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  • 1
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 397-405 
    ISSN: 0887-6266
    Keywords: mesogenic epoxy resin ; liquid crystalline thermosets ; anisotropy ; network chain orientation ; heat resistance ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The epoxy resin containing a typical mesogenic group such as biphenol was cured with catechol novolak and aromatic diamines which have neighboring active hydrogens. In the biphenol-type epoxy resin cured with catechol novolak, 4,4′ diaminodiphenylmethane, and p-phenylenediamine (PPD), the glass-rubber transition almost disappeared, and thus a very high elastic modulus was obtained in the high temperature region. It is clear that the thermal motion of the network chains is significantly suppressed in these cured systems. In addition, in the PPD-cured system, a characteristic pattern like a schlieren texture was clearly observed under the crossed polarized optical microscope. Thus we conclude that the mesogenic group contained in the epoxy molecule is oriented in the networks when the mesogenic epoxy resin is cured with phenols and diamines which have neighboring active hydrogens. On the other hand, the biphenol-type resin cured with 3,3′,5,5′-tetraethyl-4,4′-diamino diphenylmethane (TEDDM) showed a well-defined glass-rubber transition and, thus, a low rubbery modulus. In this cured system, no characteristic pattern was observed under the crossed polarized light. These results show that the large branches, such as ethyl groups on the network chains, prevent the orientation of network chains which contain the mesogenic group. © 1997 John Wiley & Sons, Inc.
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  • 2
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 439-445 
    ISSN: 0887-6266
    Keywords: cholesteric order ; electron microscopy ; periodical lamellar structure ; macromolecules ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The macromolecular cholesteric structure in the ethyl-cyanoethyl cellulose [(E-CE)C]/acrylic acid [AA] cholesteric liquid crystalline solutions is studied by directly observing the morphology and structure of the ethyl-cyanoethyl cellulose [(E-CE)C]/polyacrylic acid [PAA] using electron microscopy. A periodical lamellar structure is observed in ultrathin slices of the composites with cholesteric order by both transmission electron microscopy (TEM) and low-voltage scanning electron microscopy (LVSEM). It is suggested that the periodical lamellar structure is induced by the twist of the molecular orientation in the cholesteric phase and reflects the structural features of the macromolecular cholesteric phase. The macromolecular cholesteric phase exhibits the twisted ring morphology in the initial stage of the formation of the liquid crystalline phase. The swelling of the ultrathin slices with cholesteric order in water is heterogeneous, which suggests the tight packing of the (E-CE)C chains in the direction of the helix axis in the macromolecular cholesteric phase. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 439-445, 1998
    Additional Material: 10 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 1463-1472 
    ISSN: 0887-6266
    Keywords: adhesion ; oxide coating ; thickness effects ; fragmentation test ; adhesive strength ; cohesive strength ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Fragmentation tests in the uniaxial mode were performed on poly (ethylene terephthalate) (PET) films coated with a silicon oxide layer of thickness ranging from 30 to 156 nm. The coating's fragmentation process was investigated to reveal the crack onset strain and the crack density at fragmentation saturation. Adhesive strength was modeled from the Kelly-Tyson approach, including a Weibull distribution of the coating strength. The prediction was found to be independent of coating thickness, and equal to the substrate shear stress at saturation. The cohesive strength of the coating was characterized from the crack onset strain. The measured decrease in crack onset strain with coating thickness increase was modeled by means of Weibull and fracture mechanics theories, the latter providing the best predictions. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 1463-1472, 1997
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  • 4
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 425-431 
    ISSN: 0887-6266
    Keywords: poly(arylene ether ketone) ; gas permeability ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In this work we present the results from studies on novel poly(arylene ether ketone)s, including gas permeability, wide-angle x-ray diffraction (WAXD), and dynamic mechanical analysis (DMA). Poly(arylene ether ketone)s containing 2,2′- and 3,3′-dibenzoylbiphenyl (DBBP) moieties were characterized to study the effect of biphenyl substitution on gas transport properties. Gas permeabilities of naphthalene-containing poly(arylene ether ketone)s were also measured. Higher permeabilities were observed for polymers prepared with 6F-BPA, compared to 9,9-bis(4-hydroxyphenyl)fluorene (HPF). The naphthalene-containing polymers exhibited higher permeabilities than the DBBP polymers, except for a polymer having the 2,2′-DBBP and tetramethylbiphenyl moieties. Based on our work, and results reported in the literature, the 3,3′-DBBP polymers showed the lowest permeabilities for DBBP-containing poly-(arylene ether ketone)s. The low permeabilities are due to more efficiently packed chains brought on by greater flexibility of the backbone, compared to the other polymers studied. DMA studies confirmed the higher barriers to rotation which are believed to be responsible for 2,2′-DBBP polymers having similar selectivities compared to 3,3′-DBBP polymers. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 425-431, 1998
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  • 5
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 11 (1973), S. 989-1001 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Methyl methacrylate (MMA) was polymerized by radical initiation at 90°C by its own preformed tactic polymers, i.e., conventional (c-PMMA), isotactic (i-PMMA), and syndiotactic (s-PMMA) PMMA, and also by a preformed 1:1 stereocomplex of i-PMMA and s-PMMA. The collected polymers were separated into two fractions by extraction with boiling acetone and characterized by 60 MHz NMR spectra and viscometry. Higher polymerization rates were obtained in the presence of stereo-regular PMMA than in the presence of c-PMMA. Moreover, it appeared that i-PMMA promoted the formation of s-PMMA, and conversely s-PMMA the formation of i-PMMA, especially in the initial stages of the reaction. A higher M̄v of the preformed polymer yielded a higher rate and a higher stereospecificity of the polymerization. No polymerization took place in the absence of performed PMMA. The results support a replica mechanism proposed by Szwarc, in which polymerization is preceded by a specific arrangement of monomeric units along the polymeric chain into a distinctive pattern. Such arrangement coupled with a strong tendency of the isotactic and syndiotactic species to associate may lead to the present stereospecific replica polymerization. This association is demonstrated by rapid gelation during polymerization and by lowering of reduced viscosity in very dilute mixtures of i-PMMA and s-PMMA in MMA.
