Equilibrium sorption isotherms of iodine on cellulose fibres have been determined in an aqueous solution in the presence of potassium iodide at 25°C. It was found that the sorption isotherms give the familliar curves obeying Langmuir equation so the parameters of this equation could been used to measure the degree of crystallinity and accessibility. This method is not convenient as a measure of estimation for estimating the degree of crystallinity, but is usefull to detect the variation in the fine structure of the freshly regenerated cellulose gel when it is dried or stretched.
The partial carbamoylethylation of polyvinyl alcohol fibers with acrylamide was studied, using the aqueous solution or curing method. Suitable reaction conditions are as follows; For the aqueous solution method, - AM/PVA mol ratio 0.6, AM concentration 30g/l, Na2SO4 25%, Na3PO4 2%, 60°C, 4hr. For the curing method, - composition of impregnating solution; AM 35%, NaOH 7% curing condition; 120°C, 5min. Under both conditions, the, value of the degree of substitution was 2_??_4 mol%, for the unheated and heat-treated PVA fibers. From the improvement of elastic recovery by the formalization of partial carbamylethylated fibers, a certain degree of intermolecular cross-linking is deduced. Also, The Mannich reaction was observed when the amine treatment of partial carbamoylethylated fibers was caried out. The affinities for some dyestuffs of these after-treated fibers are improved, and especially good result is obtained for dimethylamine-treated and then formalizee fibers.
Peculiarity of the elastic modulus of the fibers made from polyethylene oxybenzoate (PEOB), an aromatic polyester, is discussed in terms of a series model. The elastic moduli of PEOB fibers are mucn less than that of polyethylene terephthalate (PET) fibers. Influence of drawing and heat treating on the elastic moduli of the fibers were examined, and even in very well oriented PEOB fibers, elastic moduli greater than 1000kg/mm2 were never observed. As Dulmage and Contois6) have previously reported, elastic moduli of crystalline and amorphous regions in high oriented polymers can be estimated by the extensions of their fiber identity period, their macroscopic moduli and their degree of crystallinity. Elastic moduli of the crystalline and amorphous regions of PEOB fiber are 1230 and 500kg/mm2, and those of PET fiber are 13000 and 600kg/mm2 respectively, These values show that low elastic moduli of PEOB fibers are caused by the crystalline structure of contracted molecular chain configration.
When a thin ethylmetaacylate plate which has been heated to around 100°C is hot-pressed, 2_??_3kg/cm2 pressure, on woven material (treated with either ethyl alcohol/formalin mixture or osmic acid solution), the plate picks up lousiness found in fabrics as is and adheres to the plate. The surface of the plate was vapor-coated with carbon and then shadowed with chrome. This plastic was disolved with acetone and lousiness test piece made. Electron microscopic study of the test piece was made with follwing results; 1) Lousiness consisted of fibrils (round and flat, ribbon-type long fibrils) of diameters around 500Å, 0.2_??_0.4μ, 0.6_??_0.8μ, 1.0_??_1.2μ, 2_??_5μ and those composed with Brin. In general it is evident that out of these fibrils, those of diameters from 500Å to 1.2μ and Brin are predominant. 2) Lousiness in silk fabrics is studied from the point of the flocking of fibrils, grouping density and foreign matters which inter-mix, not belonging to the proteid group. The lousiness (interm-ingled fibrils of 500Å to 5μ diameter) is formed in the types A and B, sub-divided into type AI, AII, BI and BII, Type AI has large nucleus and thick grouping density in the fibrils and Type AII, small nucleus and thin grouping density, Type B is scattered in larger, area and has no nucleus, Type BI and BII have thick and thin grouning density of fibril respectivelly. Lousiness of Type C is made up of foreign matters belonging to the non protain materials and those of fibrils, while those which containes Brin is Type D. Large type lousiness on silk fabrics was found besides the above six types. This lousiness is composed of fibrils of 500Å to 5μ diameter and is made up of combinations of the six types(AI, AII, BI, BII, C and D) such as AI-AII, AI-AII-BII, AI-BI-BII, AI-BI-C, BI-C-D, AI-AII-BII-C, AI-AII-BI-C-D, etc. Large type lousiness is classified as Type E.
It is assumed that the dyeing system consists of two sub-systems- the fibre phase and the dyebath-, and is discontinuous. The entropy production in dyeing proces is calculated and then the phenomenological equations are obtained. It is shown that (i) the diffusion coefficient of dye within the fibre depends on ξ-potential of the fibre and increases with the increase of concentration of the foreign electrolyte, (ii) in the steady state, the rate of adsorption of dye by the fibre depends on the difference of the chemical potential of inactive component.
The acidity of free acid of azo dyes having benzene-azo-benzene and naphthalene-azo-naphthalene as the skeletal structure has been studied. The pure free dye acid was prepared from the purified sodium salt by passing through the column of ion exchange resin. The acidities of free dye acids were measured by potentiometric titration with caustic soda. Titration curve of free dye acid is indistinguishable from that of hydrochloric acid. Set the value of dissociation constant of sulphonic acid group be K1, and that of hydroxyl group K2, then the former generally becomes the order of 10-3. In general, for o-hydroxyazo dyes the pK2=ca. 11, for p-hydroxyazo dyes the pK2=ca. 8. Amongst o-hydroxyazo dyes, dyes having NW acid (1, 4-Naphtholsulphonic acid) as coupling component are anomalous in titration curve (Fig. 5), e. g. for Naphthionic acid →NW acid pK2=8.1; it accords with the pK2 of NW acid. This observation means that the hydroxyl group scarecely chelate although it lies in the ortho position to the azo linkage. It is suggested that in dyeing of protein or polyamide fibres, all of p-hydroxyazo dyes and some of o-hydroxyazo dyes in which hydroxyl group is not restricted with inner molecular hydrogen bonding, are able to be adsorbed by a mechanism, probably hydrogen bonding with fibres in addition to the electrostatic attraction between sulphonic acid group of dye and amino group of these fibres. Thus the anomalous dyeing behaviour of these dyes to 6-nylon fibre may be explained. The value of the standard affinity of some acid azo dyes to 6, 6-nylon decreases with increasing acidity of free dye acid of these dyes. (Fig. 7)
By using 4, 4′-bis-dimethylamino diphenylmethane (M1) which has good yield and simple synthetic process instead of 4, 4′-bis-dimethylaminobenzhydrol, chloranil, p-nitrosodimethylaniline and aromatic amines or phenols, the condensation-combination dyeing for vinylone was studied with following results: Various shaded dyeings were obtained. In these dyeings, it is good to use M1 which dissolves dil. acetic acid of about pH 2. The non-ionic surface active agent is useful as the disperse agent. Salt-effect is not so strong, but the use of 2 valence metal salts is somewhat effective. The mata chrome process is more desirable. This process has the action of the oxidizing agent and chrome mordant agent. M1 does not react with aromatic amines or phenols but it reacts to form triphenyl methane dyes only in the presence of p-nitrosodimethylaniline, chroranil or oxidizer.