Micro-flowers of poly(p-phenylene pyromelliteimide) crystals

Morphology control of poly(p-phenylene pyromelliteimide) (PPPI) crystals was examined using reaction-induced crystallization of oligomers during solution polymerization of self-polymerizable N-(4′-aminophenyl)-3-carboxyl-4-alkoxycarbonylphthalimide. Micro-flowers of the PPPI needle-like crystals were formed in which the needle-like crystals grew radially from the center part as petals. The molecules aligned regularly along the long axis of the needle-like crystal. The structure of alkoxy group in the monomer and the monomer concentration influenced the size of the needle-like crystals, and their average length and width were changeable from 640 nm to 1.69 μm and from 110 nm to 210 nm, respectively. The average thickness was 20 nm. The obtained micro-flowers possessed high crystallinity and exhibited excellent thermal stability.     

In situ binary sol–gel reaction of various trifunctional alkoxysilane in the silane‐grafted polyolefin matrix and its effect upon the mechanical properties

The vinyltrimethoxysilane‐grafted ethylene‐propylene copolymer/trifunctional methoxysilane (EPR‐g‐VTMS/RTMS) composites were prepared via in situ silica sol–gel reactions. Five trifunctional methoxysilane compounds (n‐hexyltrimethoxysilane, n‐decyltrimethoxysilane, n‐tetradecyltrimethoxysilane, n‐octadecyltrimethoxysilane, and phenyltrimethoxysilane) have been selected for this study. The water‐cross‐linked EPR‐g‐VTMS/RTMS composites were characterized by attenuated total reflectance‐Fourier transform infrared spectroscopy, gel content, solid‐state ²⁹Si CP/MAS NMR, wide‐angle x‐ray scattering, tensile strength, and field emission scanning electron microscopy measurements. The type of RTMS additive has a substantial influence on the nature of siloxane band networks and eventually the mechanical tensile properties. This finding suggests that the interaction and/or entanglement between the EPR‐g‐VTMS matrix and the substituent of the RTMS additives are crucial for the modifying mechanical properties. Moreover, for the water‐cross‐linked EPR‐g‐VTMS/CnTMS (n = 6, 10, 14, and 18) composites, the joint evidence provided by attenuated total reflectance‐Fourier transform infrared spectroscopy, ²⁹Si CP/MAS NMR, and wide‐angle x‐ray scattering results suggested the formation of ladder‐type poly(n‐alkyl silsesquioxane)s and the presence of the highly ordered structure with a thickness equal to the length of two n‐alkyl groups in all‐trans conformation. POLYM. ENG. SCI., 2011. © 2010 Society of Plastics Engineers.     

Polymers degradable under environmental conditions through end-modification of poly(α-methylstyrene) derivatives

To induce degradabilities in polymers in response to environmental conditions, the end-modification reactions of poly(α-methylstyrene) derivatives were carried out. When diphenylphosphine chloride was used as a modifier for the living end of para-substituted PMS, the coupling efficiency was ca. 50%. 2-Phenylallyl halide derivatives such as 2-phenylallyl bromide, 2-(4-tolyl)allyl bromide, and α-trifluoromethylstyrene were found to be suitable end-modification agents. For example, ω-2-phenylallyl PMS was prepared with almost quantitative functionality by the reaction of the living PMS with 2-phenylallyl bromide. In a similar way, ω-3,3-difluoro-2-phenylallyl and ω-2-(4-tolyl)allyl PMS derivatives were synthesized. Based on thermogravimetric analysis, onset of the degradation temperature of the end-modified PMS derivatives decreased in the following order: ω-hydrogen- > ω-3,3-difluoro-2-phenylallyl- > ω-2-phenylallyl- > ω-2-(4-tolyl)allyl-PMS. Actually, the onset temperature of ω-2-(4-tolyl)allyl-PMS derivatives was 50°C lower than that of ω-H-PMS derivatives. These results indicate that the active species is produced effectively at the end unsaturated bond, which initiates the depolymerization of the polymer at rather low temperatures. Ionic degradation of these polymers was also investigated using butyllithium as an anionic initiator and methanesulfonic acid as a cationic initiator. Tendencies similar to the thermal degradation were observed. Therefore, it is concluded that a 2-phenylallyl substituent at the end of the PMS chain induces effective degradation through several mechanisms such as radical, anionic and cationic depolymerization reactions.     

