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71.
NH chemical shift temperature coefficients have been measured in a large series of N-substituted-3-piperidinethiopropionamides in which the NN distances are short but of varied length, as well as in a couple of the corresponding amides and in some simpler amides and thioamides. Geometries are calculated by means of ab initio DFT methods. The N-substituted-3-piperidinethiopropionamides show in most cases strong intramolecular N–HN hydrogen bonds according to IR spectra and ab initio calculations. For compounds with rather short NN distances the S=C–N–H moiety is non-planar. Dihedral angles as small as 160° are found. The NH chemical shift coefficients measured in non-polar solvents in all the N-substituted-3-piperidinethiopropionamides are more negative (−8 to −17 ppb/K) than in non-hydrogen bonded thioamides. For the latter in non-polar solvents like CDCl3 and toluene the temperature coefficients are as small as −1 to −4 ppb/K. The large negative effects can be related not only to the non-planarity of the thioamide group in a way that the more pronounced the non-planarity the more negative the temperature coefficients, but also to strong hydrogen bonding and the fact that the acceptor is a nitrogen. For similar amides with non-planar amide groups and nitrogen acceptor large negative temperature coefficients are likewise seen. In polar solvents like DMF the effects in simple thioamides are uniform and close to −6 ppb/K, whereas in the more complex compound like 4p(t) the temperature coefficient is close to 0. An essential feature of measuring temperature coefficients of compounds without strong intramolecular hydrogen bonds in non-polar solvents and at low temperatures is to keep the concentration low enough to avoid dimerisation. 相似文献
72.
Jocelyn Sabatier Serge Poullain Patrick Latteux Jean Luc Thomas Alain Oustaloup 《Nonlinear dynamics》2004,38(1-2):383-400
Robust speed control of a low damped electromechanical system with backlash is studied, controlled load angular speed being not measured. The proposed control strategy combines a Luenberger observer (load angular speed and load torque disturbance estimations) and a robust CRONE controller. The observer provides estimation of the load angular speed and of the disturbance torque applied on the load. Through the computation of only three independent parameters (as many as a PID controller), the CRONE controller permits to ensure the robust speed control of the load in spite of plant parametric variations and speed observation errors. The proposed control strategy is applied to a four mass experimental test bench. 相似文献
73.
Large eddy simulations of two basic configurations (decay of isotropic turbulence, and the academic plane channel flow) with heat transfer have been performed comparing several convection numerical schemes, in order to discuss their ability to evaluate temperature fluctuations properly. Results are compared with the available incompressible heat transfer direct numerical simulation data. It is shown that the use of regularizing schemes (such as high order upwind type schemes) for the temperature transport equation in combination with centered schemes for momentum transport equation gives better results than the use of centred schemes for both equations. Copyright © 2004 John Wiley & Sons, Ltd. 相似文献
74.
A method for computing low Mach number flows using high‐resolution interpolation and difference formulas, within the framework of the Marker and Cell (MAC) scheme, is presented. This increases the range of wavenumbers that are properly resolved on a given grid so that a sufficiently accurate solution can be obtained without extensive grid refinement. Results using this scheme are presented for three problems. The first is the two‐dimensional Taylor–Green flow which has a closed form solution. The second is the evolution of perturbations to constant‐density, plane channel flow for which linear stability solutions are known. The third is the oscillatory instability of a variable density plane jet. In this case, unless the sharp density gradients are resolved, the calculations would breakdown. Under‐resolved calculations gave solutions containing vortices which grew in place rather than being convected out. With the present scheme, regular oscillations of this instability were obtained and vortices were convected out regularly. Stable computations were possible over a wider range of sensitive parameters such as density ratio and co‐flow velocity ratio. Copyright © 2004 John Wiley Sons, Ltd. 相似文献
75.
Yu. Satov B. Sharkov H. Haseroth Yu. Smakovski K. Makarov S. Kondrashev V. Roerich A. Stepanov H. Kugler R. Scrivens O. Camut A. Shumshurov A. Balabaev A. Charushin 《Journal of Russian Laser Research》2004,25(3):205-216
Experimental and numerical calculation results devoted to development of an optical system for an ion source based on a repetition rate CO2 laser are described. The laser chain consists of a master oscillator, gas absorber cells, and a four-pass amplifier. The optical system provides smooth laser pulses with variable duration and high spatial quality that ensures efficiency for plasma heating and ion generation. The parameters of the plasma ion component measured in the CERN laboratory are applied for a lead target illumination. 相似文献
76.
A. N. Logunov 《Journal of Russian Laser Research》2004,25(4):331-348
A physical multidimensional local model of the propagation process of a laser pulse in air having no analogy to famous models in laser physics is constructed. It is based on the representations of classical wave mechanics characteristic of the theory of scalar wave fields. 相似文献
77.
