Comparative X-ray scattering,microscopical, and mechanical studies on rectangular plates injection molded from different types of isotactic polypropylene

Rectangular plates were injection molded from two grades of commercial polypropylene (PP) differing in the molar mass distribution. The mold was mechanically sealed when a desired pressure p_i,max (up to 1560 bar) was reached. Samples were taken from each plate at different distances from the gate and were investigated by applying various methods. In spatially resolved wide-angle X-ray studies, the cross section of the sample was scanned with a fine X-ray beam (collimated by a Kratky small-angle camera) and the intensity of scattering was registered by a linear detector as a function of position in the cross section. The evaluation of the scattering data delivered profiles of several parameters, describing the distribution of crystallite modification β-PP and γ-PP, the degree of orientation, the size of crystallites, and interplanar spacing, depending on the distance from surface. These results and those from measurements of birefringence and elongation at break, and from polarization microscopy and transmission electron microscopy, provided details of the layered structures in the plates, at different flow lengths, and allowed far-reaching statements about the influence of molecular properties and processing conditions on the development of texture in the plates.     

On the Origin of a Low Angle Spacing in Starch

The structure of starch granules from different botanical sources was studied by transmission electron microscopy and small-angle X-ray diffraction. Electron micrographs of negatively stained starch granule fragments show a rippled fibrous structure. The ripples are interpreted as being stacks of thin crystalline lamellae comprising the linear α-(1→4) chains of the amylopectin. Optical diffraction analysis of the electron micrographs showed that the spacing of the ripples varies from 9.2 nm in potato starch to 10.4 nm in barley starch. This correlates well with the position of a Bragg peak at appr. 10 nm measured by small-angle X-ray diffraction. These observations indicate that the Bragg peak arises from the alternating amorphous and crystalline regions seen as ripples in the electron micrographs.     

4-Acyl-2-acylamino-4,5-dihydro-1,3,4-thiadiazole durch Acylierung von Thiosemicarbazonen

4-Acyl-2-acylamino-4,5-dihydro-1,3,4-thiadiazoles by Acylation of Thiosemicarbazones Thiosemicarbazones and acid anhydrides or halides react to 4-acyl-2-acylamino-4,5-dihydro-1,3,4-thiadiazoles ( 2a – 2v ) in high yields. 3-Acyl-2-amino-4,5-dihydro-1,3,4-thiadiazoles 5 are proved as intermediates in this conversion. In special cases they can be isolated or submitted to further acylation with an other acylating agent. ¹H-n.m.r., ¹³C-n.m.r. and mass spectroscopic data of compounds 2a – 2v and 5a – 5e are given. The preparation of the compounds 2 can also be carried out starting with a carbonyl compound and thiosemicarbazide without isolation of the thiosemicarbazone.     

ortho-Spezifische Bromierung von Phenolen

Ortho-Specific Bromination of Phenols Phenol as well as 3-substituted phenols are brominated exclusively in the orthopositions by N.N-dibromomethylamine, yielding 2.6-dibrominated phenols in excellent yields. Phenols bearing an ortho-substituent need N-bromomethylamine as the brominating agent to take up one bromine atom into the free ortho-position. para-Bromination is not observed in either case. 1-Naphthol gives 2-bromo-1-naphthol, 8-hydroxyquinoline gives 7-bromo-8-hydroxyquinoline with 80% and 98% yield respectively. ortho-Specific chlorination of phenols was carried out in some cases using N-chloro-alkylamines.     

N-Aminierung von Isochinolinbasen

N-Amination of Isoquinoline Bases 3, 3-Pentamethylene oxaziridine 1 forms an N N-bond with secondary isoquinoline bases 2a – f to give the cyclohexylidene hydrazines 3a – f . In some cases nitrogen elimination yielding indane derivatives 13b, 13e competes with hydrazone formation. The cyclic Schiff'base 14 and the β-carboline derivative 16 can also be aminated.     

Neue Azoolefine und deren saure Spaltung zu Aryldiiminen

New Azoolefines and their Acidic cleavage to Aryldiimines 3-Amino-1-aryl-3′,3′-dimethyl-pyrazolin-4-spiro-2′-oxiran-5-ones ( 3a – c ) undergo ring opening with methoxide forming methyl 3-amino-3-arylazo-propenoates ( 5a – c ). 5a – c are cleaved under acidic conditions. The main products of the cleavage of 5c with methanolic hydrochloric acid are nitrogen, 2, 4, 6-trichloro-benzen ( 6 ), 2, 4, 6-trichloro-aniline ( 9 ) and 2, 4, 6-trichlorophenylhydrazine ( 10 ). Intermediates of the cleavage of 5 are aryldiimines trapped with benzaldehyde as the corresponding benzhydrazides ( 12a , b ).     

Ringöffnungs- und SubstitutionsReaktionen von 4,4-Dihalogen-pyrazolin-5-onen durch Nucleophile

Ring Opening and Substitution Reactions of 4,4-Dihalo-pyrazolin-5-ones with Nucleophiles 1-Aryl-4,4-dihalo-3-methyl-pyrazolin-5-ones ( 1a – c ) undergo ring opening with alkoxides and form alkyl 3-arylazo-2-halo-2-butenoats ( 2a – d ). Analogous reactions take place with ammonia and amines. 4-Nitro-phenoxide reacts with substitution of both halogens to the 4,4-bis(4-nitro-phenyl)-compound ( 5 ). Phenols are selectively orthobrominated by the title compounds 1a and b .     

Analysis of the Temperature and Strain-Rate Dependences of Strain Hardening

A classical constitutive modeling-based Ansatz for the impact of thermal activation on the stress–strain response of metallic materials is compared with the state parameter-based Kocks–Mecking model. The predicted functional dependencies suggest that, in the first approach, only the dislocation storage mechanism is a thermally activated process, whereas, in the second approach, only the mechanism of dynamic recovery is. In contradiction to each of these individual approaches, our analysis and comparison with experimental evidence shows that thermal activation contributes both to dislocation generation and annihilation.     

Plasma viscosity and the risk of coronary heart disease: results from the MONICA-Augsburg Cohort Study, 1984 to 1992

Plasma viscosity is determined by various macromolecules, eg, fibrinogen, immunoglobulins, and lipoproteins. It may therefore reflect several aspects involved in cardiovascular diseases, including the effects of classic risk factors, hemostatic disturbances, and inflammation. We examined the association of plasma viscosity with the incidence of a first major coronary heart disease event (CHD; fatal and nonfatal myocardial infarction and cardiac death; n=50) in 933 men aged 45 to 64 years of the MONICA project of Augsburg, Germany. The incidence rate was 7.23 per 1000 person-years (95% confidence interval [CI], 5.37 to 9.53), and the subjects were followed up for 8 years. All suspected cases of an incident CHD event were classified according to the MONICA protocol. There was a positive and statistically significant unadjusted relationship between plasma viscosity and the incidence of CHD. The relative risk of CHD events associated with a 1-SD increase in plasma viscosity (0.070 mPa x s) was 1.60 (95% CI, 1.25 to 2.03). After adjustment for age, total cholesterol, high density lipoprotein cholesterol, smoking, blood pressure, and body mass index, the relative risk was reduced only moderately (1.42; 95% CI, 1.09 to 1.86). The relative risk of CHD events for men in the highest quintile of the plasma viscosity distribution in comparison with the lowest quintile was 3.31 (95% CI, 1.19 to 9.25) after adjustment for the aforementioned variables. A large proportion of events (40%) occurred among men in the highest quintile. These findings suggest that plasma viscosity may have considerable potential to identify subjects at risk for CHD events.