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  • 1
    Electronic Resource
    Electronic Resource
    Palo Alto, Calif. : Annual Reviews
    Annual Review of Physical Chemistry 23 (1972), S. 415-438 
    ISSN: 0066-426X
    Source: Annual Reviews Electronic Back Volume Collection 1932-2001ff
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    [s.l.] : Nature Publishing Group
    Nature 227 (1970), S. 702-703 
    ISSN: 1476-4687
    Source: Nature Archives 1869 - 2009
    Topics: Biology , Chemistry and Pharmacology , Medicine , Natural Sciences in General , Physics
    Notes: [Auszug] At low pressures (〈 10~5 torr), previous single collision experiments1'2 indicated that the main negative ion species formed in SF6 by electron collisions were SF6~ and SFg. In addition, the negative ion currents were observed to depend on pressure rather than on the square of the pressure, ...
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Springer
    Journal of thermal analysis and calorimetry 46 (1996), S. 719-731 
    ISSN: 1572-8943
    Keywords: aromatic polyimide fiber ; as-spun fiber ; crystallization ; crystal structure ; crystal unit cell ; draw ratio ; dry-jet wet spinning ; isotropic solution ; modulus ; self-elongation ; tensile strength ; thermal shrinkage stress ; thermal shrinkage strain ; thermomechnical analysis ; triclinic ; wide angle X-ray diffraction ; zone drawing
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Three aromatic polyimides based on 3,3′,4,4′-biphenyl-tetracarboxylic dianhydride (BPDA) and three different diamines 2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl (PFMB), 2,2′-dimethyl-4, 4′-diaminophenyl (DMB) or 3,3′-dimethylbenzidine (OTOL) have been synthesized. These polyimides are soluble in hotp-chlorophenol,m-cresol or other phenolic solvents. Fibers have been spun from isotropic solutions using a dry-jet wet spinning method. The as-spun fibers generally exhibit low tensile properties, and can be drawn at elevated temperatures (〉380° C) up to a draw ratio of 10 times. Remarkable increases in tensile strength and modulus are achieved after drawing and annealing. The crystal structures of highly drawn fibers were determinedvia wide angle X-ray diffraction (WAXD). The crystal unit cell lattices have been determined to be monoclinic for BPDA-PFMB and triclinic for both BPDA-DMB and BPDA-OTOL. Thermomechanical analysis (TMA) was used to measure thermal shrinkage stress and strain. A selfelongation has been found in the temperature region around 450°C. This phenomenon can be explained as resulting from the structural development in the fibers as evidencedvia WAXD observations.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Springer
    Journal of thermal analysis and calorimetry 47 (1996), S. 957-973 
    ISSN: 1572-8943
    Keywords: DSC ; Gibbs energy ; liquid crystalline polyethers
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A series of polyethers have been synthesized from 1-(4-hydroxy-4′-biphenyl)-2-(4-hydroxyphenyl)propane and α, Ω-dibromoalkanes having different numbers of methylene units [TPPs]. Both odd- and even-numbered TPPs [TPP(n=odd)s and TPP(n=even)s) exhibit multiple transitions during cooling and heating and they show little supercooling dependence, indicating close-to-equilibrium nature of these transitions. Combining the structural characterization obtainedvia wide angle X-ray diffraction powder and fiber patterns at different temperatures and the morphological observations from microscopy techniques, not only the nematic liquid crystalline phase but also highly ordered smecticF, smectic crystalG andH phases have been identified. The phase diagrams for both TPP(n=odd)s and TPP(n=even)s have been constructed [1–3]. Thermodynamic properties (enthalpy and entropy changes) during these transitions are studied based on differential scanning calorimetry experiments. The contributions of the mesogenic groups and methylene units to each ordering process can be separated and they indicate the characteristics of these processes thereby providing estimations of the transition types.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Springer
    Journal of thermal analysis and calorimetry 46 (1996), S. 921-933 
    ISSN: 1572-8943
    Keywords: aromatic polyimide ; films ; in-plane orientation ; relaxation process ; thermal stability
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A new high molecular weight polyimide based on 4,4′-oxidiphthalic anhydride (ODPA) dianhydride and 2,2′-dimethyl-4,4′-diaminobiphenyl (DMB) diamine has been synthesizedvia a one-step polymerization method. This polyimide is soluble in phenolic solvents. Films from 7 to 30 μm thick were cast from the polymer solution and show in-plane orientation on a molecular scale detected by Fourier transform infrared spectroscopy experiments. This anisotropic structure leads to anisotropic optical properties arising from two different refractive indices along the inplane and out-of-plane directions. ODPA DMB possesses high thermal and thermo-oxidative stability. The glass transition temperature has been determined to be 298 °C. Dynamic mechanical analyses show two relaxation processes appearing above room temperature: the β- and the α-relaxation processes. The α-relaxation corresponds to the glass transition while the β-relaxation is a secondary relaxation process associated with the non-cooperative subsegmental motion.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    Springer
    Journal of materials science 31 (1996), S. 4423-4431 
    ISSN: 1573-4803
