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  • 1
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 108 (1998), S. 6492-6497 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: We report quasielastic neutron scattering results on an amorphous polyimide (AURUM) in a temperature range from 10 to 300 K below the glass transition temperature Tg(=250 °C). As temperature increases from 10 K, anharmonic excess scattering intensity appears at around 200 K or about 300 K below Tg. This excess scattering is very similar to the so-called fast process in picosecond order observed for glass-forming polymers as well as organic and inorganic low molecular weight glass-forming materials. We first analyzed the spectra in a simple way assuming validity of the Bose scaling for the vibrational density of states and a Lorentzian for the additional relaxational process, and found that the excess scattering intensity appears in the frequency range below the Boson peak and the characteristic time is independent of temperature which are common features for the fast processes reported previously. The second analysis using the recent vibration-relaxation (VR) model, which is more realistic, indicated that softening of the vibrational modes may play an important role for the change of spectra from inelastic-like to quasielastic-like. Nevertheless, relaxational process is still necessary to describe the excess scattering although the temperature range examined is very far below Tg. © 1998 American Institute of Physics.
    Materialart: Digitale Medien
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  • 2
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 109 (1998), S. 10456-10463 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: Inelastic and quasielastic neutron-scattering measurements have been performed on an amorphous poly(ethylene terephthalate) (PET) fiber in parallel and perpendicular scattering geometries, i.e., when the fiber axis f is parallel and perpendicular to the scattering vector Q, respectively. The so-called boson peak is observed at around −1.4 meV in neutron energy transfer at low temperatures below about 150 K in both the geometries; as temperature increases, the fast process of picosecond order appears at a certain temperature below the glass-transition temperature Tg(=348 K). Although no drastic differences in the dynamics can be observed, a closer look at the spectra revealed some interesting features of the low-energy modes. From the mean-square displacements evaluated with two different energy resolutions, it was found that the fast process appears only in the direction perpendicular to the polymer chain (not the fiber axis f) in the energy region between −1 and −0.2 meV. In the inelastic scattering spectra, we found that the boson peak is stronger in intensity for the parallel direction while the intensity of the fast process is larger for the perpendicular one. The quantitative analysis based on the recent vibration–relaxation model revealed that the fast process can mainly be explained by the softening of the vibrational modes; the softening occurs at lower temperatures in the perpendicular geometry than in the parallel one. On the other hand, the conventional single-Lorentzian fit to the fast process, in which the fast process is assumed to be a relaxational process and described by a Lorentzian, showed that the onset temperature of the fast process is lower in the perpendicular geometry than in the parallel one. These have been tentatively attributed to weaker force constants, for motions perpendicular to a polymer chain, such as torsional and librational motions, than those along the chain. © 1998 American Institute of Physics.
    Materialart: Digitale Medien
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  • 3
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 105 (1996), S. 4342-4349 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: We have studied the glass transition dynamics of trans-1,4-chloroprene from microscopic view points using a quasielastic neutron scattering technique in a time range of ∼4×10−13 to ∼4×10−10 s. It was found that the so-called fast process of picosecond order appears at around the Vogel–Fulcher temperature T0, similarly to cis-1,4-polybutadiene having no large side groups [J. Chem. Phys. 98, 8262 (1993)]. It is considered that the onset temperature at around T0 must be characteristic to polymers having no large side groups or no large internal degrees of freedom. In addition to the fast process, the slow process of subnanosecond order sets in at around the glass transition temperature Tg and the activation energy of the relaxation time was found to be ∼2.5 kcal/mol. The nature of the slow process is discussed in terms of conformational transition near Tg. © 1996 American Institute of Physics.
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  • 4
    Digitale Medien
    Digitale Medien
    s.l. : American Chemical Society
    Macromolecules 27 (1994), S. 5609-5615 
    ISSN: 1520-5835
    Quelle: ACS Legacy Archives
    Thema: Chemie und Pharmazie , Physik
    Materialart: Digitale Medien
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  • 5
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 114 (2001), S. 8671-8677 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: In a few decades, several characteristic regimes and subregimes have been theoretically presented as functions of concentration C and contour length for flexible polyelectrolyte solutions. However, experimentally only the dilute and semidilute regimes have been well acknowledged. In this study, solutions of sodium poly(styrene sulfonate) are studied at various concentrations ranging from the semidilute regime to the bulk through the concentrated regime using small-angle and intermediate-angle x-ray scattering techniques. We have observed a single scattering peak being characteristic of polyelectrolyte solutions until C=4.1 mol/l. Above C=4.9 mol/l, such a characteristic peak disappears and instead, another new peak appears at higher q's. In the plot of the maximum position qmax vs C, two crossover concentrations are found at C**=1.2 mol/l and C***=4.5 mol/l. The former is a continuous crossover from qmax∼C1/2 to qmax∼C1/4 which can be assigned to the crossover of the semidilute-to-concentrated regime, while the latter is a discontinuous crossover which may be assigned to that of the concentrated-to-swollen regime. In the swollen regime the characteristics of polyelectrolyte solutions are lost. The discontinuous crossover concentration C*** is about half the bulk concentration Cbulk=8.4 mol/l. © 2001 American Institute of Physics.
