Studies on biaxial stretching of polypropylene film. IX. Melting behavior of biaxially stretched film in one step

Melting temperature of a film biaxially stretched in one step in air at 152 or 140°C increases with increase of vA, whereas heat of fusion and density decrease with increase of vA, where vA is the degree of stretching in area. The rapid decrease in density occurs for vA > 10. Extrapolation of the plot of the density versus vA^?1/2 gives a value of 0.870 g/cm³ at infinite vA, which has been reported as the amorphous density of isotactic polypropylene by Farrow. This is so because the fine structure of the film becomes more and more amorphous with further stretching and reaches completely amorphous state at infinite vA. The temperature of stretching has a strong effect on the thermal behavior of a film; a low stretching temperature (140°C) brings about lower melting temperature, heat of fusion, and density. Crystallinity after melt press has not so large an effect on the melting behavior as the stretching temperature. Melting temperature and the shape of the thermogram also depend on the heating rate. There is an appropriate heating rate depending on vA which gives the minimum melting temperature. With stretched samples, a small side peak or a shoulder appears at a relatively low temperature in the thermogram when a high heating rate is used.     

Fat splitting by the twitchell process at low temperature

Summary A study was made of the degree of splitting of coconut and soybean oils by the Twitchell process at 35±0.1°C. with no shaking or stirring, using an agent consisting mainly of tetrabutyl naphthalene sulfonic acid with water or dilute sulfuric acid. The degree of splitting was greater with sulfuric acid than with water. In general, the degree of splitting of soybean oil was greater when the sulfonic acid was dissolved in the oil layer than when it was in water. The reverse was true with coconut oil. Although addition of glycerol had no effect on the degree of splitting, addition of glacial acetic acid to the coconut oil system decreased fat splitting to a considerable extent. Addition of coconut fatty acids to the coconut oil system had little effect, but soybean fatty acids added to the soybean oil system markedly increased the degree of splitting. For the first time it has been demonstrated that, at 35±0.1°C., splitting of a fat by the Twitchell process occurs in a stepwise way. Coconut oil in contact with 1N sulfuric acid containing the sulfonic acid, corresponding to 1% by the weight of the oil, was about 90% split in 15 to 30 days, depending on the area of contact of the two layers. The diglyceride concentration reached a maximum during the early days of the reaction and then decreased somewhat. Monoglyceride concentration appeared to reach a maximum more slowly and then continued at that level as the concentrations of free fatty acids and glycerol steadily increased. Presented at the symposia on fat of the Chemical Society of Japan, Nov. 10, 1954, and Nov. 8, 1955, Nagoya, Japan; and the 8th annual meeting of the Chemical Society of Japan, Apr. 2, 1955, Tokyo, Japan.     

Miscibility and Probe Tack of Acrylic Pressure Sensitive Adhesives—Acrylic Copolymer/Tackifier Resin Systems

Miscibility between acrylic copolymers and tackifier resins are investigated in terms of phase diagrams, and the probe tack of the blends are measured as a function of both temperature and rate of separation in order to obtain the master curves. It is found that the probe tack of the pressure sensitive adhesives are closely related to the miscibility between the components. The master curves of the miscible blends shift along the X(rate)-axis according to the change of T_g of the bulk materials with a gradual variation of the peak heights. However, those of the immiscible blends will not shift along the X(rate)-axis, but the magnitude will decrease with increase of a dispersed phase.     

Isotactic polypropylene hollow microfibers prepared by CO2 laser‐thinning

An isotactic polypropylene hollow microfiber was continuously produced by using a carbon dioxide (CO₂) laser‐thinning method. To prepare the hollow microfiber continuously, the apparatus used for the thinning of the solid fiber was improved so that the laser can circularly irradiate to the hollow fiber. Original hollow fiber with an outside diameter (OD) of 450 μm and an internal diameter (ID) of 250 μm was spun by using a melt spinning machine with a specially designed spinneret to produce the hollow fiber. An as‐spun hollow fiber was laser‐heated under various conditions, and the OD and the ID decreased with increasing the winding speed. For example, when the hollow microfiber obtained by irradiating the CO₂ laser to the original hollow fiber supplied at 0.30 m min^?1 was wound up at 800 m min^?1, the obtained hollow microfiber had an OD of 6.3 μm and an ID of 2.2 μm. The draw ratio calculated from the supplying and the winding speeds was 2667‐fold. The hollow microfibers obtained under various conditions had the hollowness in the range of 20–30%. The wide‐angle X‐ray diffraction patterns of the hollow microfibers showed the existence of the highly oriented crystallites. Further, the OD and ID decreased, and the hollowness increased by drawing hollow microfiber obtained with the laser‐thinning. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2600–2607, 2006     