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  • 6
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 11 (1973), S. 2975-2989 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Methyl methacrylate (MMA) was polymerized by radical initiation at 25°C or 35°C in various solvents in the presence of stereoregular poly(methyl methacrylate) (PMMA). The occurrence of stereospecific replica polymerization appeared to be related to the capability of stereoassociation of isotactic and syndiotactic PMMA. The solvents can be roughly divided into three types. Type A solvents are polar solvents, which promote stereoassociation resulting in gelation and precipitation. Examples are dimethylformamide, dimethyl sulfoxide, and acetone. Type B solvents are nonpolar aromatic solvents like benzene and toluene, wherein stereoassociation is weaker but still leads to gelation. Type C solvents are very good solvents, in which stereoassociation does not occur. Chloroform and dichloromethane belong to this class. In solvents of type A as well as type B, polymerization in the presence of i-PMMA as a polymer matrix was syndiospecific. However, in the presence of s-PMMA as a polymer matrix the polymerization was isospecific only in type A solvents. The syndiotactic or isotactic triad contents of the polymer formed could be as high as ca. 90% at low conversions. In solvents of type C, polymerization in the presence of stereoregular PMMA proceeds according to a normal radical mechanism. Syndiotacticity was always less than 70%. Stereocomplexes formed in situ during replica polymerization were partly crystalline as detected by x-ray diffraction. The highest crystallinity was detected in those formed in type A solvents.
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  • 7
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 1267-1275 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Melting point, the iodine color reaction, and foam fractionation were studied on model poly(vinyl alcohol) (PVA) having short branches of one or two monomer units in length. An increase in the amount of short branching units caused a marked decrease in color intensity of the PVA-iodine reaction and in the melting point. These tendencies were more remarkable when the short branching was two monomer units in length than when it was one monomer unit. It was also found that foam fractionation of an aqueous PVA solution produced PVA fractions with different degree of short branching, the degree increasing with increase in the fraction number. The color intensity of the PVA-iodine reaction has been confirmed to decrease with increase in the fraction number, but this result cannot be explained solely in terms of the short branching. It is concluded that the phenomenon of foam fractionation of PVA and the iodine color reaction of the fraction appear to be governed by many factors such as molecular weight, stereoregularity, and short branching.
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  • 8
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 16 (1978), S. 399-406 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Photopolymerization of methyl methacrylate was studied in the presence of the system of the tetraphenylporphine-iron(III) complex, free amine, and carbon tetrachloride at 0°C in methanol solution. It was found that the activity of the complex for polymerization does not depend upon the structure of the free amines added. The effect of the polymeric amines on the polymerization was also examined. The photochemical reaction process among the iron(III) complex, amine, and carbon tetrachloride was followed also under similar conditions by ultraviolet and visible spectroscopy. The scheme for the initiation species presented is supported by the results on the posteffect of the photopolymerization.
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  • 9
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: N-Vinylpyrrolidone (NVP) was polymerized in dimethylformamide (DMF) at 60°C in the presence of poly(methacrylic acids) (PMAA) of different tacticities and molecular weights. The rate enhancement, which was ascribed to chain growth of the poly(vinylpyrrolidone) (PVP) radical along the polyacid template, became more pronounced with increasing chain length and syndiotacticity of the PMAA template. The results can be expressed by vR = aPvn, where vR is the polymerization rate relative to that of the blank experiment, Pv is the viscosity-average degree of polymerization of PMAA, and a and n are constants depending on the reaction conditions and tacticity of PMAA. In the presence of excess monomer the rate enhancement decreased when the quantity of PVP produced corresponded to a stoichiometric ratio of 1:1 with the available PMAA. It is proposed that the template effect is caused mainly by delay of the bimolecular termination step of growing PVP radicals associated with PMAA. Diffusion of polymer radicals, and consequently termination, will be more impaired if the attached PMAA has a greater length (size) and if the binding forces between PVP radical and PMAA template are stronger. The latter implies that PVP forms the strongest complexes with syndiotactic PMAA. This is supported by experiments concerning complex stability.
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  • 10
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 301-312 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Behavior of the free radical copolymerization of N-β-methacryloyloxyethyl derivatives of adenine with that of thymine was studied in chloroform solution, taking account of the specific base-base interaction of these monomers. Hydrogen bonding interaction between such monomers was observed by NMR spectroscopy. The acceleration of copolymerization was found to be greater either at lower monomer concentration or at lower polymerization temperature. When N-β-methacryloyloxyethylcarbazole was used as a comonomer, the rate of copolymerization showed a similar trend as in the case of usual free radical copolymerizations. From r1 and r2 values obtained, the copolymerization was found to be alternating, particularly in the case of copolymerization between monomers having complementary nucleic acid bases. The results suggest that the hydrogen bonding interaction between adenine and thymine plays a role in the propagation step.
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