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract A new polyimide has been synthesized from 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA) and 2,2′-dimethyl-4,4′-diaminobiphenyl (DMB). A high-strength, high-modulus, high-temperature fibre has been developed from this polyimide via a dry-jet wet spinning method. The tensile strength of BPDA-DMB fibres is 3.3 GPa and the tensile modulus is around 130 GPa. The compressive strength of the fibres has been investigated through a tensile recoil test (TRT), while the fibre morphology after compression has been studied via polarized light microscopy (PLM) and scanning electron microscopy (SEM). From the TRT measurements, we have observed that the compressive strength of this fibre is 665 (±5) MPa, which is higher than those of other aromatic polymer fibres. The effect of fibre diameter on the compressive strength of BPDA-DMB fibres is not substantial. The critical compressive strain for this fibre at which the kink bands start appearing under the observation of PLM is at 0.51–0.54%. Subglass relaxation processes have been observed and the measure of an apparent relaxation strength may serve as one of the factors which significantly affect the compressive strength of the fibres. Tensile tests of pre-compressed fibres reveal a continuous loss in tensile strength (up to 30%) with increasing the compressive strain (up to 2.6%). PLM and SEM observations show that during the compression BPDA-DMB fibres form regularly-spaced kink bands at ±60 ° (±2 °) with respect to the fibre axis. The kink band density initially increases with the compressive strain, and reaches a maximum at around 1.1%. Further increase of the compressive strain decreases this density due to the merge of the neighbouring bands. The size of kink bands also correspondingly increases within this compressive strain region. The morphological observation via SEM implies the existence of a skin-core structure and microfibrillar texture which are common features in polymer fibres.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 56 (1995), S. 837-851 
    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: In this article, we present detailed processing characteristics and structure development in a thermoplastic polyimide BTDA-DMDA in the solid-state extrusion process. This fully imidized polyimide polymer is known to crosslink at fast rates when it is brought to a molten phase even for short periods of time. This characteristic makes it difficult to process it in the molten phase and attempts at melt processing result in melt fracture and highly distorted extrudates. However, this polymer can be shaped into high-quality extrudates when it is processed below its melting temperature directly from its postpolymerization powdered state. The solid-state extrusion of precompacted BTDA-DMDA powder was studied in the temperature range from 250 to 320°C. At the temperatures from 290 to 320°C, high-quality extrudates were obtained. Below 290°C, solid-state extrusion was not possible due to the limitation of the load cell capacity of the capillary rheometer used in this research. Above 320°C, the extrudates were found to be of poor quality as a result of degradation and crosslinking in the molten phase. Structural characteristics of the samples produced by solid-state extrusion was investigated by the microbeam X-ray diffraction technique. The thermal behavior of the extrudates was also characterized by differential scanning calorimetry (DSC). The DSC results show that at low extrusion temperatures the samples exhibit dual endothermic peaks and are highly crystalline in an extruded state. The higher melting peak located at about 350°C is due to the melting of the new crystalline phase that has developed partially during the solid-state extrusion process and partially during the recrystallization process that takes place at temperatures at and slightly above the primary melting process during the DSC heating scan. This has been confirmed by DSC, depolarized light hot-stage video microscopy, and wide-angle X-ray diffraction studies. The long spacing of the higher melting crystals was found to be much larger than that of the lower melting crystals, as evidenced by the small angle X-ray scattering studies. © 1995 John Wiley & Sons, Inc.
    Additional Material: 21 Ill.
    Type of Medium: Electronic Resource
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  • 8
    ISSN: 1076-5174
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Double-charge-transfer spectroscopy was used to measure the double-ionization energies of chromium hexacarbonyl and molybdenum hexacarbonyl molecules to triplet electronic states of the corresponding dications. The spectra were interpreted using data calculated using a modified MSXα method. The measured double-ionization energy to the ground triplet state is 22.8 ± 0.5 eV for Cr(CO)6 and 22.4 ± 0.5 eV for Mo(CO)6; both values match, within experimental error, an earlier measurement of 22.8 ± 0.5 eV for W(CO)6. The spectra for the three hexacarbonyls are remarkably similar, probably reflecting that the electronic structures of the three molecules are almost identical in the valence region. The similarity is reflected in the calculated data; the Coulomb repulsions between the two positive holes which characterize the dictations' states are 4.54, 4.44 and 4.45 eV for Cr(CO)62+, Mo(CO)62+ and W(CO)62+, respectively. These values correspond to the repulsive energy for two single charges separated by just over 3 Å, this separation being consistent with the size of the molecules.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 9
    ISSN: 0323-7648
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: X-ray methods have been used to investigate the structure of fibers of aromatic copolyimides prepared from 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA), o-tolidine (OTOL) and p-phenylene diamine (PPD). We have shown previously that the non-periodic layer lines in the X-ray fiber diagrams of these copolymers are indicative of a random comonomer sequence. In the present paper, we analyze the shifts in the layer line positions that occur with increasing draw ratio. These changes are to be understood primarily in terms of increases in the correlation lengths for the stiff chain conformation. At high draw ratios there is also evidence for the development of a more extended chain conformation, probably due to torsional variation changes in the torsion angles. It is shown that the data are sufficiently sensitive to allow quantitative analysis of these separate effects, and their dependence on comonomer ratio.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
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