巻号一覧
26 巻, 2 号
選択された号の論文の7件中1～7を表示しています
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小出 直人1970 年 26 巻 2 号 p. 53-60
発行日: 1970/02/10
公開日: 2008/11/28
ジャーナル フリーIn order to examine the pyrolytic behavior of the silk samples treated with an aqueous solution of Sn (IV)-complex, ammonium (A-salt) or potassium (K-salt) hexachlorostannate, thermogravimetric analysis (TGA) was carried out in vacuum, and high-resolution mass spectra (MS) of pyrolysis products of the silk treated with A-salt or treated with K-salt were also measured, and the results were compared with those of the silk untreated, treated with SnCl4 solution or with 0.1 N HCl.
In order to clarify the bonding mechanism between A or K-salt and silk fibroin, TGA of the mixed samples of silk and Sn-complex by a ratio of 10:1 Was also measured.
Mass spectrometry was carried out according to the storage method on the pyrolyzed gas (300±10°C) and molecular ions were determined. The results obtained were as follows:
1. The peaks of velocity (dw/dt)-temperature curve of treated silks obtained from TGA measurements were somewhat shifted to higher temperature than those of untreated silk.
2. From the results of TGA, A-salt seemed to suppress the thermal degradation of silk due to NH3-gas generated from itself. But K-salt showed the different effect, so weak bonding between silk and K-salt was expected.
3. Many parent and fragment ions appeared in MS in the m/e range of 31-131. For example, benzene, phenol, toluene, aniline as carbocylic compounds, and also pyrrole, pyrazole, pyrazoline, γ-pyrone as heterocyclic compounds.
It was cosidered that these carbocyclic compounds were pyrolysis products of aromatic aminoacid residue, hence thermal degradation process of some aminoacids were easily clarified. On the other hand, some compounds such as pyrazole, pyrazoline and γ-pyrone were not pyrolysis droducts but rearranged ions. Further more, other ions such as hydrocarbons, aldehydes, lower alcohols, alkylamine and CO2 were also detected. The peaks of C2H4, N2 at m/e 28 and NH3, OH at m/e 17 were also recognized from different MS.
4. Presence of these pyrolyzed products qualitatively indicates the degree of thermal degradation of silk. Especially in the case of silk treated with A-salt, the number of the components of pyrolyzed gas was small. Hence it is concluded in this experiment that A-salt suppress the thermal degradation of silk.抄録全体を表示PDF形式でダウンロード (527K) -
前田 洋治, 金綱 久明1970 年 26 巻 2 号 p. 61-65
発行日: 1970/02/10
公開日: 2008/11/28
ジャーナル フリーA calorimeter assembly was made in order to investigate the thermodynamic properties of high polymers in bulk. This calorimeter was designed based on adiabatic, continuous heating method.
Firstly, measurements were carried out for KBr, Al2O3 and NaCl in order to determine the reproducibility and the accuracy of the apparatus. The specific heat of polyethylene was measured with an annealed sample in a temperature range from 30 to 150°C. The experimental values obtained within error of ±1_??_4 per cent. The heat of fusion estimated for polyethylene of 100% crystallinity was 68.5±4.4 cal/g, which agrees with the data reported by B. Wunderlich and M. Dole within a range of experimental error.抄録全体を表示PDF形式でダウンロード (365K) -
細井 正広, 河合 徹, 栗山 将1970 年 26 巻 2 号 p. 66-73
発行日: 1970/02/10
公開日: 2008/11/28
ジャーナル フリーTextures of polyethylene polymerized by γ-ray irradiation in gas phase were studied by electron microscopy, thermal analysis, X-ray analysis including the effects of annealing and the fuming nitric acid treatment.
Electron microscopy revealed that the as-polymerized polyethylene consisted of irregular aggregation of ill-defined lamellae. Fibrillar network was occasionaly observed but these are considered as resulted by some mechanical action during or after the polymerization.
DTA thermograms and the peak temperature also suggest that the crystals formed are unstable showing rather low peak temperature (120.4°C_??_125.2°C) and that the lower the polymerization temperature, the more unstable. The effect of the fuming nitric acid treatment (for instance, weight loss) is bigger for the product of polymerization at lower temperature. As the branch content was higher for the product at higher temperature, on the other hand, the X-ray crystallinity and the peak temperature were lower for the product at higher temperature.
