A backward extrusion analysis by the rigid–plastic integralless–meshless method

The rigid–plastic integralless–meshless method is applied to the analysis of plane strain backward extrusion. The rigid–plastic integralless–meshless method, based on the moving least squares approximation and the partial differential equations of mechanical equilibrium, is a truly meshless method. In addition, since there is no any integration in the formulation of the rigid–plastic integralless–meshless method, this method is also an integralless method. Compared with the conventional rigid–plastic FEMs, the rigid–plastic integralless–meshless method has some advantages that are briefly no mesh generation, no remeshing and no integration. Compared with BEMs and FBEMs, the rigid–plastic integralless–meshless method is found to have some merits such as sparse matrix, no singularity, no integration and no fundamental solution. Contours of the equivalent strain rate, the equivalent strain, the equivalent stress and the shear stress, etc. of the backward extrusion analysis using the rigid–plastic integralless–meshless method are obtained successfully.     

New polylactide/layered silicate nanocomposites. 5. Designing of materials with desired properties

Understanding the structure/property relationship in polymer/layered silicate nanocomposites is of great importance in designing materials with desired properties. In order to understand these relations, a series of polylactide (PLA)/organically modified layered silicate (OMLS) nanocomposites have been prepared using a simple melt extrusion technique. Four different types of OMLS have been used for the preparation of nanocomposites, three were modified with functionalized ammonium salts while fourth one was a phosphonium salt modified OMLS. The structure of the nanocomposites in the nanometer scale was characterized by using wide-angle X-ray diffraction and transmission electron microscopic observations. Using four different types of layered silicates modified with four different types of surfactants, the effect of OMLS in nanocomposites was investigated by focusing on four major aspects: structural analysis, thermal properties and spherulite morphology, materials properties, and biodegradability. Finally, we draw conclusions about the structure/property relationship in the case of PLA/OMLS nanocomposites.     

Structural development in cycloolefin copolymers under uniaxial elongational flow

Development of structures in new cycloolefin copolymers (COCs) of ethylene–norbornene (E–NB) and ethylene–tetracyclododecene (E–TD) of different NB/TD compositions were investigated under uniaxial elongational flow. For E–NB copolymer, which has multiblock sequences, a shoulder in WAXD at 0.76 nm was evident besides its amorphous halo, and the relative intensity of the peak increased with increasing comonomer content (NB). The appearance of a new peak for E–TD copolymer, and a relatively higher intense peak for E–NB copolymer at the same position of 0.76 nm, indicated that local ordering of the segments occurred when the COC was subjected to uniaxial flow. A lower comonomer composition of elongated COC, at a constant Hencky strain rate, exhibited two T_g values, whereas a higher composition showed a single T_g. Both local ordering and segmentization occurred in low comonomer content COCs but only local ordering occurred in higher comonomer content COCs. Both the shear viscosity and roll processing experiments exhibited similar phenomena of segregation. A model is proposed to illustrate the structure of COC after uniaxial elongation/deformation. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3421–3427, 2004     

Catching a molecule at the air-water interface: Dynamic pore array for molecular recognition

As a soft and flexible porous structure, a pore array of a steroid cyclophane SC(OH), which consists of the rigid 1,6,20,25-tetraaza[6.1.6.1]paracyclophane ring connected to four steroid moieties (cholic acid) through flexible L-lysine spacers, was prepared at the air-water interface. As confirmed by surface pressure (π)-molecular area (A) isotherms, transition between open conformation and cavity conformation of the SC(OH) molecule was reversibly induced upon repeated compression and expansion of its monolayer at pH 11 where amino groups of the lysine residues are not fully deprotonated. Capture and release of an aqueous fluorescent guest (TNS) by SC(OH) was observed upon dynamic cavity formation through surface fluorescence spectroscopy. At pH 12, dynamic cavity formation of SC(OH) was sufficiently suppressed, and the capture and release of an aqueous TNS by the monolayer was not virtually observed. Lessened electrostatic repulsion between the SC(OH) molecules due to conversion of ammonium to free amine may prevent the cavity from reopening. The importance of dynamic nature of cavity formation on the guest binding was also proved by control experiments using SC(H), which cannot form cavity conformation at any surface pressures at both pH 11 and 12.     

Multi-step precipitation separation system using mixture of thermosensitive polymers

Summary Multi-step precipitation separation system was developed by using aqueous mixtures of some thermosensitive polymers. The following three polymers were used here; poly(N-n-propylacrylamide), poly(N-isopropylacrylamide), and poly(N-isopropylmethacrylamide). A mixture of the three polymers showed three endothermic peaks, and the peak top temperatures were almost consistent with that of the each polymer solution. The polymers were purified by thermal precipitation to obtain fractions which can respond in narrow temperature ranges prior to use. In the case of the precipitation separation of two polymers mixtures, purities of the obtained precipitate and supernatant fractions became high comparing with the case in which the unpurified polymers were used. Parts of the polymers which were not the precipitation targets were also precipitated by the separation procedures. This was caused not only by insolubilization of the non-targeted polymers due to their phase transitions but also by their non-specific entanglement with the targeted polymers. The purities of the fractions also improved when the difference of the phase transition temperature between two polymers was large enough to avoid the coprecipitation. In the case of the precipitation separation of mixtures of the three polymers, purities of each fraction also improved when the purified polymers were used.     

