Orientation behavior of reciprocal lattice vectors of crystalites in orthogonal-biaxially stretched PVA film was investigated by means of pole figure analyses of X-ray diffraction. The orthogonal-biaxially stretching was performed under the following three fashions; simultaneous, strip biaxial, and two-step biaxial. 1) For the simultaneous biaxial stretching, it was found that (101) plane tends to orient parallel to the film plane, but it randomly orients around the normal of film plane, and that (10_??_) plane becomes parallel to the normal of film plane. 2) For the strip and two-stpe biaxial stretching, (101) plane tends to orient parallel to the film plane, but the behavior of (10_??_) plane changes with the deformation of orthogonal biaxial stretching.
In the previous report, it was investigated the orientation behavior of reciprocal lattice vectors of crystallites in orthogonal-biaxially stretching PVA film, by using pole figure analyses of X-ray diffraction. In this report, the orientation behaviors of crystallites and non-crystalline chain segments in orthogonal-biaxially stretched VPA film are investigated by means of the equilateral triangle evaluation of mean square of direction cosine by X-ray diffraction, dichroic ratio and birefringence measurements. 1) For the orthogonal-biaxially stretching, the plane of hydrogen bond in PVA, i.e., (101) plane tends to orient parallel to the film plane. This phenomena is interpreted in terms of slipping of (101) plane by the shear stress originated by the compression force parallel to the thickness direction within the bulk film. 2) The orientation behavior of crystal b-axis and the other reciprocal lattice vectors follow on the slip of (101) plane. 3) The noncrystalline chain segment tends to orient parallel to the film surface with the orthogonal-biaxially stretching, and its behavior follows in the external stress of the machine direction.
The diffusion of 1: 2 type metal complex dyes into nylon film was measured by roll film method. Used dyes were the symmetrical 1: 2 type chromium complex of 1-(2-hydroxyphenylazo)-2-naphthol (I) and 1-(2-hydroxy-5-sulfamoylphenylazo)-2-naphthol (II), they were prepared from each azo compound and purified by column chromatography. 6-Nylon film (amino end group content 3.81×10-5mol/g, thickness 25μ) was cut into 3×100cm and made into a roll. Dyeing conditions were as follows: dyebath concentration 5×10-6_??_10×10-5 mol/l, dyeing temperature 80°C, dyeing time 3_??_9 days. After dyeing, obtained diffusion profiles on each case were assumed as type H which is consisted of type L (Boxlike diffusion) and type C (Fickian diffusion), then these profiles were divided into type L and type C parts and the surface concentration of type L part was corresponded to the saturated value of hydrochloric acid. Diffusion coefficients of each part were calculated by Matano's method for L part and Sekido's method for C part. Diffusion coefficients of both fall in 2_??_8×10-9cm2/min. Plots of whole amounts of dye diffused in L part and C part against √t give nearly straight lines. The ratio of dye diffused in L part H (overall diffused dyes) is about 70_??_80% in the case of low dye bath concentration (5×10-6mol/l), and as the dye bath concentration increases, the C part increases rapidly. Thus, it may be assumed that the apparent behaviours of diffusion of more hydrophobic metal complex dyes of higher molecular weight are type C in the bath concentration usually used.
The heat of adsorption of mineral acids on polyamide powders A_??_D (sample A_??_D have different amount of amino end group) were measured with application of the thermal detection type automatic recording liquid chromatography as a flow type micro calorimeter. The heat of adsorption was obtained by total variation of temperature (peak area) which corresponded to overall calorific values in the thermal detection column with calori-corrector unit and adsorption amounts. Observed values of heat of adsorption are influenced considerably by experimental temperature, concentration of acid, state of the amorphous region of polyamide. Observed values were corrected by the ratio of adsorption amounts on equilibrium (48 hr) and contact time on flow method (ca. 30min). Corrected values (-ΔHc°) are plotted with θ (=[H]f/[S]f) and these at saturated adsorption (-ΔH°c•θ=1)are obtained by extrapolation to θ=1. Good agreement is observed among the values of -ΔH°c•θ=1 for different samples A_??_D. As the temperature increases (30°_??_50°C), -ΔH°c•θ=1 values of HCl, HBr and HI increase. Proposed value of -ΔH°c•θ=1 of acids are 8.2 kcal/mol (HCl, 30°C), 8.9 kcal/mol (HCl, 40°C), 10.4 kcal/mol (HCl, 50°C), 11.3 kcal/mol (HBr, 40°C) and 13.5 kcal/mol (HI, 40°C). It is assumed that these differences by acids used depend on differences of the heat of adsorption of anion (Cl-, Br- and I-)to protonated amino end group (-NH3+) on polyamide.
In order to investigate the effects of the surfactants on photo-fading of the aminoanthraquinone disperse dyes, the aqueous solutions of 1, 4-diaminoanthraquinone containing anionic surfactants, nonionic surfactants and polyoxyethylene glycol were exposed to light of the 400-watt high-pressure mercury-vapour lamp (Toshiba H 400 P) and rates of photo-fading of the dye were examined. The experimental results suggested the following: (1) The photo-fading reaction of 1, 4-diaminoanthraquinone in the aqueous solutions is of the first order in the initial stage. (2) Among the samples used in present work, sodium dodecyl sulfate, polyoxyethylene glycol and polyoxyethylene dodecylether accelerate the photo-fading reaction of the dye, while the other four retards the reaction more effectively in the order of sodium dodecylbenzene sulfonate < polyoxyethylene nonylphenylether < sodium butylnaphthalene sulfonate < sodium β-naphthalene sulfonate-formaldehyde condensate. This retardation effect may be attributed to the aromatic ring in these molecules and the naphthalene ring is more effective than benzene ring. (3) The surfactants having aromatic ring exhibit twofold retardation effects on photo-fading reacttion of the dye i.e., the roles as the filter and as the inactivating agent for the activated dye by interacting with the dye. (4) The retardation effect of sodium β-naphthalene sulfonate-formaldehyde condensate, especially exerted by interacting with the dye, is the largest of all the samples used. This may be due to the polymeric feature of the condensate.