Polyacrylonitrile/Nylon 6 Blends: Preparation and Characterization

Summary: Polyacrylonitrile (PAN) particles with micro‐size ranges (0.15–2 μm) were prepared by emulsion and dispersion polymerizationa and in supercritical carbon dioxide media. The PAN particles were blended with Nylon 6 (PA6) at 220 °C by using a miniature mixer; it was found that melt‐mixing was possible for PAN‐rich compositions as high as 70 wt.‐%. Blends were characterized by scanning electron microscopy, IR, viscosity measurements, differential scanning calorimetry, and dynamic mechanical thermal analysis (DMTA). The size and shape of original PAN particles were retained in PAN/PA6 blends. The useful range to blend PAN particles size was less than 1 μm in terms of shape retention of the PAN particles in blends. Blends with 40 wt.‐% PAN content were found to be melt‐processable. The elastic modulus was higher for PAN/PA6 blends than pure PA6.

SEM photograph of PAN‐SC/PA6 blend with a 40/60 weight ratio.     

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.     

Improvement in Thermoelectric Characteristics of n-type Iron Disilicide by Local Composition Modification

High thermoelectric figure of merit semiconducting ceramics of n -type iron disilicide with modified local compositions have been developed. Sintering and annealing of the composite powder composed of iron disilicide and precipitated cobalt (II) hydroxide resulted in the dissolution of excess Co and oxygen into the iron disilicide phase. Excess Co segregated to the grain boundary region, while interstitially incorporated oxygen was distributed homogeneously in the microstructure. The maximum figure of merit achieved was 5.2 × 10⁻⁴/K at 673 K.     

DSC and synchrotron-radiation X-ray diffraction studies on crystallization and polymorphic behavior of palm stearin in bulk and oil-in-water emulsion states

The crystallization and polymorphic behavior of palm stearin (PS) in a bulk state and in oil-in-water (O/W) emulsion droplets (average diameter, 1.7±0.3 μm) was observed by using DSC, optical microscopy, and in situ X-ray diffraction with synchrotron radiation (SR-XRD). For the bulk sample the DSC measurements revealed three main exothermic peaks at approximately 31 (large), 21 (small) and 3°C (medium) on cooling, and broad endothermic peaks at approximate −3 (small), 8, 15 to 25 (medium), and 37 and 53°C upon heating. The SR-XRD patterns taken during cooling from 60 to −5°C clarified that the DSC exothermic peaks around 31 and 3°C corresponded to crystallization of the α form of high-melting and low-melting fractions, respectively, and that the occurrence of β′ corresponded to the small exothermic peak around 21°C. The XR-XRD patterns taken during heating from −5 to 60°C demonstrated that the DSC endothermic peaks corresponded to the following transformation processes: melting of α of the low-melting fraction (−3°C), melt-mediated transformation from α to ∇′ (15–25°C), melting of β′ (36°C), and melting of β (53°C) of the high-melting fraction. As for the O/W emulsion sample, the DSC and SR-XRD measurements during the cooling and heating processes exhibited basically the same behavior as that of PS in the bulk state, except that β′ did not crystallize during the cooling process, and the temperatures of crystallization of α, melt-mediated α→β′→β transformation, and melting of β were lower in the emulsion droplets than in the bulk state.     

Thermal behavior of hydrostatically extruded polycarbonate and high-impact polystyrene

Effects of hydrostatic extrusion on the thermal properties of polycarbonate (PC) and of high-impact polystyrene (HIPS) were studied using differential scanning calorimeter (DSC) measurements. A glass transition temperature (T_g) and a peak temperature were determined from the DSC curves for both PC and HIPS extrudates. The T_g values of the PC extrudates, with a percentage reduction in area, R, from 40 to 50%, change appreciably from the value for the as–received PC. The results of the hydrostatic extrusion of the PC billets suggest that a two stage deformation process of molecular chains may be involved. Shear-banding is observed for HIPS extrudates with R = 30 to 60%; this fact indicates that a sub-glass transition (β-transition) occurs at temperatures below T_g. It is suggested that the molecular chains of the HIPS extrudate with R = 70% are oriented in the direction of hydrostatic extrusion. The deformation mechanism of molecular chains caused by the hydrostatic extrusion is discussed.     

Oxidative coupling of methane over LaCoO3−δ-based mixed oxides

The catalytic activity of LaCoO_3–-based mixed oxides for the oxidative coupling of methane has been tested by TPR and cyclic reaction. Characterization has been done by XRD, TGA and Mössbauer spectrometry. It is likely that the perovskite-crystal structure containing hypervalent metal ions has an important role and that unique structural oxygen species in the perovskite contribute to the partial oxidation of methane.     

Studies on miscibility in homopolymer/ random copolymer blends by equation of state theory

The miscibility of poly(methyl methacrylate) (PMMA) and styrene-acrylonitrile random copolymers (SAN) blends was investigated on the basis of the Flory—Orwoll—Vrij equation of state theory. To obtain the equation of state parameters (P*, V*_sp, T*: characteristic parameters), the pressure—volume—temperature (PVT) behaviour was measured for PMMA and a series of SANs with various acrylonitrile contents. The exchange energy parameter X_ij was also calculated by fitting the theory to some phase diagrams of PMMA/SAN blends. The Flory—Huggins interaction parameter χ was separated into two contributions based on the equation of state theory for mixtures: the exchange energy term χ_inter and the free volume term χ_free. Both the temperature and copolymer composition dependences of χ_inter and χ_free were estimated by calculations using the equation of state parameters. There exists a region in which χ_inter is negative, leading to a miscibility window in PMMA/SAN blends. However, the immiscibility at high temperatures in the blends cannot be explained only by χ_inter; it is caused by the free volume contribution, χ_free. The miscibility window behaviour in PMMA/SAN blends may be explained within the framework of the equation of state theory.     

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.     

Mie scattering from sphere structures in polymer blends

Polymer blends of transparent poly(methyl methacrylate) and polystyrene become opaque due to light scattering at the boundaries of the two polymers. The polymer blend is light brown when it is illuminated by white light. The coloring depends on the spherical domain structures existing in the polymer blend. The coloring was analyzed by using the rigorous Mie theory. The Mie results were compared with the semiempirical results previously reported by the authors. The wavelength dependence of theoretical scattering efficiencies on radii of scattering spheres from 0.05 to 1.2 μm was obtained for polystyrene spheres in poly(methyl methacrylate) matrix, and vice versa. The scattering at the short wavelength region is stronger than at the long wavelength region. The scattering efficiencies become almost constant in the visible wavelength region for sufficiently large spheres.     

Shape memorizing properties of a hydrogel of poly(vinyl alcohol)

Hydrogel prepared by repetitive freezing and thawing of poly(vinyl alcohol) aqueous solution was chemically crosslinked with glutaraldehyde. The chemically crosslinked hydrogel hardly changed its physical appearance, and showed good elasticity and strength as original gel. However, after treating in boiling water, it swelled a little, depending on the condition of the chemical treatment. The melted gel thus obtained showed shape memorizing property, that is, it could firmly hold nearly 200% of strain, keeping its original high elasticity. The strain could be released very quickly (< 1 s) in boiling water, and the gel was suggested to be applied to a new type of gel actuator. X-ray diffraction study revealed that the melted gel does not necessarily reform the physical crosslinks in exactly the same manner as the original gel in the process of shape restoring, but the distribution of the physical crosslinks can be restored as they were. It was suggested that the chemical crosslinks which remember the distribution of the physical crosslinks plays a critical roll in the shape restoring process.