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  • 1
    ISSN: 1435-1536
    Keywords: Cellulose acetate ; hydroxypropylcellulose ; cross-linking ; liquid-crystalline state ; anisotropic state ; novel orientation technique ; oriented films ; mechanical properties ; maximum extensibility ; tensile modulus ; tensile strength ; birefringence
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The networks of cellulose acetate and hydroxypropylcellulose prepared in the first part of this investigation were studied with regard to their mechanical properties. The quantities of particular interest were increases in tensile modulus and tensile strength obtained by drying the swollen films under strain, both uniaxial and equi-biaxial. These increases or improvements in mechanical properties were determined as a function of polymer concentration during cross-linking, polymer molecular weight, degree of cross-linking, and elongation during drying. In all cases, the improvements increased with increase in elongation during drying, and the largest increases were obtained in the case of the highest molecular weight polymer which had been lightly cross-linked in dilute (isotropic) solutions. The extent of ordering in these systems was gauged approximately by measurements of birefringence, which were correlated with their tensile moduli and tensile strengths.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 1435-1536
    Keywords: Gelatin ; crosslinking ; drawing ; oriented films ; dymeanie mechanical properties
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract This study is an extension of previous work on cellulosics [(1994)Colloid Polym Sci 272: 284, 393] that showed that unusually good mechanical properties can be obtained by drying a swollen network of semirigid chains in a state of strain. This novel approach is applied in this investigation to gelatin, because of its attractive environmental characteristics but poor mechanical properties in the unmodified form. Since drawing of non-crosslinked gelatin is not practical, crosslinking by formaldehyde was used, followed by swelling, drawing and drying at fixed length. Mechanical tests were performed in static and dynamic modes. In this way improvements of Young's modulusE, and stress at breakσ b were determined as a function of gelatin concentration during drying. An increase inE andσ b up to 2–3 times, and in the dynamic modulusE′ up to 6 times, was obtained when the draw ratio λ reached 4–5, after whichE, E′, andσ b were found to decrease. Such behavior is explained by the highest orientation being achieved at λ=4–5, as proved by x-ray analysis. At λ=10–20 the orientation is lost due to relaxation of chain segments, which is preceded by partial destroying of the network structure (chemical and physical), possibly via chain scission, but probably mostly by the pulling out of chains from crystallites. In any case, the mechanical properties become poor again. The improvements reported above were referred to the undrawn but crosslinked gelatin. Compared to the starting isotropic non-crosslinked material, the improvement is slightly higher. The observation that the improvements are less than those obtained for the cellulosics is explained by the coexistence of interpenetrating chemical and physical networks, which is typical of gelatin. This structural feature drastically reduces the orientability of the chains and the improvements that can be expected in the mechanical properties.
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 1435-1536
    Keywords: Key words Gelatin ; crosslinking ; drawing ; oriented films ; dynamic mechanical properties ; glass transition
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract  This second part of a systematic study of the properties of crosslinked-oriented gelatin involves the effects of orientation and water content on the glass transition temperature T g and on the melting behavior. The samples were the same as those in the preceding study, and their transition temperatures were determined by both differential scanning calorimetry and dynamic mechanical thermal analysis. The crosslinked gelatin which had been room-conditioned showed two transition temperatures: the lower one was attributed to T g of the water-plasticized gelatin, and the higher one was interpreted as T g of dried gelatin superimposed by melting. A rather unusual situation arose because of the fact that the T g and melting temperatures T m (217 and 230 °C, respectively) are so similar. Using water as plasticizer not only decreases T g but produces imperfect crystallites which melt below the T g of the system. The presence of the amorphous phase in the glassy state would presumably make it essentially impossible to define a melting point or crystallization temperature in the normal manner, as an equilibrium between crystalline and amorphous phases.
