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  • Wiley-Blackwell  (42)
  • American Institute of Physics  (3)
  • 1
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A general description is given for relations among the optical quantities obtained from fluorescence polarization measurements on bulk polymer stained by fluorescent groups: the moments of distribution of orientations of the fluorescent groups, and those of the structural units of the polymer (chain segments) on which the groups are adsorbed. Two assumptions as to the biaxial symmetry of the bulk polymer and the cylindrical symmetry of the optical anisotropy of the fluorescent element, both for the absorption and emission processes, reduce the intensities of the polarized fluorescence to a 3 × 3 matrix L which is asymmetric (Lij ≠ Lji), as has frequently been observed in experiments. The components of the L matrix are related to those of the J matrix which is so defined as to describe the fourth moments of the distribution of orientations of the structural units on the basis of a random distribution of the rotational angle of the unit about the segment axis. It is found that the use of the method of fluorescence polarization combined with absorption dichroism and/or emission gives the values of the optical anisotropy ratios of the fluorescent unit, and that the effects of the thermal agitation of the structural unit can be separated from the moments of the orientation distribution for the simplest case.
    Additional Material: 2 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 797-816 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The orientation behavior of stereoregular poly(vinyl alcohols) was investigated during stretching and after releasing the stress on the bulk polymers at relatively high humidity (80% R. H.) A structural model, differing from polyethylene, was proposed in which the crystallites were embedded in a considerably swollen amorphous matrix without any definite physical interaction so as to form an aggregation of crystallites, a superstructure. The crystal orientation followed, in principle, “the first borderline case” of Kratky, but with some difference from theory in orientation, while the noncrystalline orientation was represented by the freely jointed equivalent chain model of Kuhn and Grün with a value of N/γ as small as around 5. The difference between crystal orientation found and the theorietical orientation is discussed and some factors which prevented the crystal orientation are considered.
    Additional Material: 11 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 1439-1443 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 4 Ill.
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  • 4
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A mathematical representation of the transformation of an orientation function between two sets of Cartesian coordinates is discussed in terms of a series expansion of the distribution function in generalized spherical harmonics. A general procedure for calculating the mechanical anisotropy of a single-phase system (a polycrystalline material) from the orientation of its structural units and the intrinsic mechanical anisotropy of the structural unit is discussed in relation to the transformation of the orientation distribution function, i.e., mutual conversion of the coefficients in the expansion of the distribution function between the two sets of Cartesian coordinates. The procedure is extended to a two-phase systems (semicrystalline polymers) containing structural units composed of crystalline and noncrystalline materials in three different geometrical arrangements.
    Additional Material: 7 Ill.
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  • 5
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Electron microscopic textures of A-B type block copolymers of styrene and isoprene cast from several solvents were investigated by means of the osmium tetroxide fixation technique. The two-phase structure, i.e., the semimicro heterogeneous structure due to the microphase separation of block segments, was observed to change systematically with the fraction of block segments and the kind of solvent. Three types of fundamental domain structure were found. With the assumption that domain structure originates from micellar structure at a critical concentration in relatively dilute solution during solvent casting, the formation of the three types of domain structure and the sizes of their elements were treated in terms of the equilibria governing the formation of micelles at the critical concentration. This analysis takes into account such thermodynamic and molecular parameters as the incompatibility between the A and B segments, the solvation of the segments, the casting temperature, the total chain length of the block copolymer, and the weight fraction composition of the block copolymer. It was concluded that the block segments are preferentially oriented along the direction perpendicular to the interface between the two phases. This particular orientation-aggregation of the block segments must make the bulk properties of the block copolymer much different from those of merely mechanical mixtures of the corresponding homopolymers, even if the same semimicro heterogeneous structures are formed in the mechanical mixtures.
    Additional Material: 11 Ill.
