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  • 1945-1949  (12)
  • 1
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    Journal of the American Chemical Society 68 (1946), S. 2547-2552 
    ISSN: 1520-5126
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    Journal of the American Chemical Society 68 (1946), S. 1138-1138 
    ISSN: 1520-5126
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The paper offers a verification by x-ray experiments of Kratky's theory of affined transformation (affine Raumverzerrung), aiming at an explanation of the mechanism of deformation of swollen cellulose gels upon stretching. Isotropic model filaments of various degrees of swelling were stretched to various extents and x-ray photographs were then taken. Following Kratky, the intensity distribution along the sickles of two paratropic planes of the ribbon-shaped crystallites, the lamellar plane, A0 and the A3 plane (perpendicular to the latter) were measured and the average orientation, expressed in terms of the orientation factor, fx, was calculated. The superposition of the (021) interference on that of the A3 sickle, which had been neglected by Kratky, was accounted for. The experimental results are in conformity with certain characteristic features of the theory; (a) the orientation of the A0 planes advances more rapidly than that of the A3 planes; (b) regardless of the initial degree of swelling of the isotropic filament, the average orientation is actually a univocal function of the elongation, va. On the other hand, the rate of orientation appears to be much greater than that required by theory; the average orientation, expressed in terms of the orientation factor, increases almost twice as rapidly. It is shown, moreover, that, apart from low degrees of orientation, Kratky's theory fails to explain the velocity function of the relative rotation of the crystallites, as derived from the experimental data according to a procedure proposed by Kratky. It is concluded that further work is required to elucidate the mechanism of deformation.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
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  • 4
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A discussion is offered of the x-ray patterns of partially acetylated and saponified cellulose model filaments with varying acetyl contents. They are substantially in conformity with the swelling experiments previously described in Part I (page 397) of this paper. (1) In nonrecrystallized filaments, chemical reaction takes place in the crystallites and the intercrystalline regions from the very beginning of the experiment. The rate of chemical conversion, however, is larger in the latter. (2) Acetylation of the hydrate cellulose crystallites results in a gradual increase in the (101) spacing, A0; the A3 and A4 reflections [corresponding to (101) and (002), respectively] remain unimpaired up to a gross acetyl content of at least 1.5 acetyl groups per glucose residue. (3) Maximally acetylated filaments containing 2.3 acetyl groups per glucose residue may be recrystallized by heating in methanol or ethanol. The diagram of the recrystallized product is identical with the pattern of cellulose triacetate II. With about halfway acetylated or saponified products, recrystallization is not realizable by means of a heating process in water or methanol. (4) Enhanced degree of local order as the result of previous recrystallization of maximally acetylated products produces a more pronounced difference in rate of saponification between the “crystalline” and “amorphous” fiber portions.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 5
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The orientation of model filaments stretched to various extents in three different states of swelling was investigated by quantitative x-ray analysis before and after drying. The change in orientation upon drying was found to be either very small or zero. This shows that the crystallites do not even approximately follow the rules of affined transformation which would require a very considerable increase in orientation on drying. There must be an entirely different mechanism which prevents the crystallites from being dragged along with the matrix in which they are embedded.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 6
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Ten series of model filaments with increasing orientation and swelling degrees ranging between 16 and 1.2 were prepared from three viscoses containing 4, 6, and 10.5% cellulose. Their birefringence was measured and their x-ray diagrams taken and quantitatively evaluated in order to determine the over-all orientation of the iiber substance and that of the crystalline portion. It is shown that a general relation exists between the orientation of the crystallites and that of the entire fiber substance which is the same in all fibers stretched in the swollen state. Once the birefringence of a filament is known, the orientation factor of its crystallitee can be computed without taking an x-ray photograph. From the data further evidence can be derived to the effect that the orientation of the crystallitm cannot be accounted for by the theory of affined deformation.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 7
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The recently developed x-ray method of crystallinity determination is applied to products of heterogeneous acid hydrolysis of cellulose fibers. Upon treatment of viscose rayon fibers with boiling 2.5 N sulfuric acid, the crystalline fraction is increased from 39 to 49% within half an hour, and remains constant upon prolonged treatment. Ramie does not show any change in percentage crystallinity when subjected to the same treatment. Its crystalline fraction is, however, transformed into cellulose IV. The observed changes in moisture regain of the hydrolyzed products are in line with the x-ray results.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 8
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The paper deals with a tentative plan to extend quantitative x-ray measurements for determining the degree of crystallinity of polymers (as used earlier in cellulose determinations), to the investigation of rubber, polythene, and a polyamide. Strictly monochromatized copper radiation was used. The results show that further work along these lines may be promising. The raw rubber sample used was identical with one of those investigated by Goppel and by Arlman. It yielded a crystallinity figure higher than that reported by Goppel, but conformed with that found by Arlman. The figures obtained for polythene at different temperatures are compared with those derived from density and heat capacity measurements by other workers. The degree of crystallinity of polythene at room temperature is found to be ∼ 55%, and in samples of polyhexamethylene sebacamide, previously treated in different ways, figures between ∼50 and 70% are obtained. It is shown that the possibility of using the background intensity as a measure of the disordered fraction is confined to not too high angles of diffraction. A method is described (and experimentally checked) allowing for reducing the curves of intensity distribution as a function of 2θ as observed in various polymers to a comparable scale. It is further emphasized that, in polymers where hydrogen bonds play a decisive role in intermolecular cohesion, the x-ray results suggest that the “crystalline” or ordered fraction may to a considerable extent involve states of two-dimensional order.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 4 (1949), S. 135-144 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The method for the evaluation of the percentage crystallinity in cellulose preparations from x-ray intensity measurements, previously described in detail (J. Appl. Phys., in press) is reviewed briefly and new material presented consisting of crystallinity percentages between 8% and 70%. Cotton, flax, and ramie possess equal crystallinity (70%) and so do the majority of rayons, independent of their degree of orientation and including cuprammonium and Lilienfeld rayons. Cellulose acetates saponified under varying conditions also yield almost the same value as rayon (40%). The New product Fiber G (du Pont) holds an exceptional position with 53% crystalline substance. In the series of native celluloses, wood pulp has about 65%, Valonia 65-70%, and bacterial cellulose about 40%. By dry grinding of rayon, a powder was obtained containing only slightly less than 10% crystalline substance, which on recrystallization in water, yields 2 product having the same crystallinity as rayon. The difference between the heats of wetting of the criginal and the recrystallized powder affords additional support of the results obtained.
    Additional Material: 6 Ill.
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  • 10
    Publication Date: 1946-12-01
    Print ISSN: 0002-7863
    Electronic ISSN: 1520-5126
    Topics: Chemistry and Pharmacology
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