    Type of Medium: Electronic Resource
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  • 4
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Molecular theories of rubberlike elasticity are surveyed, starting with the earliest attempts carried out in the 1930's and ending with work still very much in progress. The models are variously based on phenomenological arguments, affinely-deforming networks, phantom networks, constrained junctions, constrained chains, slip-links, molecular tubes, van der Waals concepts, or rotational isomeric chains. Most of the theories are analytical, but some involve computer simulations based on Monte Carlo methods. The theories are generally for networks of Gaussian chains, but there have been significant advances for non-Gaussian networks as well, and these are particularly important with regard to a better understanding of ultimate properties. The major outstanding problem on the theory side, however, seems to be a quantitative treatment of chain entanglements.There have also been numerous advances on the experimental side. These include preparation of model networks of known structure, accumulation of elasticity data for deformations other than the much-studied simple elongation, development of new characterization techniques (such as fluorescence polarization, and X-ray and neutron scattering), investigation of the phenomenon of gel collapse, borrowing of ideas from the area of bioelastomers, and preparation of novel reinforcing fillers.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
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  • 5
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Conformational energies of the poly-N-methyl-L-alanine chain have been calculated as a function of the rotational angles of its skeletal bonds, taking into account torsional potentials, van der Waals repulsions, and London attractions. Four pronounced minima in the energy were found; the relative magnitudes of the energies at these minima suggest that the preferred conformation of this chain is either a right-handed, approximately threefold helix, or a slightly distorted, left-handed α-helix. Inclusion of an estimate of the dipolar contribution to the total conformational energy does not significantly affect this conclusion.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 15 (1976), S. 1853-1856 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 2 (1979), S. 87-97 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: New synthetic techniques are now available for the preparation of “model” polymer networks of known and carefully controlled molecular structure. The preparation of such networks and their utilization in elucidating molecular aspects of rubberlike elasticity are illustrated using highly elastomeric, unfilled networks of polydimethylsiloxane. In one such preparative technique, hydroxyl-terminated chains are end-linked using either a tetrafunctional or trifunctional silicate, in either the undiluted state or in solution. Because of the selectivity and completeness of the reaction, the molecular weight and molecular weight distribution of the network chains are to good approximation those of the chains prior to their end-linking into the network structure. The experimentally determined stress-strain isotherms and degrees of equilibrium swelling of the resulting networks are then used to evaluate the molecular theories of rubberlike elasticity, particularly with regard to the dependence of the elastic modulus and ultimate properties on the degree of cross linking and the cross-link functionality. Another preparative technique employs random and block copolymers containing reactive vinyl groups in known amount and known distribution along the chains. Selectively cross-linking through these sites then yields model networks ranging from random to highly non-random in chain length distribution. These networks are particularly useful for characterizing the effects of very short chains on the average degree of cross-linking or average network chain length as obtained from stress-strain and swelling equilibrium measurements.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 183 (1982), S. 2555-2563 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Poly(pentamethylene sulfide)Structure-based name: poly(thiopentamethylene). (P5MS) [—S(CH2)5—]x was prepared by the condensation polymerization of nearly equimolar amounts of pentamethylene dibromide and the sodium salt of 1,5-pentanedithiol. Selective precipitations were used to obtain a fraction of the polymer, and dielectric constant measurements on solutions of it in benzene were used to obtain dipole moments over the range 20-60°C. Rotational isomeric state calculations based on conformational energies obtained from semiempirical potential energy functions gave results in fair agreement with experiment. Since extensive previous studies on a number of polyoxides have demonstrated the difficulty in calculating the energy of the O…CH2 interactions, the energy of the corresponding S…CH2 interactions in P5MS was adjusted to obtain better agreement between theory and experiment.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 187 (1986), S. 2861-2866 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Four tetraalkoxysilanes Si(OR)4 were absorbed into networks of polydimethylsiloxane and then hydrolyzed, using a variety of catalysts, to give reinforcing silica particles. On the basis of the amount of silica precipitated and the extent of reinforcement, the (decreasing) order of effectiveness was found to be tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, and tetramethoxysilane.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 183 (1982), S. 2565-2572 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Several earlier studies of poly(alkylene sulfides) have not yielded evidence for a sulfur gauche effect, in contrast to the large attractive gauche effect found particularly in the lower members of the poly(alkylene oxides). In this study the dipole moments at 25°C and the corresponding temperature coefficient of poly(1,3-dithiocane)Structure based name: poly(thiomethylonethiopentamethylene). [—SCH2S(CH2)5—]x are calculated in the rotational isomeric-state approximation, and the results compared to the values determined by experiment. In the calculations the energy Eσ′ = [Eg± - Et] associated with S. . .CH2 interactions in the SCH2—SCH2 segment is adjusted to attain agreement between theory and experiment. The results indicate that an extra stabilization energy of ca. 0,9 kcal . mol-1 must be added to these gauche states relative to the trans state (beyond that determined by conformational energy calculations based on semiempirical potential energy functions). This provides the first evidence of a large attractive sulfur gauche effect in the polysulfides, about equal in magnitude to that found for the analogous poly(methylene oxide).
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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