Rapid Quenching Technique Using Thermal-Image Furnace for Glass Preparation

A new technique combining a thermal-image furnace and a twin roller is described for quenching the melt to form glass. The technique was applied to the simple system Li₂O-SiO₂, since its fundamental parameters in the estimation of critical cooling rate are available. Glass flakes were obtained in the composition Li₄SiO₄, for which a very large critical cooling rate (∼10⁹ K·s⁻¹) was needed for glass formation.     

Reactive processing of polymer blends: Analysis of the change in morphological and interfacial parameters with processing

The change in morphology and interface quantities have been analyzed for an immiscible polymer blend during reactive processing. A model polymer/polymer combination, hydroxy-terminated poly(ε-caprolactone)/liquid rubber with α, ω-carboxy groups, was employed. The blend was subjected to light scattering measurements, ellipsometry, and gel permeation chromatography (GPC). Size reduction of the dispersed phase during processing was followed by a systematic decrease in the correlation distance ζ and an increase in the specific interfacial area Ssp, both by the Debye-Bueche plot of light scattering profiles. Also observed was the time variation of the volume fraction of interface V_λ estimated as a product of the Ssp and the interfacial thickness by ellipsometry. The changes in ζ, Ssp, and V_λ with processing were accelerated when a coupling agent,γ-aminopropyltriethoxysilane (APS), was added. The amount of block copolymer formed in-situ in the APS-loaded system was estimated by GPC with RI and UV detectors. For the size reduction kinetics in both APS-loaded and -unloaded systems, Rittinger's law was found to be applicable.     

Structure and properties of nanocomposites based on poly(butylene succinate) and organically modified montmorillonite

Poly(butylene succinate) and organically modified montmorillonite nanocomposites with there different compositions were prepared via melt blending in a twin‐screw extruder. The structure of the nanocomposites was studied with X‐ray diffraction and transmission electron microscopy, which revealed the formation of intercalated nanocomposites, regardless of the silicate loading. Dynamic mechanical analysis revealed a substantial increase in the storage modulus of the nanocomposites over the entire temperature range investigated. The tensile property measurements showed a relative increase in the stiffness with a simultaneous decrease in the yield strength in comparison with that of neat poly(butylene succinate). The oxygen gas barrier property of neat poly(butylene succinate) improved after nanocomposite preparation with organically modified montmorillonite. The effect of the layered‐silicate loading on the melt‐state linear viscoelastic behavior of the intercalated nanocomposites was also investigated. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 777–785, 2006     

Organic–silicate hybrid catalysts based on various defined structures for Knoevenagel condensation

Two types of organic–inorganic hybrid base catalysts are prepared. Organic-functionalized molecular sieves (OFMSs), particularly “amine-immobilized porous silicates”, are designed based on common idea to immobilize catalytic active sites on silicate surface. Silicate–organic composite materials (SOCMs), such as “ordered porous silicate–quaternary ammonium composite materials”, are the precursors of ordered porous silicates obtained during the synthesis. Both the OFMS and the SOCM are used as the catalysts for Knoevenagel condensation. Among the OFMSs, there is clear tendency that the use of molecular sieve with larger pore volume and/or surface area gives the product in higher yield. Aminopropylsilyl (AP)-functionalized mesoporous silicates such as AP-MCM-41 gives the product in high yield under mild conditions. No loss of activity is observed after repeated use for three times. The SOCMs are also active for the same reaction. The precursors of the mesoporous silicates are more active than those of microporous silicates. This material can be repeatedly used without significant loss of activity. High activity is not due to the leached species. The active sites of the SOCM catalysts are considered to be SiO⁻ moieties located on the pore-mouth. Activity of the SOCM increases when the reaction is carried out without solvent, whereas decrease in activity of the OFMS is observed in the solvent-free system.     

Stabilization of poly(vinyl chloride). I. Change in color of poly(vinyl chloride) compounded with some metal soaps

Poly(vinyl chloride) (PVC) with one or more metal salts added was colored by the action of heat to investigate the stabilization mechanism. The coloration and the color difference of heated PVC compound films varied according to the metal salt added. The decoloration of the colored compound films was advanced markedly in THF, DMF, acetone, and ammonia. On the other hand, the heated achromatic PVC film containing Cd/Ba soaps underwent an opposite change, from colorless to yellow orange, in the above materials. This means that the coloration of heated compound films may result from the formation of some complex (for example, π complex of the polyene with the metal chloride). Furthermore, the colored film with cadmium stearate was decolored by roll mixing with the colored film containing barium stearate. These results indicate that the stabilization with metal soaps may be founded on a physical phenomenon such aa an effect of complementary color.