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Thermo-oxidative and thermo-mechanical stabilities of radiation-cured acrylates and epoxides were examined by TG, DMA and DSC.The polymeric trifunctional acrylates PETIA, TMPTA and THEIC displayed the highest temperatures of onset of degradation. The high crosslinking density of the films resulted in an almost temperature-independent complex E-modulus, as measured by DMA. With increasing degree of ethoxylation or propoxylation of the monomers, decreases in thermal stability and strength were found. For difunctional polymeric acrylates and epoxides, the glass transition temperature was measured.The average degree of curing of UV-cured epoxy films can be determined from the temperature of the maximum in the loss modulus (Emax.This revised version was published online in November 2005 with corrections to the Cover Date. 相似文献
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Y. X. Xia J. I. Friese D. A. Moore P. P. Bachelor L. Rao 《Journal of Radioanalytical and Nuclear Chemistry》2007,274(1):79-86
The complexation of plutonium(IV) with sulfate at variable temperatures has been investigated by solvent extraction method.
A NaBrO3 solution was used as holding oxidant to maintain the plutonium(IV) oxidation state throughout the experiments. The distribution
ratio of Pu(IV) between the organic and aqueous phases was found to decrease as the concentrations of sulfate were increased.
Stability constants of the 1:1 and 1:2 Pu(IV)-HSO4
− complexes, dominant in the aqueous phase, were calculated from the effect of [HSO4
−] on the distribution ratio. The enthalpy and entropy of complexation were calculated from the stability constants at different
temperatures using the Van’t Hoff equation. 相似文献
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Exploring Regioselective Bond Cleavage and Cross‐Coupling Reactions using a Low‐Valent Nickel Complex 下载免费PDF全文
Addison N. Desnoyer Florian W. Friese Weiling Chiu Marcus W. Drover Dr. Brian O. Patrick Prof. Dr. Jennifer A. Love 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(12):4070-4077
Recently, esters have received much attention as transmetalation partners for cross‐coupling reactions. Herein, we report a systematic study of the reactivity of a series of esters and thioesters with [{(dtbpe)Ni}2(μ‐η2:η2‐C6H6)] (dtbpe=1,2‐bis(di‐tert‐butyl)phosphinoethane), which is a source of (dtbpe)nickel(0). Trifluoromethylthioesters were found to form η2‐carbonyl complexes. In contrast, acetylthioesters underwent rapid Cacyl?S bond cleavage followed by decarbonylation to generate methylnickel complexes. This decarbonylation could be pushed backwards by the addition of CO, allowing for regeneration of the thioester. Most of the thioester complexes were found to undergo stoichiometric cross‐coupling with phenylboronic acid to yield sulfides. While ethyl trifluoroacetate was also found to form an η2‐carbonyl complex, phenyl esters were found to predominantly undergo Caryl?O bond cleavage to yield arylnickel complexes. These could also undergo transmetalation to yield biaryls. Attempts to render the reactions catalytic were hindered by ligand scrambling to yield nickel bis(acetate) complexes, the formation of which was supported by independent syntheses. Finally, 2‐naphthyl acetate was also found to undergo clean Caryl?O bond cleavage, and although stoichiometric cross‐coupling with phenylboronic acid proceeded with good yield, catalytic turnover has so far proven elusive. 相似文献
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Weihua Zhang Judah Friese Kurt Ungar 《Journal of Radioanalytical and Nuclear Chemistry》2013,296(1):69-73
In this study, soil samples were collected at Canadian embassy in Tokyo (about 300 km from Fukushima) on 23 March and 23 May of 2011 for purposes of estimating concentrations of radionuclides in fallout, the total fallout inventory, the depth distribution of radionuclide of interest and the elevated ambient gamma dose-rate at this limited location. Some fission products and actinides were analyzed using gamma-ray spectrometry, alpha spectrometry and liquid scintillation counting. The elevated activity concentration levels of 131I, 132I, 134Cs, 137Cs, 136Cs, 132Te, 129mTe, 129Te, 140Ba and 140La were measured by the gamma-ray spectrometer in the first sample collected on 23 March. Two months after the accident, the 134Cs and 137Cs became only detectable nuclides. A mass relaxation depth of 3.0 g/cm2 was determined by the activities on the depth distribution of 137Cs in a soil core. The total fallout inventory was thus calculated as 225 kBq/m2 on March sampling date and 25 kBq/m2 on May sampling date. The ambient gamma dose-rates in the sampling area estimated by the fallout fission products inventory and 137Cs depth distribution ranged from 184 to 38 nGy/h. There was no detectable americium or plutonium in the soil samples by alpha spectrometry. Although 90Sr or 89Sr were detected supposedly as a result of this accident, it was less than the detection limit, which was about 0.4 Bq/kg in the soil samples. 相似文献
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In DMF-d7 tetrabenzimidazole cavitands 2 exist as monomeric species and vase-like conformers. Several possible arrangements of the four benzimidazole NHs are indicated by 1H NMR spectroscopy. The cavitands form 1:1 inclusion complexes with tetraethyl ammonium and phosphonium cations only when strong hydrogen bonding anions like chloride or acetate are present. These complexes are stable on the NMR time scale at 295 K feature a C2V-symmetrical arrangement of benzimidazole functions. The stability of the C2V-symmetrical tetramethylammonium acetate complex is independent of the temperature. In contrast, tetramethylammonium and phosphonium chloride complexes exist at 233 K as several isomers. This complicated behavior is, in part, attributed to the hydrogen bonding interactions between the anions and the NH groups of benzimidazole functions. 相似文献