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  • 6
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 115 (2001), S. 8217-8220 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: A previously reported phase diagram of polyelectrolyte solutions as functions of degree of polymerization and the concentration is improved. The new phase diagram is also intended for salt-free solutions of polyelectrolytes with the constitutional repeating unit -C-CX-, X being a charged group. The main improved point is the crossover concentrations between the dilute and semidilute regimes in the low concentration range of less than 10−2 mol/l, which is based on the recent most reliable experimental data on the persistence length of flexible polyion chains. This phase diagram as well introduces both the concentrated regime, which has been not only theoretically predicted but also experimentally confirmed, and the experimentally newly found swollen regime. Furthermore, it is proposed that the dilute regime is separated into four regions, gaslike, poor order, liquidlike order and crystal. The degrees of orderliness in these regions have been assumed to depend on the ratio δ/ξcent of the amplitude of thermal fluctuations to the mean intermolecular distance. Typically, δ/ξcent=1/5 as the critical Lindemann ratio of melting is assigned for the crossover between the liquidlike order and crystal regions. Interestingly, the most probable region for the formation of a 3-D lattice is located within the experimental approach. © 2001 American Institute of Physics.
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  • 7
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 95 (1991), S. 5332-5340 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: In order to investigate low-energy excitations below 10 meV, inelastic neutron-scattering measurements have been carried out on various organic amorphous polymers at 10 and 50 K and three inorganic glasses at 150 and 295 K. It was found that a broad excitation peak is observed for all amorphous materials in the ω range of 1.5–4.0 meV irrespective of different chemical structures. On the other hand, highly crystalline polyethylene with a degree of crystallinity 0.96 shows no such broad peak, indicating that the low-energy excitation is characteristic of amorphous materials. We have employed an asymmetric double-well potential as a common origin for the low-energy excitation in amorphous materials and analyzed the results of amorphous polyisobutylene to confirm validity of this model and alternatively to determine parameters of the potential. Analysis of the temperature dependence of the inelastic-scattering intensity of the low-energy excitation leads to a concept of phonon-assisted tunneling in the asymmetric double-well potential.
    Materialart: Digitale Medien
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  • 8
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 94 (1991), S. 8413-8419 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: Structure factors S(Q) of deuterated polyethylene (PE) in the solid and liquid states have been measured at 20, 130, and 170 °C in a wide range of Q from 0.55 to 25 A−1 by means of pulsed neutron total scattering technique. Very local intrachain structure of the PE melt, such as C–D and C–C bond lengths and (angle)CCC, (angle)DCD, and (angle)CCD bond angles, is determined from a high Q part of S(Q), and is compared with that of solid PE. Interchain structure of the melt is also discussed, assuming that the PE chains are built of small segments of five –CD2 – units like pearl necklaces and furthermore, that orientations between the segments are completely uncorrelated and chain connectivity is entirely ignored. The experimental S(Q) is reproduced reasonably well by this simple model with an effective diameter σ of the segments of 4.34 A and a packing fraction η of the segments of 0.28, which are consistent with the experimental number density of the PE melt. The different size of the segments like four or six –CD2 – units, however, gives poor results with the values of σ and η being inconsistent with the experimental number density.
    Materialart: Digitale Medien
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  • 9
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 104 (1996), S. 3841-3850 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: The dynamics of atactic polystyrene (PS) has been studied by a quasielastic neutron scattering technique in a temperature range of 21–475 K covering the glass transition temperature Tg (=373 K). The so-called fast process in picosecond order is observed similarly to other glass-forming materials in supercooled states so far reported. However, the onset temperature of the fast process is ∼170 K below Tg in PS, which is far below Tg in contrast to the previous observations. This result implies that the fast process is not necessarily the β process predicted by the recently noted mode coupling theory. By comparing the result of hydrogenated PS with that of partially deuterated polystyrene (PS-d5) where only phenyl rings were preferentially deuterated, the origin of the fast process occurring far below Tg has been assigned to librational motion of phenyl rings, which is coupled with main chain motion near Tg. Analysis of the spectra by curve fit has suggested that the nature of the fast process changes at a temperature ∼30 K above Tg. This change also involves the appearance of a slow relaxation process in the energy range of several tens μeV. The origin of the slow process is discussed in terms of conformational transitions of the main chain. © 1996 American Institute of Physics.
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  • 10
    Digitale Medien
    Digitale Medien
    s.l. : American Chemical Society
    Macromolecules 27 (1994), S. 7103-7108 
    ISSN: 1520-5835
    Quelle: ACS Legacy Archives
    Thema: Chemie und Pharmazie , Physik
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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