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  • Chemistry  (769)
  • Wiley-Blackwell  (769)
  • American Chemical Society
  • American Physical Society
  • International Union of Crystallography (IUCr)
  • 2000-2004
  • 1990-1994  (769)
  • 1980-1984
  • 1955-1959
  • 1992  (769)
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  • Wiley-Blackwell  (769)
  • American Chemical Society
  • American Physical Society
  • International Union of Crystallography (IUCr)
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  • 2000-2004
  • 1990-1994  (769)
  • 1980-1984
  • 1955-1959
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  • 1
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 30 (1992), S. 1321-1327 
    ISSN: 0887-6266
    Keywords: polyimides. stiff, optical and dielectric properties in their films of ; optical anisotropy and chain orientation stiff polyimide thin films ; dielectric properties of stiff polyimide thin films ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Thin films of poly(p-phenylene biphenyltetracarboximide) (BPDA-PDA), prepared by thermal imidization of the precursor poly(amic acid) on substrates, have been investigated by optical waveguide, ultraviolet-visible (UV-VIS), infrared (IR), and dielectric spectroscopies. The polyimide films exhibit an extraordinarily large anisotropy in the refractive indices with the in-plane index n∥ = 1.806 and the out-of-plane index n⊥ = 1.589 at 1064 nm wavelength. No discernible effect of the film thickness on this optical anisotropy is found between films of ca. 2.1 and ca. 7.8 μm thickness. This large birefringence is attributed to the preferential orientation of the biphenyltetracarboximide moieties with their planes parallel to the film surface, coupled with the strong preference of BPDA-PDA chains to align along the film plane. The frequency dispersion of the in-plane refractive index n∥ is consistent with the results calculated by the Lorentz-Lorenz equation from the UV-visible spectrum exhibiting several absorption bands in the 170-500 nm region. The contribution from the IR absorption in the range 7000-400 cm,-1 computed by the Spitzer-Kleinmann dispersion relations from the measured spectra, adds ca. 0.046 to the in-plane refractive index n∥. Tilt-angle-dependent polarized IR results indicate nearly the same increase for the out-of-plane index n⊥. Application of the Maxwell relation then leads to the out-of-plane dielectric constant ε⊥ ≃ 2.7 at 1.2 × 1013 Hz, as compared with the measured value of ca. 3.0 at 106 Hz. Assuming this small difference to remain the same for the in-plane dielectric constants ε∥, we obtain a very large anisotropy in the dielectric properties of these polyimide films with the estimated in-plane dielectric constant ε∥ ≃ 3.4 at 1.2 × 1013 Hz, and ε∥ ≃ 3.7 at 106 Hz. © 1992 John Wiley & Sons, Inc.
    Additional Material: 6 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Biomedical Materials Research 26 (1992), S. 273-289 
    ISSN: 0021-9304
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine , Technology
    Notes: We have studied the surface chemistry of two lots of Biomer™ (BSP067 and BSUAOOl), and widely used commercial poly(ether urethane) (PEU). Although transmission infrared adsorption studies revealed no differences in the bulk chemistry of the two lots, the surface chemistry, as seen by x-ray photoelectron spectroscopy (XPS) and static secondary ion mass spectrometry (SIMS), was different. Lot BSP067 showed softsegment enrichment at the surface, which is typical of PEU. Lot BSUAOOl showed no evidence of either hard- or soft-segment PEU components at the surface. The surface of this lot was completely covered with a nonextractable additive identified as poly(diisopropy1 amino ethyl methacrylate). Small amounts of a low-molecular-weight antioxidant were observed at the surface of both samples. Because the biological response to polymers is dependent on surface structure, these results are of considerable importance to biomaterials research.
    Additional Material: 7 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    Chichester [u.a.] : Wiley-Blackwell
    Surface and Interface Analysis 19 (1992), S. 23-26 
    ISSN: 0142-2421
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Films of amorphous NbSi prepared by magnetron sputtering were found to have a higher concentration of silicon at the surface than in the bulk material. In this paper we report on measurements of both ultraviolet photoemission spectroscopy and Auger electron spectroscopy carried out on samples prepared in situ at the UK Synchrotron Radiation Source, Daresbury. Spectr taken immediately after sputter deposition show that the surface is rich in silicon, while following argon ion bombardment the bulk composition is slowly revealed with a much greater concentration of niobium. This is observed by a comparison of the relative heights of peaks in the Auger spectra and by resonance effects and the sharpening of the Fermi edge in the UP spectra. Of particular interest are changes around the metal-insulator transition that occur at approximately 11 at.% niobium.
    Additional Material: 4 Ill.
