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81.
Below a critical thickness, of about 60 nm, the glass transition temperature of polystyrene (PS) films decreases with film thickness, as demonstrated using free‐standing films. A geometrical model is developed here describing this phenomenon in the case of ideal (Gaussian) chains. This model, which can be considered as an application of the free volume model, assumes that the decrease of the glass transition temperature from thick to ultrathin films is due to the modification of the interpenetration between neighboring chains. The theoretical curve deduced from the model is in excellent agreement with the PS experimental results, without using any adjustable parameters. From these results, it can be concluded that new chain motions, usually buried in bulk samples, are expressed by the presence of the surface. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 10–17, 2007 相似文献
82.
Gravimetric measurements of thermodesorption of n-hexane and n-heptane were performed under quasi-equilibrium conditions. Differential thermodesorption profiles for ZSM-5 and ZSM-11 showed two peaks, but for Y zeolites, only one thermodesorption peak was observed. A model function, derived from the Langmiur adsorption model, was fitted to the experimental data, and the model parameters (the adsorption entropy and enthalpy) were estimated. The two-step desorption profiles observed for ZSM-5 and ZSM-11 were attributed to the commensurate freezing effect, i.e. a transition in the adsorbed phase resulting in ordering of the adsorbed molecules in the zeolite channels. The results observed for ZSM-11 indicate that the zigzag channels typical for ZSM-5 micropore system are not necessary for this transition to occur. 相似文献
83.
R. Ochoa-Land?&#x;n M. Flores-Acosta R. Ram?&#x;rez-Bon H. Arizpe-Chávez F.F. Castillón-Barraza 《Journal of Physics and Chemistry of Solids》2003,64(11):2245-2251
CdS clusters were synthesized in A type zeolite by reaction in alkaline aqueous solution at temperatures from 30 to 70 °C. The optical properties of the samples were studied by diffuse reflectance and photoluminescence spectroscopy. Their crystalline structure and morphology were studied by X-ray diffraction and by transmission and scanning electron microscopy. We found that at lower temperatures the CdS clusters are encapsulated in the zeolite cages. We compared the properties of these clusters with those encapsulated in the cages of zeolites X and Y, prepared by similar methods. CdS clusters smaller than the CdS exciton diameter are also formed outside the cages in the zeolite matrix. The size of these clusters increases with temperature producing a red-shift of the absorption edge in the optical absorption spectra. 相似文献
84.
Mihai Tib?r 《Topology》2003,42(3):629-639
We show that the complex link of a large class of space germs (X,x0) is characterized by its “simplicity”, among the Milnor fibres of functions with isolated singularity on X. This amounts to the minimality of the Milnor number, whenever this number is defined. Such a phenomenon has been first pointed out in case (X,x0) is an isolated hypersurface singularity, by Teissier (Cycles évanescents, sections planes et conditions de Whitney, in: Singularités à Cargèse 1972, Asterisque, Nos. 7 et 8, Soc. Math. France, Paris, 1973, pp. 285-362). 相似文献
85.
Andrey Semichaevsky Markus E. Testorf Robert V. McGahan Michael A. Fiddy 《Waves in Random and Complex Media》2004,14(2):S415-S434
A linear spectral estimation technique, the PDFT algorithm, is used as part of a nonlinear iterative reconstruction scheme to obtain improved radar images. The iterative PDFT algorithm is used to address the limited resolution problem inherent to imaging objects buried in soil and hidden under foliage. This is achieved by subsequent application of two properties of the PDFT algorithm: the energy parameter of the PDFT algorithm is used to determine the target shape, while the shape information in turn is used to obtain super-resolved images. We describe algorithms able to exploit both properties automatically and without manual intervention. Two methods are investigated in particular, one iteratively optimizing the constraints by monitoring the energy parameter, the other method computing energy values for all points, from which a weighted prior function is determined. In addition, we discuss variants of both algorithm which provide an optimized trade-off between computation time and performance. Additional attention is given to situations, where a known target is embedded in an unknown background. Imaging results are presented for both synthetic and measured data. 相似文献
86.
Arthur Maki Robert L. Sams Jeffrey Barber Engelene t.H. Chrysostom Alfons Weber 《Journal of Molecular Spectroscopy》2004,225(2):109-122
Several new infrared absorption bands for 32S16O3 have been measured and analyzed. The principal bands observed were ν1+ν2 (at 1561 cm−1), ν1+ν4 (at 1594 cm−1), ν3+ν4 (at 1918 cm−1), and 3ν3 (at 4136 cm−1). Except for 3ν3, these bands are very complicated because of (a) the Coriolis coupling between ν2 and ν4, (b) the Fermi resonance between ν1 and 2ν4, (c) the Fermi resonance between ν1 and 2ν2, (d) ordinary l-type resonance that couples levels that differ by 2 in both the k and l quantum numbers, and (e) the vibrational l-type resonance between the A1′ and A2′ levels of ν3+ν4. The unraveling of the complex pattern of these bands was facilitated by a systematic approach to the understanding of the various interactions. Fortunately, previous work on the fundamentals permitted good estimates of many constants necessary to begin the assignments and the fit of the measurements. In addition, the use of hot band transitions accompanying the ν3 band was an essential aid in fitting the ν3+ν4 transitions since these could be directly observed for only one of four interacting states. From the hot band analysis we find that the A1′ vibrational level is 3.50 cm−1 above the A2′ level, i.e., r34=1.75236(7) cm−1. In the case of the 3ν3 band, the spectral analysis is straightforward and a weak Δk=±2, Δl3=±2 interaction between the l3=1 and l3=3 substates locates the latter A1′ and A2′ “ghost” states 22.55(4) cm−1 higher than the infrared accessible l3=1 E′ state. 相似文献
87.
The determination of the sensitivity of the acoustical characteristics of vibrating systems with respect to the variation of the design parameters predicting these characteristics is a necessary and important step of the acoustic design and optimization process. Acoustic design sensitivity analysis includes the computation and evaluation of the sensitivity information required for this procedure. In this study, a boundary element code performing the sensitivity analysis of the acoustic pressure by using the matrix sensitivities with respect to different design variables has been developed. The effect of the precision of boundary element discretization on the acoustic pressure sensitivity is examined via this code. The formulation is applied to a multi-source system and the dimension sensitivity analysis of near field pressures of two-dilating-spherical source is performed. The last application is devoted to a real sound source: a washing machine sitting on the floor. Sensitivity of the field pressures to the machine’s dimensions (size), surface velocity and frequency is examined on the bases of the boundary element model of the machine and half-space condition. The impacts of these variables are compared; and a limiting speed for the machine responding both the acoustical and operational requirements is determined. 相似文献
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