The residue of the fuming nitric acid treatment showed, however, higher crystallinities than the original samples and the crstallinity and melting temperature of the etched crystals of the higher temperature product became higher than that of the lower temperature product. Moreover annealing of the 30°C product give rise to much bigger increased crystallinity (as revealed by the weight loss due to the etching) than that of 90°C product. The size of the individual lamellar crystals as revealed by a X-ray method seems bigger for high temperature product. All the above results imply that the as-polymerized products are composed of irregular lamellar which are rather unstable against the heat and the attack of the chemical agent and that such features are more pronounced for the lower temperature product. The effects of the branching (i. e. the increase in the branch content with polymerization temperature) of the poymerization temperature are opposed by those of the crystallization (polymerization) temperature.抄録全体を表示PDF形式でダウンロード (1519K) -
竹森 広, 宮坂 啓象, 石川 欣造1970 年 26 巻 2 号 p. 74-79
発行日: 1970/02/10
公開日: 2008/11/28
ジャーナル フリーThe effects of drawing condition and wet heat-treatment on the melting behavior of nylon 66 were studied. Double melting peaks are observed on the sample drawn at lower temperature than the glass transition temperature, while one broad peak which corresponds to lower one, is observed on the sample drawn at relatively higher temperature.
When the sample is annealed, the lower melting peak also appears even in the sample drawn at higher temperature. The lower melting peak grows with annealing, and the melting temperature becomes higher with increased annealing temperature, whereas the higher one which appears in the as-drawn samples does not shift, but diminishes gradually with annealing. As the temperature shift of the lower melting peak is related to the change of the long spacing of the sample, the equilibrium melting temperature can be estimated according to the Hoffman-Weeks relation. Two cases are postulated for the relation between the long spacing and the thickness of crystals in the Hoffman plot. The equilibrium melting temperature is estimated as 294°C from the more reasonable one of the two cases. The double orientation of crystals can be also observed when drawing is performed at lower temperatures than the glass transition temperature, as we have already reported in the case of nylon 6.抄録全体を表示PDF形式でダウンロード (1044K) -
嘉本 律, 江原 勝夫, 松元 孝子, 河合 徹, 前田 弘邦1970 年 26 巻 2 号 p. 80-88
発行日: 1970/02/10
公開日: 2008/11/28
ジャーナル フリーCrystallization of polyethyleneterephthalate (PET) was carried out in a steady state flow using a cone-plate type viscometer. The resultant texture was examined by means of (micro) differential thermal analysis (DTA) and of electron microscopy mainly as a function of shear rate (i.e., rotation speed of the cone). In order to avoid the rearrangement occuring during the DTA measurements, the crystallized films were treated with 70% aqueous solution of monoethyl amine and the extracted crystals were also examined by DTA and electron microscopy. The DTA thermograms revealed that two types of crystals with different melting temperatures were formed during the isothermal crystllization. The relative amount of the crystals with the higher melting temperature increased with the increasing rate of shear. The crystals with the lower melting temperature were susceptible to the amine treatment and apt to rearrange on heating, suggesting their instability. The electron microscopy revealed that in the case of the low shear, lamellae grown mormal to the direction of the shear were piled up along the shear direction just as in the case of polyethylene but in the case of higher shear, the two kinds of lamellae, big and very small, coexisted, the fomer having aligned along the direction of shear. It is postulated that the big lamellae might be grown from the bundle-like nuclei formed by intermolecular crystallization, which would be facilitated by molecular orientation and would show a higher melting temperature than that of the irregular lamellae resulted from the usual chain folding.抄録全体を表示PDF形式でダウンロード (3524K) -
畠山 立子, 金綱 久明1970 年 26 巻 2 号 p. 89-90
発行日: 1970/02/10
公開日: 2008/11/28
ジャーナル フリーBy means of differential scanning calorimeter (DSC), thermal behavior of QIANA was investigated. The glass transition temperature (Tg) of the original QIANA was found over the range from 90°C to 150°C. Tg of the quenched sample was similar to that of the original, but the transition peak of Tg was appeared. Three melting peaks were recognized at 262°C, 272°C and 281°C. The heat of fusion was 1.2cal/g which was the least in the copolyamides.
The higher Tg of QIANA is attributed to the rigid cyclohexyl rings and the broadness of the transiton may be due to the molecular motion of methylene group and cyclohexyl ring which begin at different temperatures.抄録全体を表示PDF形式でダウンロード (118K) -
前田 正彦, 宮坂 啓象, 石川 欣造1970 年 26 巻 2 号 p. 91-93
発行日: 1970/02/10
公開日: 2008/11/28
ジャーナル フリーThe drawing of mats of linear PE single crystals prepared from the dilute solution is possible at temperatures higher than about 90°C. The structure and properties of the drawn specimen are remarkably different from those of the ordinary bulk drawn specimen1).
In this paper the drawn mat was investigated by a calorimetric method, Differential Scanning Calorimeter. The experimentalresults characteristically obtained for the drawn mat specimen are summarized as follows:
1) Broad melting curve
2) Remarkable super-heating depending on the rate of heating
3) Constancy of the melting point and the heat of fusion with annealing
4) Remarkable discrepancy from the heat of fusion-density relationship obtained on the ordinary bulk drawn specimen. This is due to the higher density of the amorphous region of the drawn mat compared with that of the bulk drawn specimen.
These results imply that the structure of the mat drawn specimen is characterized by the larger number of the tie chains connecting the neighbouring crystals, and agrees with the structure postulated in the previous paper1).抄録全体を表示PDF形式でダウンロード (190K)
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