Influence of Metal Ions on the Order-Disorder Transition Temperature of the Ba-M-O (M: La, Y, In, or Ga) System

Preparation of BaLa₂O₄, B_a3,Y₄O₉, B_a,In₂O₅, and Ba₃Ga₂O₆ powders and their sintering were investigated in Ar or air. These sintered bodies with perovskite-related structure were synthesized by reaction sintering, using mixed powders in the atomic ratios of Ba/La = 1, Ba/Y = 0.75, Ba/In = 1, and Ba/Ga = 1.5. The order-disorder transition temperatures of the BaLa₂O₄, Ba₃Y₄O₉, Ba₂In₂O₅, and Ba₃Ga₂O₆ sintered bodies were 270°, 350°, 880°, and 123O^oC, respectively. It was found that the temperatures were influenced by the ionic radius of cations in B sites, and the transition temperatures decreased with increasing ionic radius.     

Synthesis and properties of bismaleimide resins containing ether bonds

New bismaleimides containing ether bonds were prepared. The thermal properties of the bismaleimides were investigated by differential scanning calorimetry (DSC). The effects of structure of the bismaleimides and curing conditions on the thermal and mechanical properties of the cured resins such as initial decomposition temperature (T_d), glass transition temperature (T_g), and flexural strength were studied. The introduction of ether bonds to bismaleimide resins decreased the brittleness of the resins without reductions in their heat-resistant properties.     

Crystallization of running filament in melt spinning of polypropylene

The crystallization kinetics of the running filament in melt spinning have been studied for three cases: isothermal crystallization of an isotropic melt, non-isothermal crystallization of an isotropic melt, and non-isothermal crystallization of a non-isotropic melt. Both the temperature and the orientation dependences of nucleation rate and growth rate are estimated for polypropylene. Calculated curves for non-isothermal crystallization of a non-isotropic melt with partial high orientation closely approximate the experimental data. In particular, the experimental data are best explained by crystallization with two-dimensional growth. The crystallization processes in melt spinning may be governed by localized molecular orientation of the supercooled melt in the initial stage.     

Production of antimicrobially active silk proteins by use of metal‐containing dyestuffs

The work presented here discusses a new technique for preparing silk fibers and films with persistent antimicrobial activity through use of metallic dyestuffs during the fiber dyeing process. The length of the silk fibers investigated contracted when the fibers were immersed in concentrated neutral salt solutions, such as calcium or potassium nitrate, at elevated temperature levels. The birefringence and molecular orientation of the silk fibroin molecules became less ordered by the action of the neutral salt solutions, resulting in increased dyestuff absorption. Subsequently, contracted silk fibers were dyed with metallic dyestuffs containing Cr or Cu for the purpose of obtaining silk fibers with antimicrobial activity. Silk fibers dyed with metallic dyestuffs showed significant antimicrobial activity against the plant pathogen Cornebacterium and the human pathogen Coli bacillus. Tensile strength of the silk fibers after the salt shrinking and dyeing processes did not show a significant change, whereas the elongation at break was increased slightly. The techniques described here for preparing significantly active antimicrobial silk fibers are effective and economic ways of providing new materials for industrial and biomedical applications. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1181–1188, 2002     

Thermal Expansion Behavior of the Si3N4-Whisker-Reinforced Soda-Borosilicate Glass Matrix Composite

Thermal expansion behaviors of a Si₃N₄-whisker-reinforced sodaborosilicate glass matrix composite are studied. An abrupt increase of the coefficient of thermal expansion is observed and is attributed to formation of crystobalite in the sodaborosilicate glass matrix. This thermal expansion behavior is discussed with special reference to the phase transformation of the crystobalite.     

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.