Transmission electron microscope observation of organic–inorganic hybrid thin active layers of light-emitting diodes

Low-resistivity indium tin oxide [ITO] film was successfully deposited on oxygen plasma-treated polyethylene terephthalate [PET] surfaces at room temperature. X-ray diffraction [XRD] measurements demonstrated that the film deposited on the PET surface that had not been treated with oxygen plasma had an amorphous structure. In contrast, after the low-power oxygen plasma treatment of the PET surface, the ITO film deposited on the PET surface had a poly-crystalline structure due to interactions between electric dipoles on the PET surface and electric dipoles in the ITO film. The minimum resistivity of the poly-crystalline ITO was about 3.6 times lower than that of the amorphous ITO film. In addition, we found that the resistivity of ITO film is proportional to the intensity of the (400) line in the film's XRD spectra.     

Improvement of the Performance of Liquid Crystal Displays by Doping with Supramolecule-Protected Metal Nanoparticles

Metal nanoparticles are now creating a new class of materials that are different from either conventional bulk materials or atoms, giving one of the smallest building blocks of matter. Metal nanoparticles have various properties based on high surface area and quantum size effects. Here we focus on the application of metal nanoparticles to liquid crystal displays, which is providing a new field in science and technology. The doping of nanoparticles into liquid crystal materials induces the modification of almost all of the physical properties of the liquid crystal, causing a reduction in the response time of liquid crystal displays. These techniques may be an alternative approach for improving the properties of liquid crystals other than chemical synthesis.     

Joining of SiC by Al infiltrated TiC tape: Effect of joining parameters on the microstructure and mechanical properties

SiC ceramics were successfully joined by Al infiltrated TiC tapes at 900-1100 °C for 0.5-2 h in vacuum. Phase constituents, microstructure and mechanical strength of the prepared SiC joints were characterized. The prepared SiC joints display dense interlayer and crack-free interface. The interlayer primarily consists of TiC and Al phases, together with small amount of TiAl₃ and trace of Al₄C₃. With increasing the joining temperature or time, the interface layer either thickens or grows to multiple layers. The bending strengths of the SiC joints are higher than 190 MPa as bonded at present conditions, and are closely related with the property of interface and interlayer.     

Investigation on the Interactions between Self-Assembled β-Sheet Peptide Nanofibers and Model Cell Membranes

Self-assembled peptide nanofibers (NFs) obtained from β-sheet peptides conjugated with drugs, including antigenic peptides, have recently attracted significant attention. However, extensive studies on the interactions of β-sheet peptide NFs with model cell membranes have not been reported. In this study, we investigated the interactions between three types of NFs, composed of PEG-peptide conjugates with different ethylene glycol (EG) lengths (6-, 12- and 24-mer), and dipalmitoylphosphatidylcholine (DPPC) Langmuir membranes. When increasing the EG chain length, those interactions significantly decreased considering measurements in the presence of the NFs of: (i) changes in surface pressure of the DPPC Langmuir monolayers and (ii) surface pressure–area (π–A) compression isotherms of DPPC. Because the observed trend was similar to the EG length dependency with regard to cellular association and cytotoxicity of the NFs that was reported previously, the interaction of NFs with phospholipid membranes represented a crucial factor to determine the cellular association and toxicity of the NFs. In contrast to NFs, no changes were observed with varying EG chain length on the interaction of the building block peptide with the DPPC membrane. The results obtained herein can provide a design guideline on the formulation of β-sheet peptide NFs, which may broaden its potential.     

Phase structure in the blend of atactic poly(vinyl alcohol) with atactic poly(vinyl alcohol‐block‐vinyl acetate)

An almost fully saponified atactic poly(vinyl alcohol) and an atactic poly(vinyl alcohol‐block‐vinyl acetate) of which degree of saponification is 89 mol % were blended by a solution casting method. The phase structure of the blend film was analyzed by optical microscopy, ¹³C‐NMR, and differential scanning calorimetry. The most remarkable structure of the blend was composed of cylindrical domains penetrating the film. The swelling behavior of the blend films was also investigated in the dimethylsulfoxide and water mixed solvents to find differences in solubility and diffusion behavior between the matrix and the domain. The cylindrical domains could be selectively dissolved away in water and the film became porous. We tried to change the size of the cylindrical domain with various film preparation conditions. This aimed to turn the film into the useful filter membrane. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1807–1815, 2002