Yuri M. Boiko Anders Bach Jørgen Lyngaae-Jørgensen 《Journal of Polymer Science.Polymer Physics》2004,42(10):1861-1867
Films of amorphous polystyrene (PS) with a weight-average molecular weight (Mw) of 225 × 103 g/mol were bonded in a T-peel test geometry, and the fracture energy (G) of a PS/PS interface was measured at the ambient temperature as a function of the healing time (th) and healing temperature (Th). G was found to develop with (th)1/2 at Th = Tg-bulk − 33 °C (where Tg-bulk is the glass-transition temperature of the bulk sample), and log G was found to develop with 1/Th at Tg-bulk − 43 °C ≤ Th ≤ Tg-bulk − 23 °C. The smallest measured value of G = 1.4 J/m2 was at least one order of magnitude larger than the work of adhesion required to reversibly separate the PS surfaces. These three observations indicated that the development of G at the PS/PS interface in the temperature range investigated (<Tg-bulk) was controlled by the diffusion of chain segments feasible above the glass-transition temperature of the interfacial layer, in agreement with our previous findings for fracture stress development at several polymer/polymer interfaces well below Tg-bulk. Close values of G = 8–9 J/m2 were measured for the symmetric interfaces of polydisperse PS [Mw = 225 × 103, weight-average molecular weight/number-average molecular weight (Mw/Mn) = 3] and monodisperse PS (Mw = 200 × 103, Mw/Mn = 1.04) after healing at Th = Tg-bulk − 33 °C for 24 h. This implies that the self-bonding of high-molecular-weight PS at such relatively low temperatures is not governed by polydispersity. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1861–1867, 2004 相似文献
78.
Study on the Superhydrophilicity of the SiO2-TiO2 Thin Films Prepared by Sol-Gel Method at Room Temperature 总被引:2,自引:0,他引:2
Dasen Ren Xiaoli Cui Jie Shen Qun Zhang Xiliang Yang Zhuangjian Zhang Lu Ming 《Journal of Sol-Gel Science and Technology》2004,29(3):131-136
Nanoscale SiO2-TiO2 composite thin films with the thickness of about 100 nm were prepared by sol-gel method at room temperature in air. The chemical states of the elements on the surface and near the surface were measured by XPS. The results showed that the Ti on/near the surface of the thin films existed not only as TiO2 but also as Ti2O3. Part of the TiO2 was changed to Ti2O3 after UV irradiation. The crystalline structure of the TiO2 in the SiO2-TiO2 thin films was anatase with the crystallite size of 14–20 nm. It was found that the thin film prepared at room temperature in air has good superhydrophilic property and has strong adherence to the substrate. 相似文献
79.
Kangseok Lee Sang Eun Shim Byung H. Lee Seong Uk Hong Soonja Choe 《Journal of Polymer Science.Polymer Physics》2004,42(6):1114-1126
The desorption behavior of a surfactant in a linear low‐density polyethylene (LLDPE) blend at elevated temperatures of 50, 70, and 80 °C was studied with Fourier transform infrared spectroscopy. The composition of the LLDPE blend was 70:30 LLDPE/low‐density polyethylene. Three different specimens (II, III, and IV) were prepared with various compositions of a small molecular penetrant, sorbitan palmitate (SPAN‐40), and a migration controller, poly(ethylene acrylic acid) (EAA), in the LLDPE blend. The calculated diffusion coefficient (D) of SPAN‐40 in specimens II, III, and IV, between 50 and 80 °C, varied from 1.74 × 10?11 to 6.79 × 10?11 cm2/s, from 1.10 × 10?11 to 5.75 × 10?11 cm2/s, and from 0.58 × 10?11 to 4.75 × 10?11 cm2/s, respectively. In addition, the calculated activation energies (ED) of specimens II, III, and IV, from the plotting of ln D versus 1/T between 50 and 80 °C, were 42.9, 52.7, and 65.6 kJ/mol, respectively. These values were different from those obtained between 25 and 50 °C and were believed to have been influenced by the interference of Tinuvin (a UV stabilizer) at elevated temperatures higher than 50 °C. Although the desorption rate of SPAN‐40 increased with the temperature and decreased with the EAA content, the observed spectral behavior did not depend on the temperature and time. For all specimens stored over 50 °C, the peak at 1739 cm?1 decreased in a few days and subsequently increased with a peak shift toward 1730 cm?1. This arose from the carbonyl stretching vibration of Tinuvin, possibly because of oxidation or degradation at elevated temperatures. In addition, the incorporation of EAA into the LLDPE blend suppressed the desorption rate of SPAN‐40 and retarded the appearance of the 1730 cm?1 peak. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1114–1126, 2004 相似文献
80.
Xiao‐Dong Pan 《Journal of Polymer Science.Polymer Physics》2004,42(13):2467-2478
For properly chosen elastomer compounds, thermorheological characterization is combined with an examination of the variation of the wet sliding friction with temperature. A conceptual argument leads to the assumption that the wet sliding friction should maximize at the energy dissipation peak associated with the dynamic softening transition at a characteristic frequency determined by the sliding speed and the effective smallest surface asperity scale. The dynamic softening transition is characterized with the peak in tan δ/G′n, where tan δ is the loss tangent, G′ is the elastic modulus, and n is a constant between 0 and 1. The William–Landel–Ferry transform is uncritically applied for extrapolating the position of the peak in tan δ/G′n at high frequencies. Even based on the criterion of tan δ, the results obtained on a concrete surface indicate that the effective smallest asperity scale is of order of 100 μm. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2467–2478, 2004 相似文献