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31 巻, 6 号
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1975 年 31 巻 6 号 p. T240
発行日: 1975年
公開日: 2008/11/28
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勝浦 嘉久次1975 年 31 巻 6 号 p. P170-P174
発行日: 1975/06/10
公開日: 2008/11/28
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柴垣 健1975 年 31 巻 6 号 p. P175-P180
発行日: 1975/06/10
公開日: 2008/11/28
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町田 守久, 山本 雄三, 斉藤 安史, 木下 茂武1975 年 31 巻 6 号 p. T193-T201
発行日: 1975/06/10
公開日: 2008/11/28
ジャーナル フリーThe morphological changes of polymer crystals during isothermal annealing are usually observed in the medium of air. Single crystal mats of polyetylene (unfractionated) used here were annealed isothermally in xylene for various times. The treated samples were quenched in 0°C methanol and dried in vacuo at room temperature.
The observations of weight loss, long period, molecular orientation and melting point for dried samples were compared with those of the mats annealed directly in air, as a function of treating temperature aT and time-interval ta. The main results obtained are as follows;
(1) At the temperature below Ta=90°C, the weight losses of dried samples were not detectable, where the long spacings of the samples also remained unchanged on the small-angle X-ray pattern like that of untreated original one. It was assumed that xylene acted only as swelling agent for polyethylene at considerably low temperatures.
(2) Upon increasing the temperature higher than Ta=92°C, the weight losses of dried samples became more noticeable, at the approach of Ta=100°C loss-isotherms levelled off after few minutes. In these stages the dissolved polymers recrystallized rapidly at the surfaces of the remaining crystals. It was interesting to note that the small-angle diffraction patterns of the samples treated at Ta=92°C (ta=10min.) or Ta=95°C (ta=1min.) showed coexisting of two long periods corresponding to the initial and the increased new thicknesses.
(3) At the temperature between Ta=92°C (ta<600min.) and 100°C (<10min.), the characteristic phenomena on WAXS patterns for the dried samples were that the orientations remained unchanged, and those on DSC thermograms were that the single sharp melting peaks were preserved during the fusion of samples.抄録全体を表示PDF形式でダウンロード (996K) -
関根 哲, 山本 雄三, 斉藤 安史, 木下 茂武1975 年 31 巻 6 号 p. T202-T213
発行日: 1975/06/10
公開日: 2008/11/28
ジャーナル フリーMorphological changes of poly (ethylene terephthalate) (PET) film during degradation in an aqueous ethylamine solution at room temperature were examined using photomicrographies. Sample films used in this study were prepared by stretching and annealing the melt quenched amorphous PET film, as shown schematically in Fig.1.
The more crystalline and highly oriented the specimen is, the lower is the rate of the weight loss during the aminolysis (Fig.2-4). This indicate that ethylamine selectively etches the amorphous PET chains.
In the case of non-crystalline film (Fig.5), the etching pattern was sensitive to the chain orientation anisotropy. For the crystalline films (Fig.6-8), the etching pattern mainly occurs perpendicularly to the draw direction in accordance with the formation of folded-chain crystals during annealing.
The changes of weight loss and of the melting behavior are in accordance with the results from the microscopy.抄録全体を表示PDF形式でダウンロード (1792K) -
松本 喜代一, 黒木 俊之, 今村 力造1975 年 31 巻 6 号 p. T213-T220
発行日: 1975/06/10
公開日: 2008/11/28
ジャーナル フリーThis paper reports on the mechanical properties and behavior of molecular orientation of the Nylon-6 films by means of the uniaxial and biaxial stretching by wet-process in a hot-water bath.
Unoriented low crystalline Nylon-6 film T-die extruded with a thickness of ca. 200μ was stretched at constant rate of 400%/min in a recirculating hot water at 70°C by various methods using a filmstretcher; i. e. uniaxial stretching under free width and/or constant width, and simultaneous biaxial stretching. The molecular orientation was studied by both measurements of birefringence for a tilted specimen and x-ray diffraction. The mechanical properties of the stretched films such as tensile strength, elongation at break, Young's modulus and F5 value were measured at 20°C under 65% R. H. using an Autograph tensile tester. The dynamic viscoelasticity, i. e. the temperature dependencies of dynamic loss modulus E″ were measured at 100Hz using a Viscoelastic Junior Spectrometer.
The following results were obtained;
(1) The characteristics of stretched films prepared by wet-process were noted that lower Young's modulus, lower F5 value and higher degree of crystallinity as compared with that of stretched films prepared by dryprocess. These properties are due to difference of the behavior of molecular orientation and the size of crystallite in the both stretched films.
(2) Irrespective of stretch ratio the anisotropy of mechanical properties for the films uniaxially stretched under free width is greater than that of the stretched under constant width at the same stretch ratio of machine direction. Particularly, the Young's modulus of latter films are nearly equal in both the machine and the transverse directions.
