巻号一覧
30 巻, 12 号
選択された号の論文の11件中1～11を表示しています
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三浦 義人1974 年 30 巻 12 号 p. P415-P421
発行日: 1974/12/10
公開日: 2008/11/28
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久世 栄一1974 年 30 巻 12 号 p. P422-P427
発行日: 1974/12/10
公開日: 2008/11/28
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小泉 修介1974 年 30 巻 12 号 p. P428-P433
発行日: 1974/12/10
公開日: 2008/11/28
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化学シフトによる検討南後 守, 堀江 幹寿, 片山 明, 黒木 宣彦1974 年 30 巻 12 号 p. T541-T544
発行日: 1974/12/10
公開日: 2008/11/28
ジャーナル フリーThe interactions of organic cations, such as alkylamine hydrochlorides, RNH+3Cl-(R=CH3, C2H5, C3H7, C4H9) and tetraalkylammonium bromides, R4N+Br- (R=C2H5, C3H7, C4H9) with an organic anion, 2, 7-naphthalenedisulfonic acid (NDS) in aqueous solutions have been studied by using nmr spectroscopy. For comparison, the interactions of aliphatic alcohols (ROH, R=C2H5, C3H7, C4H9) with NDS were studied.
The chemical shifts of aliphatic protons of such compounds in the presence of NDS were displaced to higher field (relative to external TMS). The large upfield shifts can be explained by the proximity of the aliphatic moieties to the anisotropic aromatic in aqueous solutions. In this paper were listed the shifts, Δδ, observed for alcohols, alkylamine hydrochlorides and tetraalkylammonium bromides (1 mol/l) when the medium was changed from pure water to NDS aqueous solutions (1 and 1.5 mol/l).
The results obtained are as follows:
(1) Alcohols. The shifts, Δδ, increased with increasing the length of the alkyl chains. Methyl and methylene proton signals were shifted to about the same extent.
(2) Alkylamine hydrochlorides. The shifts increased with increasing the length of the alkyl chains. The methyl proton singals were shifted more than the methylene protons.
(3) Tetraalkylammonium bromides. The shifts decreased with increasing the length of the alkyl chains. The methylene proton signals were shifted more than the methyl protons.
From the above results the spatial mode of the interaction between the organic ions in aqueous solutions was discussed.抄録全体を表示PDF形式でダウンロード (268K) -
木村 光雄, 山口 達郎, 谷口 哲雄, 清水 融1974 年 30 巻 12 号 p. T544-T548
発行日: 1974/12/10
公開日: 2008/11/28
ジャーナル フリーThe heat of adsorption of hydrohalogenic acids (HCl, HBr and HI) on polyamide was measured by the flow method at 30°, 40° and 50°C. From the heat of adsorption at saturated adsorption and -Δμ°I (obtained from adsorption isotherm), the entropy change of adsorption (ΔS°C•I) was calculated. The value of at same temperature was HCl<HBr<HI and ΔS°C•I was HCl>HBr>HI, and as the temperature increases increases and ΔS°C•I decreases.
From the measurement of NMR absorption spectra of water proton in D2O+H2O solution of these acids, a parameter (Δδ) which corresponded with the state of hydration of these acids in aqueous solution was obtained. The positive value of, Δδ shows the destructiveness of water structure and the negative one shows the formativeness. The Δδ of these acids shows a negative value and this value is equal to the sum of ΔδH+ (water structure formation) and ΔδX- (Water structure destruction). The value of ΔδX- was Cl-<Br-<I-, that is, I- is more destructive than Cl- for the water structure. Plots of ΔS°C•I against Δδ show a straight line.
From these results, it is assumed that the difference of entropy change of adsorption of these acids correspond with the difference of the water structure destructiveness of acid anions, i.e., the difference of correspond with the difference of the endothermic process of acid anions. It is also assumed that the increase in with increasing temperature is closely related to the decrease in the structure of water.抄録全体を表示PDF形式でダウンロード (346K) -
木村 光雄, 山口 達郎, 清水 融1974 年 30 巻 12 号 p. T549-T552
発行日: 1974/12/10
公開日: 2008/11/28
ジャーナル フリーThe heat of adsorption of alkylmonosulfonic acids (CnH2n+1SO3H, n=1_??_4) on polyamide was measured by the flow method at 30° and 40°C. Observed values of heat of adsorption are influenced considerably by the measured temperature and concentration of acid similarly to the case of hydrohalogenic acids (HX). From the heat of adsorption at saturated adsorption and -Δμ°I (obtained from adsorption isotherm), the entropy change of adsorption(ΔS°C•I) was calculated. The value of decrease with increasing alkyl group in acid, and all these values are smaller than those of HX. A parameter which is concerned with the state of hydration of these acids in the aqueous solution was obtained from the measurement of NMR absorption spectra, and the relationship between ΔS°C•I and Δδ is discussed. Plots of ΔS°C•I against Δδ show a straight line.
Differences in and Δδ between these acids except buthansulfonic acid correspond to those in enthalpies and entropy changes for the transfer of normal aliphatic hydrocarbons (CnH2n+2, n=1_??_3) from the liquid state to the aqueous solution at 25°C, respectively.
From these results, it is assumed that the process of dehydration of these acid anions is an important factor for the adsorption of alkylsulfonic acids on polyamide similarly to the case of HX, and in these cases, differences in ΔS°C•I correspond with those in the interaction of alkyl group in acid anions with water. It is also assumed that ΔS°C•I of these acids are positively larger than those of HX and decrease by the decrease of the structure of water with dehydration of alkyl group.抄録全体を表示PDF形式でダウンロード (275K) -
脇田 登美司, 青木 一三, 黒木 宣彦1974 年 30 巻 12 号 p. T553-T559
発行日: 1974/12/10
公開日: 2008/11/28
ジャーナル フリーWhile heat setting of acrylic fiber has been studied extensively with regard to the relation between the heating condition and the changes of fine structure and dyeing property.