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  • 4
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Mixtures of 1,1,3,3-tetrafluoroacetone and perfluorodi-n-propyl ketone have been photolyzed together over the temperature range 50° to 200°C, and the disproportionation/combination ratio for n-C3F7 and CF2H radicals has been determined to be Δ(n-C3F7, CF2H) = 0.072 ± 0.003. A reevaluation of existing data on CH3 and CF2H radicals leads to a value of Δ(CH3, CF2H) = 0.35. The large variations in Δ for the reactions of alkyl and perfluoroalkyl radicals with CF2H radicals are discussed. © John Wiley & Sons, Inc.
    Additional Material: 2 Ill.
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  • 5
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: HNBR rubbers, which are made by selective hydrogenation of the olefinic bonds of NBR rubbers, have been developed, because they show improved resistance towards heat and chemicals. In this study, two other properties are discussed that arise from the fact that HNBR rubbers are fairly alternating copolymers of unpolar butylene and polar acrylonitrile units: At intermediate compostions, HNBR rubbers form homogeneous blends with PVC, and near the symmetric composition they exhibit strain-induced crystallisation. The thermal transitions of the HNBR rubbers and their miscibility with PVC were analyzed, as well as the crystallisation and the stress-strain behaviour of a HNBR of symmetric composition.
    Additional Material: 12 Ill.
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  • 6
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of 9-bromoanthracene (1) with benzenethiol(ate) in tetraglyme proceeds by a SNAr mechanism. The concurrent formation of anthracene is not due to a competing single-electron-transfer pathway involving either benzenethiol or benzenethiolate anion.
    Additional Material: 1 Ill.
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  • 7
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The feasibility of the titled reactions for the rapid, enantioselective synthesis of cis-tricyclo[9.3.1.03,8]pentadecane precursors to taxusin and taxol has been examined. The catalysts most well suited to inducing the appropriate 1,2-shifts have been identified. To a great extent, the rearrangement products are formed as a direct consequence of appropriate structural features (kinetic phenomenon) and strain minimization (thermodynamic driving force). Complementary MM2 calculations of the global minimum in each series provided indications that were completely in line with the experimental observations. Sophisticated NMR studies and X-ray crystallographic determinations were coordinated to remove any ambiguity of product structure and solid-state conformation.
    Additional Material: 4 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 32 (1992), S. 1500-1508 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    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: Novolak resins provide the best overall performance for “g” and “i”-line photoresists. There is a continuing need for advanced novolak designs that will provide improved lithographic, thermal, and etch characteristics that may be reproducibly synthesized. A novolak synthesis process was developed using the solution condensation technique. Cresol mixtures with m-cresol and 3,5-xylenol at specific ratios provide reproducible novolaks with controlled molecular weights. In order to achieve high thermal and etch performance, while retaining photospeed and resolution characteristics, three basic approaches were investigated: (1) increase in molecular weight, which produces novolaks with Tg ranging from 120 to 130°C with relatively slow dissolution rates; (2) incorporation of multi-hydroxyphenols such as resorcinol to tailor the dissolution rate, resolution, thermal, etch, and adhesion characteristics; (3) partial esterification of multi-hydroxy novolaks giving a Tg range of 140 to 150°C. Lithographic evaluation of the novolak resins was performed by formulating with a 2,1,4-diazonaphthoquinone (DNQ) sensitizer. Results on resin synthesis, molecular weights, lithographic, thermal, and etch characteristics are discussed.
    Additional Material: 10 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 30 (1992), S. 1647-1653 
    ISSN: 0887-624X
    Keywords: microwave processing ; imidization ; rapid curing ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Microwave radiation has been clearly shown to result in enhancement of the rate of reaction for an imidization reaction. Analysis of the kinetic parameters showed that the apparent activation energy for the reaction was reduced from 105 to 55 kJ/mol, under the conditions of this experiment. The mechanism which has been proposed to explain this enhancement is based on the concept of a nonuniform temperature on a molecular scale, rather than a true reduction in the activation energy. © 1992 John Wiley & Sons, Inc.
    Additional Material: 5 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 39 (1992), S. 679-687 
    ISSN: 0006-3592
    Keywords: immobilized enzyme distribution ; diffusion cell ; active-site titration ; controlled-pore glass ; cell profile ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The total and active immobilized enzyme (IME) distributions in porous supports are studied both theoretically and experimentally. In order to determine experimentally the enzyme distribution profiles within a single particle, we construct a diffusion cell containing controlled-pore glass particles such that the cell would mimic a large pellet support. Our purpose is to study the interplay between the diffusion process within the interparticle void space and immobilization process in the controlled-pore glass particles onto the evolution of the (total and active) enzyme distributions. A mathematical model is developed to describe the interaction of various processes within the diffusion cell. The immobilized enzymes are determined for a system of trypsin and controlled-pore glass particles. The total amount of enzymes are determined by the amino acid analysis, and the active fraction is obtained by an active-site titration. The experimentally measured total IME profiles compare very well with that predicted by the model. The determined active enzyme profile is found to be nonuniform one, and it represents about 40% of the total enzyme immobilized in the support particles.
    Additional Material: 9 Ill.
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