The effect of heat treatment on the microfibrillar network of poly(p-phenylene benzobisthiazole)

Materials exhibiting exceptional mechanical properties can be fabricated from rigid polymers. In a spinning process, an oriented solution is solidified by the action of a nonsolvent, which induces crystallization of an oriented rigid polymer. Drying and heat treatment result in the final material having the desired properties. The effect of heat treatment on the morphology of poly(p-phenylene benzobisthiazole) (PBZT) films was studied by measurements of small-angle X-ray scattering (SAXS) and wide-angle X-ray diffraction (WAXD). Films were formed by coagulation in water. The wet films were dried with supercritical CO₂ to maintain an open network structure. Coagulation in water resulted in formation of microfibrils having diameter of ∼9 nm. Heat-treatment at 600°C caused significant coalescence of microfibrils. The crystallite size was increased by heat treatment from a value that is smaller than the microfibrillar diameter indicating defects in chain packing, to a value comparable to the microfibrillar diameter.     

Preparation and characterization of 1,5-Diacyl-2,4-dioxohexahydro-1,3,5-triazines with Higher Acyl Groups

The title compounds were prepared from 2,4-dioxohexahydro-triazine (DHT) and the corresponding acid chlorides in the presence of sulphuric acid. They are active acylating agents against piperidine in dioxane as the solvent. Only the diacyl derivatives of DHT with acyl chain lengths up to C₆ react with aqueous solutions of sodium perborate forming the corresponding peroxy acids.     

Studies on the Autoxidation of Phenyl Cycloalkanes

The products of the autoxidation of phenyl cyclopropane ( I ), phenyl cyclobutane ( II ), phenyl cyclopentane ( III ), phenyl cyclohexane ( IV ), phenyl cycloheptane ( V ) and phenyl cyclooctane ( VI ) were analyzed after reduction of the reaction mixtures with LiAlH₄. As products of the attack on the α-C H bonds the corresponding 1-phenyl cycloalkanols and 1-phenyl alkan-1-ols were found. In the case of phenyl cyclopropane some S_R2 ring opening probably takes place. The oxidabilities $ {\rm k}_{\rm p} /\sqrt {{\rm k}_{\rm t}} $, the chain termination constants k_t, the absolute chain propagation constants k_p and the relative chain propagation constant (k_p)_rel were determined for the phenyl cycloalkanes I — VI . As it is to be expected on the basis of the I-strain concept the autoxidation rate of phenyl cyclopentane ( III ) is considerably higher than that of phenyl cyclobutane ( II ) and phenyl cyclohexane ( IV ).     

Studies on the base-catalyzed Solvolysis of Propane-2-sulphonic Acid p-Cresylester

Products of the reaction of propane-2-sulphonic acid p-cresylester with sodium butoxide in butanol are the sodium salt of propan-2-sulphonic acid, di-n-butyl ether, p-cresyl-n-butyl ether and p-cresol. The reaction proceeds via propane-2-sulphonic acid n-butylester which is formed from the starting compound by an elimination-addition (sulphene) mechanism. The elimination step is an E1-cB reaction.     

Zur Reduktion von Schwefeldioxid-Restmengen in Getreidestärken

On the Reduction of Residual Amounts of Sulfur Dioxide in Cereal Starches. New economically applicable methods for considerable elimination of sulfur dioxide from starch products are described. Extraction experiments show that a part of the sulfur dioxide is chemically bounded. The SO₂-content of corn starches can be decreased below 20 ppm by application of less than the stoichiometrically calculated amount of sodium hydroxide or hydrogen peroxide in aqueous solution. Because of the more favourable process conditions the hydrogen peroxide-method is preferred to the others.     

Studies on the Autoxidation of Phenylacetylene

Phenylacetylene is oxidized slowly by molecular oxygen at 110°C. The main oxidation products are benzoic acid, benzoic anhydride, and benzaldehyde. Besides the oxidation, thermal dimerization, oligomerization, and polymerization processes also take place. As individual products 1,4-diphenylbut-1-yn-3-ene and 1,3,5-triphenylbenzene were identified. About 80% of the phenylacetylene consumed are converted into products of low volatility which could not be detected by gas chromatography. The autoxidation of acetylenic hydrocarbones [1] preferably yields products of the attack at C H bonds in α-position to the CC triple bond. An attack at the CC riple bond was a first proved in the case of phenylacetylene, which besides polymeric products yielded benzaldehyde, acetophenone, and organic acids [2]. Later, in the causes of the isomeric octynes [3] and of various 1-Phenylalk-1-ynes [4] an attack at the CC triple bond was also proved. As the primary products of the oxidative attack at the CC triple bond short-lived oxirenes or their valence isomers, the corresponding ketocarbenes are to be expected. Indeed, their rearrangement products were found in the oxidation mixtures of both the isomeric ocytnes [3] and the 1-phenylalk-1-ynes [4]. Other products of the oxidative attack at the CC triple bond are lower carboxylic acids, formally produced by oxidative cleavage of the CC triple bond [3, 4].     

Residual stress measurements in irradiated solution-annealed type 304 stainless steel tubing

Immersion density and residual stress measurements were made on solution-annealed type 304 stainless steel capsule tubing irradiated up to fluence levels of 9 × 10²² n/cm² (E > 0.1 MeV). The measured residual stress is dependent on the competition between differential swelling which builds up differential stresses, and irradiation creep which relaxes these stresses. The measurements were analyzed using a bilinear swelling equation formulated with swelling data from the same heat of material. The temperatures and fluence levels of the swelling and slit tube data were each calculated with the same computer code. At high fluence, when swelling was in the steady-state region, the effective irradiation creep rate increased by a factor of about three. Further analysis was made assuming that stress-enhanced swelling and swelling-enhanced irradiation creep were the enhanced relaxation mechanisms.