A system in which the differential modulus-stress (D. M. S.) curves of materials can be measured by differentiating stress-strain curves, has been established. From the D. M. S. curves of some model specimens of nylon 6 filaments, the following results are obtained: (i) A maximum point (Y4) in D. M. S. curve indicates a point where a filament was drawn maximally in its manufacturing process. Therefore, it is possible to estimate historical draw ratio of the filament from Y4, because stress at this point depends only on the draw ratio but not on the drawing temperature or the amount of contraction of the filament. (ii) The elongation at Y4 agrees with the total amount of each historical shrinkage given after the filament was drawn. (iii) The elongation between Y4 and the breaking point of a filament is nearly constant regardless of the contraction of the filament.
Change with extension of the molecular orientation of hard elastic polypropylene has been studied by use of x-ray diffraction, birefringence and polarized dye-fluorescent intensity distribution method. The degree of orientation of the c-axis oriented crystals decreases slightly with extension, which is inferred to be not due to the bending of crystals but due to the rotation because the sharpness of the crystalline diffraction remains unchanged under high extension, though the width becomes slightly larger. Birefringence decreases remarkably after yielding point because the negative contribution of the form birefringence due to the void formation. The change of the polarized dye-fluorescent intensity distribution showed that the molecular orientation decreases with extension, suggesting that dye-dichroism in this case was related to the crystalline orientation but not to the amorphous orientation.
Graft Copolymerization of styrene onto cellulose (cellophane) has been made in the absence of mineral acid with aqueous solutions of Ce (NO3)6•2NH4(CAN) as an initiator to look for the grafting site in cellulose. In advance of the polymerization experiment, the oxidation process of cellulose with Ce4+ was traced by determining the consumption of Ce4+ due to reduction. A stoichiometric relation was found for the ratio of the number of reducing endgroups contained in cellulose sample to that of Ce4+ consumed, i.e. 1:2. Ce4+ consumption was drastically decreased for a cellulose sample in which C1-C2 glycols had been blocked by oximation. These results implied that the initial oxidation attack took place mainly on C1-C2 glycols in the reducing endgroups. In agreement with this implication, graft copolymerization did proceed only under the condition that the C1-C2 glycol was retained to be intact without suffering any chemical modification. On the basis of these experimental results it is concluded that the graft copolymerization is initiated mostly by free radicals produced at the C1-C2 glycols in the reducing endgroups, so far as the oxidation condition is mild.
Styrene has been graftcopolymerized with aqueous solutions of Ce (NO3)6•2NH4(CAN) onto cellulose samples modified chemically in different manner, i.e., oxidized, reduced and oximated. The polymerization was conducted in the absence of mineral acid. It was found that the copolymerization did proceed not for the oxidized and oximated cellulose but only for the reduced cellulose, in which intact C1-C2 glycols are retained in the reducing endgroup. From these results it was confirmed that the C1-C2 glycol acts as the grafting site. Truely grafted polystyrene side-chains were isolated from graft product by using a technique of thin-layer chromatography combined with acid hydrolysis of cellulose backbone and the chemical constitution of their chain ends have been investigated with a paper-chromatographic technique. It was found that the side chain contained aldehyde residue at their chain ends. This result implied that the grafting grew up from a free radical produced on the C1 position of reducing cellulose-endgroup.
Aminodeoxycellulose of a degree of substitution of 0.90 by amino group introduced mainly on C-6 position was synthesized as follows. 2, 3-Di-O-phenylcarbamoylcellulose (1) was efficiently tosylated on C-6 position with p-toluenesulfonyl chloride in pyridine. The cellulose derivative (2) with sulfonyloxy and chloro groups was converted into the corresponding 6-azido-6-deoxy derivative (3), which then was reduced with lithium aluminum hydride in tetrahydrofuran to afford 6-amino-6-deoxy-2, 3-di-O-phenylcarbamoylcellulose (4). It was treated with sodium methoxide in methanol to give 6-amino-6-deoxycellulose (5). 6-Amino-6-deoxy-D-glucose was found as a main product in the hydrolyzate of 5.
Cellulosic adsorbents (T and H type. See Experimental for the symbols.) prepared by crosslinking industrial or domestic wastes and another CA type adsorbent made from partially aldehydized cellulose and chitosan, were applied for the advanced treatment of colored wastewater. Typical adsorbents are TChP, CA N and (TChP)GA, a modification of TChP by gelatin coating. Although these adsorbents had pore size distributions 5-5000nm, coloring matters in wastewater were found to be adsorbed in the transitional pores of 5-500nm. The rates of adsorption of negatively charged coloring matters by these adsorbents were higher than those by an activated carbon and by a typical polymer adsorbent. Furthermore, the absorption capacities of these adsorbents for coloring matters in model and secondary treated dyehouse waste-waters were generally excellent. A newly constructed apparatus, a continuous countercurrent solid-liquid contactor with four horizontal troughs, was found to be well suited for the decolorization of secondary treated waste-water by the adsorbents; e. g., (TChP)GA could be effectively and continuously used over a few months by repeating the processes, adsorption, regeneration and rinsing.
Propyl sulfonic acid groups introduced into cotton cellulose by propane sultone treatment gave remarkable cationic dyeabilities in the dyeing and in the heat-transfer printing of the fabrics. Good colorfastness to washing was resulted by the treatment with fixing agents.
For producing a thermally self-bonded nonwoven fabric, a developmental study of bicomponent polyolefin fibers has been carried out on the fibers of polyethylene and polypropylene extruded through capillary die having an L/D ratio of 10. The spinnability of the bicomponent fiber and the peeling strength at the interface of the fiber made are affected by the flow rate ratio of polymer components, the kind of polyethylene, and the flow-rate-value of polypropylene after spinning. Polypropylene melts are encapsulated by polyethylene melts during spinning when the flow rate ratio of high density polyethylene to polypropylene is larger than about 2.0. The best spinnability for such bicomponent fiber can be obtained when the flow-rate of polypropylene component after spinning is approximately 10 under above condition. On the other hand the drawing ratio below 4.0 gives sufficient peeling strength, Thus it has been found that heterofil type polyolefin bicomponent fibers to satisfy the request of markets sufficiently are produced.
In the previous paper, the author proposed the use of C* value as the method of expressing numerically the depth of chromatic colors, but the problem to calculate such achromatic colors as white, grey and black still remained to be solved. In this paper, this subject is discussed. It is confirmed in the present study that all achromatic colors except for white and very light grey very close to white can be expressed numerically by regarding them as the shades which belong to hue of 5PB. It is also shown that the depth series of Munsell achromatic axis can be adequately approximated by the following equation, where, V is the Munsell Value. Therefore, it is concluded that Munsell achromatic axis changes in arithmetic progression for brightness, while it changes in geometric progression for depth.