(3) For the simultaneous-biaxially stretched films prepared by wet-process, the mechanical and dynamic viscoelastic properties are isotropic within the plane as seen for the films prepared by dry-process, during all stretch ratio. However the tensile strength and elongation of these films were found to be similar to general tendency of the change, on the contrary, the Young's modulus and F5 value is not varied with the stretching by wet-process.抄録全体を表示PDF形式でダウンロード (1087K) -
大村 寧1975 年 31 巻 6 号 p. T221-T226
発行日: 1975/06/10
公開日: 2008/11/28
ジャーナル フリーIn the previous reports1), 2), physical properties corresponding to sensory values of polyurethane foams were reported that compressive young's modulus is the important physical property on handling. As the modulus of elasticity of polymer is influenced by the change of the temperature, compressive young's modulus which is measured as the tangent of the initial part of stress-strain curves depends on the temperature. In this report, temperature dependency of compressive young's modulus for polyurethane foam is mainly investigated and humidity dependency is also discussed.
The results obtained are as follows:
1) Compressive young's modulus Yz of foam in parallel to rising direction depends on the temperature following the equation Yz (t)=k.Y0 (t), where k means lz/lz+2lx.(ρ/ρ0) and is the constant, and Y0 (t) is the temperature dependency on compressive young's modulus of solid elastomer of the samples.
2) Compressive young's modulus Yx (t) of foam in perpendicular to rising direction is able to be explained in the same way of Yz (t) mentioned in 1). And the fact above mentioned proves that the linear expansion of solid elastomer is isotropic.
3) Compressive young's modulus Y0 (t) of solid elastomer is the entropy elasticity at 10_??_40°C, and depend on the temperature following the equation Y0 (t)=K (273+t), (K; const.)
4) The humidity dependency of compressive young's modulus Y of foam is negsible in case of the static compression.抄録全体を表示PDF形式でダウンロード (403K) -
辻本 石男, 高橋 利禎, 渡辺 孝寛, 藤原 久, 水野 恵二, 大坂 英一郎1975 年 31 巻 6 号 p. T226-T232
発行日: 1975/06/10
公開日: 2008/11/28
ジャーナル フリーReswelling processes of drawn nylon-6 and poly(ethylene terephthalate) in tetrachloroethylene, water, and DMF were investigated. Starting specimen containing some voids was prepared by the heat treatment of drawn nylon-6 and drawn poly (ethylene terephthalate) in benzyl alcohol and DMF respectively. Structural change on swelling was studied by the small-angle X-ray scattering method. The following results were obtained.
1. Substantially tetrachloroethylene did not penetrate into the amorphous region of drawn nylon-6, while it could fill the voids, On the other hand, water could penetrate into both the amorphous region and voids.
2. Degree of swelling of nylon-6 in water was higher than that in tetrachloroethylene.
3. Swelling of nylon-6 in water attains equilibrium within a few minutes, though the time taken to reach swelling equilibrium in tetrachloroethylene is about 20 hours.
These differences in swelling behaviors of nylon-6 in tetrachloroethylene and water may be interpreted on the basis of differences in molecular sizes of solvents and the differences in interaction between solvents and nylon-6.
4. Tetrachloroethylene and DMF could penetrate into the voids and the amorphous region of drawn poly (ethylene terephthalate).抄録全体を表示PDF形式でダウンロード (1188K) -
加藤 弘1975 年 31 巻 6 号 p. T232-T240
発行日: 1975/06/10
公開日: 2008/11/28
ジャーナル フリーThe adsorption of acid azo dyes by silk was investigated. The amount of saturated adsorption and the standard affinity of acid dyes were estimated by Gilbert-Rideal theory.
The results obtained were as follows:
(1) The amounts of saturated adsorption of dye acids were estimated by the extrapolation of the relation between and For five levelling dyes, the mean of saturation values was 19.4×10-5 eq/g, which was almost equivalent to that of hydrochloric acid. This indicates that not only mono-anionic dyes, but also poly-anionic ones are sorbed stoichiometrically. Therefore, it was reasonably considered that adsorption of levelling dyes is mainly due to ionic linkage between dye anion and cationic sites in silk.
On the other hand, the amounts of saturated adsorption of Acid Blue 92 and Acid Red 85 which belong to grade III and IV, respectively in SDC Migration Test, were by about 18% larger than those of levelling dyes.These results suggest the increase of non-polar van der Waals force contribution in the adsorption.
(2) The standard affinities were hardly dependent on adsorpted amounts over the concentration range studied and reasonable agreed as revealed in Table 2-6. It was found that the standard affinities increase with the molecular weight of dyes and also are somewhat affected by the nature and position of the substituents. Moreover, the standard affinities of dye anions decreased by 2.38 kcal/mol when an additional sulphonic acid group was introduced into the dye molecules.
(3) From the difference of the standard affinities of Acid Orange 7 and Acid Yellow 36 between silk and wool, it was considered that the role of hydrogen ion for silk is more important than that for wool in dyeing by levelling dyes.
(4) In the range 40 to 80°C, the standard heats of levelling dye in adsorption were calculated as -4.5_??_-6.5 kcal/mol. These values are slightly smaller than those for wool. The standard entropy was positive as found for hydrochloric acid.抄録全体を表示PDF形式でダウンロード (592K)
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