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261.
262.
E. Gantner U. Kuhnes H. J. Ache 《Journal of Radioanalytical and Nuclear Chemistry》1992,161(2):561-574
The application, the advantage and limits of neutron monitoring techniques, such as Hf-monitors, fissile material accumulation and concentration monitors are being discussed. The active neutron counting technique applied to emptied pulsed extraction columns containing Hf-sieve plates allows conclusive answers as to the position of the plates in the columns. Pu-accumulations on Hf-sieve plates in pulsed extraction columns can be estimated within a factor of two, whereby the detection limit is about equal to or less than 1 g Pu/plate. Fissile material concentration changes of 1.1 g/l can be detected in the case of235U in solution and of 0.4 Pu/l if a239Pu/240Pu ratio of 4 to 1 is assumed. 相似文献
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Utilizing forward recoil spectrometry (FRES), we have determined the segregation isotherm which describes the interfacial excess zi* of diblock copolymers of poly (d8-styrene-b-2-vinylpyridine) (dPS-PVP) at the interface between the homopolymers PS and PVP as a function of ?∞, the volume fraction of diblock copolymer remaining in the host homopolymer. All the samples were analyzed after annealing at temperatures and times sufficient to achieve equilibrium segregation. The effect of the degree of polymerization of both the diblock copolymers and the host homopolymers on the segregation isotherm is investigated. When the degree of polymerization of the homopolymer is much larger than that of the diblock copolymer, the normalized interfacial excess (zi*/Rg), where Rg is the radius of gyration of an isolated block copolymer chain, is a universal function of that portion of the block copolymer chemical potential due to chain stretching. The existence of such a universal function is predicted by theory and its form is in good agreement with self-consistent mean field calculations. Using these results, one can predict important aspects of the block copolymer segregation (e.g., the saturation interfacial excess) without recourse to the time-consuming numerical calculations. © 1994 John Wiley & Sons, Inc. 相似文献
266.
J. P. S. Farinha J. M. G. Martinho H. Xu M. A. Winnik R. P. Quirk 《Journal of Polymer Science.Polymer Physics》1994,32(9):1635-1642
Cyclization of a polystyrene chain (Mn = 10,600; Mw/Mn = 1.09) both ends labeled with 4-(1-pyrenyl)butanoamide groups was studied in cyclohexane between 25 and 95°C. The amide groups (peptide bonds) at both ends can form an intrachain hydrogen bond between the amide hydrogen at one chain end and the carbonyl oxygen at the other. The presence of two sets of conformers, random coils, and chains cyclized through hydrogen bonding, complicates the data analysis. The pyrene excimer kinetics of this polymer is well described by a model composed of two monomers (hydrogen bonded and nonbonded chains) and one excimer, in equilibrium. The cyclization rate constant for hydrogen-bonded chains is larger than the one for nonhydrogen-bonded chains. The pyrene excimer binding energy (ca. 1.6 kcal/mol) is lower than the published value for nonhydrogen-bonded chains (~ 9 kcal/mol), suggesting that intrachain hydrogen bonding hinders the stabilization of the excimer. © 1994 John Wiley & Sons, Inc. 相似文献
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K. J. Bayer 《Fresenius' Journal of Analytical Chemistry》1885,24(1):542-546
Ohne ZusammenfassungSt. Petersburg, den 20. April 1885. 相似文献
270.
The kinetics of C6H5 reactions with n‐CnH2n+2 (n = 3, 4, 6, 8) have been studied by the pulsed laser photolysis/mass spectrometric method using C6H5COCH3 as the phenyl precursor at temperatures between 494 and 1051 K. The rate constants were determined by kinetic modeling of the absolute yields of C6H6 at each temperature. Another major product C6H5CH3 formed by the recombination of C6H5 and CH3 could also be quantitatively modeled using the known rate constant for the reaction. A weighted least‐squares analysis of the four sets of data gave k (C3H8) = (1.96 ± 0.15) × 1011 exp[?(1938 ± 56)/T], and k (n‐C4H10) = (2.65 ± 0.23) × 1011 exp[?(1950 ± 55)/T] k (n‐C6H14) = (4.56 ± 0.21) × 1011 exp[?(1735 ± 55)/T], and k (n?C8H18) = (4.31 ± 0.39) × 1011 exp[?(1415 ± 65)T] cm3 mol?1 s?1 for the temperature range studied. For the butane and hexane reactions, we have also applied the CRDS technique to extend our temperature range down to 297 K; the results obtained by the decay of C6H5 with CRDS agree fully with those determined by absolute product yield measurements with PLP/MS. Weighted least‐squares analyses of these two sets of data gave rise to k (n?C4H10) = (2.70 ± 0.15) × 1011 exp[?(1880 ± 127)/T] and k (n?C6H14) = (4.81 ± 0.30) × 1011 exp[?(1780 ± 133)/T] cm3 mol?1 s?1 for the temperature range 297‐‐1046 K. From the absolute rate constants for the two larger molecular reactions (C6H5 + n‐C6H14 and n‐C8H18), we derived the rate constant for H‐abstraction from a secondary C? H bond, ks?CH = (4.19 ± 0.24) × 1010 exp[?(1770 ± 48)/T] cm3 mol?1 s?1. © 2003 Wiley Periodicals, Inc. Int J Chem Kinet 36: 49–56, 2004 相似文献