In this paper, acrylic fiber heated in hot air was cooled under various conditions and the effect was studied on the crease recovery, the flexural rigidity, the dyeing property and the density of acrylic fiber.
The results obtained were as follows:
1) Acrylic fibers, treated with hot air at 120, 140, 160 and 180°C, were cooled gradually or rapidly in water down to 100-0°C. Crease recovery angle was greatly affected by the cooling temperature and the method. The higher the cooling temperature, the greater the crease recovery angle. Rapid cooling decreased the crease recovery angle considerably. Therefore, it is desirable to cool the fiber gradually at the neighborhood of glass transition temperature of acrylic fiber.
2) The cooling condition was also influencial to the handling of acrylic fiber. Flexural rigidity as a measure of handling was measured by cantilever method. Soft handling was obtained by the gradual cooling.
3) The density of fiber was determined by means of a density gradient tube. The density decreased by gradual cooling, while increased by rapid cooling.
4) In spite of increase of crystallinity by rapid cooling, the dyeing velocity and the sorption at dyeing equilibrium increased, possibly due to the increase of structural disorder in amorphous region.抄録全体を表示PDF形式でダウンロード (489K) -
松本 恒隆, 中前 勝彦, 中野 嘉人, 野中 敬三1974 年 30 巻 12 号 p. T559-T565
発行日: 1974/12/10
公開日: 2008/11/28
ジャーナル フリーTo clarify the relationship between the surface chemical properties of ethylene-vinyl alcohol (EVA) or ethylene-vinyl acetate copolymer (EVAc) and copolymer composition, the ζ-potentials of EVA and EVAc were measured by using the streaming-potential method.
The following results were obtained:
1) The ζ-potentials of heat treated polyethylene (PE) and polyvinyl alcohol (PVA) are -155mV, -35mV respectively. The ζ-potentials of EVA and EVAc are closely related to its water adsorption.
2) The ζ-potentials of EVA closely depend upon its VA content and do not change gradually, but give a sudden turn of chemical properties from that of PE to that of PVA at about VA 40 mol%.
3) The ζ-potential of EVAc decreases rapidly from that of PE to that of PVAc until EVAc becomes amorphous at about 21 mol%.
4) The relationships between the ζ-potentials of EVA and EVAc and copolymer composition are explained on the basis of the surface energy, especially the hydrogen bonding force component and the adsorption ability of OH- ions from solution phase.抄録全体を表示PDF形式でダウンロード (491K) -
住田 雅夫, 宮坂 啓象, 石川 欣造1974 年 30 巻 12 号 p. T566-T570
発行日: 1974/12/10
公開日: 2008/11/28
ジャーナル フリーThe orientation behaviour of vulcanized natural rubber in the course of uniaxial stretching was investigated from the fluorescence polarization with reference to a crystalline polymer, linear polyethylene.
From the polarized fluorescence patterns, it was suggested that the orientation behaviour of natural rubber may be interpreted as taking account of chains, effective and ineffective to the stretching. The amorphous orientation of polyethylene was higher than that of the natural rubber at a given draw ratio. This may be attributed to the cohesion of amorphous chains is higher in polyethylene than in the natural rubber. The fluorescence dichroic ratios of natural rubber increase abruptly after crystallization took place. This suggests that the crystallization by stretching gives rise to decrease in the effective chain length between cross-linkages.抄録全体を表示PDF形式でダウンロード (788K) -
酒井 豊子, 宮坂 啓象, 石川 欣造1974 年 30 巻 12 号 p. T571-T576
発行日: 1974/12/10
公開日: 2008/11/28
ジャーナル フリーTemperature dependence of the rate of diffusion of dyes in PET film was investigated by sublimation method. It was found that the temperature dependence of the rate of the diffusion is described by W. L. F. relation. A master curve (composite curve) can be obtained for different dyes by shifting the log D-temperature curves along the temperature axis. The composite curve thus reduced into that of PNA is expressed by W. L. F. equation. The shift temperature, defined in the composition, increases with the increase in the molecular weight of dye, though rarely the increase in the shift temperature differ between azo- and anthraquinone dyes. It seems that for a given dye the log D-temperature curves obtained for PET film with different fine structures are reduced into a composite curve by shifting of them along the log D axis without any shift along the temperature axis.抄録全体を表示PDF形式でダウンロード (1029K) -
高橋 重三, 小西 孝, 黒川 昌孝1974 年 30 巻 12 号 p. T577-T579
発行日: 1974/12/10
公開日: 2008/11/28
ジャーナル フリーThe β-form crystal structure of the poly (L-glutamic acid) fibers, spun from concentrated poly (L-sodium glutamate) (PSLG) aqueous solution with H3PO4 coagulant, were studied. Well-oriented clear X-ray diffraction patterns were obtained, and were led to assign the following orthorhombic unit cell;
a=9.26 Å (direction of hydrogen bond)
b=7.73 Å (direction of side chain)
c=6.90 Å (fiber axis)
The result of infra-red spectroscopy indicates that the β-crystal structure constituted an anti-parallel, slightly pleated sheets. The calculated and observed densities were 1.73g/cc and 1.47g/cc, respectively.
Powder-like precipitate of PGA, aggregates of minute crystals was obtained from PSLG dilute aqueous solution. The crystal structure well agreed with the β-form of the PGA fiber.抄録全体を表示PDF形式でダウンロード (1463K)
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