-defined, low-polydispersity graft polymers with an approximate graft density of 0.7 chains/nm². The molecular weight and polydispersity of the graft polymer were nearly equal to those of the free polymer produced in the solution, meaning that the free polymer is a good measure of the characteristics of the graft polymer. The graft polymer possessed exceptionally high stability and remarkably improved dispersibility of the magnetite nanoparticles in organic solvent.     

Forming of aluminium alloy at temperatures just below melting point

In order to improve the mechanical properties of products, a forming process of a solid material at a temperature just below the melting point is proposed. The material is deformed at the semi-solid temperature due to the heat generation caused by plastic deformation. The tensile strength, elongation, hardness and toughness of the aluminium alloy (Al–7%Si–0.3%Mg) billet extruded at temperatures between 500 and 550 °C are compared with those of the billet extruded in the hot forming (450 °C) and the semi-solid (560 °C) temperatures. The billet temperature during forming is evaluated by the finite element simulation. The tensile strength and hardness of the billet extruded at 550 °C just below the solidus temperature are higher than those for a billet at 450 °C, and they are almost the same as those for a billet deformed at 560 °C in the semi-solid region. The elongation and toughness of the extruded billet at 550 °C are lower than those for a billet at 450 °C. The forming load at 550 °C is almost half of that at 450 °C. Cracking on the surface of the extruded billet occurs at a high punch speed. The calculated temperature when the solid billet is extruded in the semi-solid state agrees well with the experimental one at which the tensile and hardness are improved.     

Note: detection of micro-cracks in the interlayer dielectric film by the stress based light scattering method

A phenomenon was discovered wherein light scattering strength from cracks increases when tensile stress is applied to micro-cracks produced in the interlayer dielectric film by chemical mechanical polishing treatment. It is likely that the change in light scattering intensity occurs because a region of high stress concentration (region with high variation in index of refraction) is produced near the crack tip due to stress, thus forming a type of scatterer. With this method, it is possible to detect only scatterers which respond to stress, and thus, it is possible to classify and separately detect cracks and particles.     

A new approach to the design of high-Tc superconductors: Metallised interlayers

We show from muon spin relaxation (SR) studies on mercury HTS superconductors that a 50-fold increase in irreversibility field obtained by partial substitution of Re for Hg is due to metallisation of the Hg/Re layer. Induced superconductivity on this metallic layer doubles the overall superfluid density. This suggests a new approach to the design of high performance HTS materials: metallising one of the non-CuO₂ interlayers and thereby greatly enhancing the superconducting properties.     

Straight-through microchannel devices for generating monodisperse emulsion droplets several microns in size

The authors recently proposed a promising technique for producing monodisperse emulsions using a straight-through microchannel (MC) device composed of an array of microfabricated oblong holes. This research developed new straight-through MC devices with tens of thousands of oblong channels of several microns in size on a silicon-on-insulator plate, and investigated the emulsification characteristics using the microfabricated straight-through MC devices. Monodisperse oil-in-water (O/W) and W/O emulsions with average droplet diameters of 4.4–9.8 μm and coefficients of variation of less than 6% were stably produced using surface-treated straight-through MC devices that included uniformly sized oblong channels with equivalent diameters of 1.7–5.4 μm. The droplet size of the resultant emulsions depended greatly on the size of the preceding oblong channels. The emulsification process using the straight-through MC devices developed in this research had very high apparent energy efficiencies of 47–60%, defined as (actual energy input applied to droplet generation/theoretical minimum energy input necessary for making droplets) × 100. Straight-through MC devices with numerous oblong microfluidic channels also have great potential for increasing the productivity of monodisperse fine emulsions.