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  • 6
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Mechanical properties of four kinds of natural rubber vulcanizates differing in vulcanization conditions, and consequently in degree of crosslinking (having values of the Mooney-Rivlin constant C1 ranging from 0.68 to 1.98) were observed under orthogonal biaxial stretching in a range of strain invariants Ii from 3.4 to 9.0 (extension ratios λi from 0.7 to 3.0). The results obtained were analyzed by two methods. One method employed the Valanis-Landel postulate that the strain-energy function W(λ1, λ2, λ3) is a separable symmetric function of the principal extension ratios, i.e., W(λ1,λ2,λ3) = w(λ1) + w(λ2) + w(λ3); the other utilized the contour plots of ∂W(I1, I2)/∂I1 and ∂W(I1, I2)/∂I2 surface within the (I1, I2) domain. The postulate for W was examined in detail with good agreement with experimental results. The dependences of ∂W(I1, I2)/∂I1 and ∂W(I1, I2)/∂I2 surfaces on the degree of crosslinking and temperature were further investigated, with the following conclusions. The surfaces have fairly steep slopes for the region of relatively small deformation (i.e., I1 〈 5) and become flat with increasing Ii for all the test specimens. The slope becomes less steep with decreasing degree of crosslinking. The values of ∂W/∂I1 increase linearly and the ∂W(I1,I2)/∂I2 surface becomes flat, both with increasing temperature: i.e., the temperature dependence of ∂W/∂I1 further depends on Ii. The ∂W(I1,I2)/∂I2 surface has a maximum near 40°C.
    Additional Material: 16 Ill.
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  • 7
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: As one in a series of studies relating the rheological properties of mechanical mixtures of two polymer components to the degree of mixing, the temperature dependence of tensile stress relaxation behavior of two types of mixed systems, i.e., poly(methyl methacrylate)-poly(vinyl acetate) system and lightly crosslinked poly(methyl methacrylate-poly(vinyl acetate)) system, was investigated over a temperature range covering the glass transition temperatures of both polymer components. The time-temperature superposition procedure was carried out for comparison of several parameters, such as fractional free volume and its thermal expansion coefficient, which were determined on the basis of the free volume concept from the viscosity in relation to the William-Landel-Ferry equation, with those of the individual polymer components. Although the fractional free volume and its thermal expansion coefficient thus determined for the mixed systems were apparent values, the results may, at least qualitatively, deny the simple additivity of the free volumes of the two-polymer mixed phases and suggest the existence of a sort of physical interaction between the phases, i.e., the internal pressure induced by one phase or the other due to a difference in thermal expansion coefficient between the phases.
    Additional Material: 11 Ill.
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  • 8
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: As one in a series of studies relating the rheological behavior of mechanical mixtures of two polymer components to the degree of mixing, the tensile stress relaxation behavior of a graft copolymer of poly(vinyl acetate) with styrene, obtained by 60Co γ-irradiation of poly(vinyl acetate) in styrene solution and extraction of homopolymers, was investigated as a function of the fraction of styrene component and compared with that of a mechanical mixture of poly(vinyl acetate) with polystyrene, one of the typical combinations of incompatible components. The results obtained may classify the graft copolymer as a sort of mechanical mixture giving stable mixing even for incompatible components.
    Additional Material: 16 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 24 (1978), S. 1-20 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Because of the generally immiscible nature of polymers, multicomponent polymers or polymeric alloys often exhibit microphase separation. The morphologies of these heterogeneous materials are determined not only by the composition of the system, but also by the processing conditions. The resulting microstructures exert a profound influence on the properties of the polymeric alloys. The purpose of this review is to discuss the more recent advances in the investigation of the relation between the structure of the polymeric alloys and their properties. An understanding of this relationship would be important in being able to tailor make better materials and exploit the unique properties of these materials for engineering applications.
    Additional Material: 37 Ill.
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  • 10
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A mathematical development interrelating the orientation distribution functions of three kinds of orientation units for a polymer spherulite (i.e., a crystal lamella, a crystallite, and a given reciprocal lattice vector of the crystallite) is formulated on the basis of series expansions of the distribution functions in generalized spherical harmonies. Two types of uniaxial deformation models of a polyethylene spherulite, taking account of micronecking and untwisting of crystal lamellae, and of chain tilting and untwisting of crystal lamellae, respectively, both in addition to affine deformation of the lamellae are discussed. The models are tested by comparison of the theoretical orientation distribution functions of some reciprocal lattice vectors of the crystallite with the results of x-ray diffraction experiments.
    Additional Material: 13 Ill.
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