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61.
In this work, the melting-point depression and molecular dynamics of hexamethyldisilane confined within five controlled pore
glasses, with mean diameters ranging from 7.9 to 23.9 nm, are studied by high-field (9.4 T) nuclear magnetic resonance (NMR),
and the results are discussed with reference to the bulk substance. The melting-point depression in pores with radiusR follows the simplified Gibbs-Thompson equation ΔT=k
p/(R−s) with ak
p value of 74 K · nm and ans value of 1 nm. To our knowledge, this is the first time thek
p value of hexamethyldisilane is reported. Proton spin-lattice relaxation times (T
1), spin-spin relaxation times (T
2), and diffusivities (D) are reported as a function of temperature. The confinement in the pores gives rise to substantial changes in the molecular
dynamics and the phase behavior. The line-shape measurements reveal a two-phase system assigned to a relatively mobile component
at the pore walls and a crystalline solid at the center of the pores. However, theT
2 measurements show that the mobile phase also embraces a minor component attributed to nonfrozen liquid in pockets or micropores.
The diffusivity of the major narrow-line component is approximately three orders of magnitude larger than that in the plastic
bulk phase, reflecting fast diffusion of mobile molecules. Below the melting region,T
1 of the narrow line is significantly shorter thanT
1 of the broad line, suggesting that the molecular reorientation is more hindered close to the surface than at the center of
the pore. 相似文献
62.
W M Niessen M A de Kraa E R Verheij P J Bergers G F La Vos U R Tjaden J van der Greef 《Rapid communications in mass spectrometry : RCM》1989,3(1):1-4
On-line sample pretreatment by means of the phase-system switching approach is an interesting technique for the analysis of aqueous samples, e.g., plasma, by means of supercritical-fluid chromatography. In order to analyse plasma samples the following analytical procedure is used. The plasma sample is injected on to a short precolumn, which is washed with water and subsequently dried with nitrogen. Next, the solutes are desorbed with the supercritical mobile phase, analysed with packed-column supercritical-fluid chromatography and detected with either a UV detector or a mass spectrometer, equipped with a moving-belt interface. The herbicide diuron is selected as a test compound to study the feasibility of this approach. Using a selective detector the procedure is sufficiently sensitive to detect diuron in plasma, but not appropriate to detect the diuron metabolites in a post-mortem plasma sample. These have been identified with liquid chromatography/mass spectrometry. The detection limit of diuron in plasma using the procedure described is about 30 ng/mL. 相似文献
63.
Erich Miersemann Hans D. Mittelmann W. Trnig 《Mathematical Methods in the Applied Sciences》1989,11(1):95-104
In this paper we generalize recent theoretical results on the local continuation of parameter-dependent non-linear variational inequalities. The variational inequalities are rather general and describe, for example, the buckling of beams, plates or shells subject to obstacles. Under a technical hypothesis that is satisfied by the simply supported beam, we obtain the existence of a continuation of both the solution and the eigenvalue with respect to a local parameter. A numerical continuation method is presented that easily overcomes turning points. Numerical results are presented for the non-linear beam. 相似文献
64.
65.
The room temperature structure of perovskite CeAlO3 has been reinvestigated by X-ray powder diffraction. The Rietveld refinement has confirmed the tetragonal symmetry; but revealed a super cell, a=5.32489(6) Å and c=7.58976(10) Å, with the space group I4/mcm. In CeAlO3, the distortion from the ideal cubic perovskite is caused by the cooperative tilting of the AlO6 octahedra around the primitive cubic [001]p-axis. 相似文献
66.
67.
68.
69.
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
70.