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31.
Simultaneous DSC-TG and DTA-TG were used to investigate the calatytic effect of the metal on the thermal decomposition of
a cellulose matrix containing small copper particles. The techniques were also used to demonstrate the effect of the metal
particles on the subsequent activation of the carbon matrix, a process which develops the pore structure necessary to expose
the metal particles to the gas phase. Temperature programmed desorption was used to study the initial mass loss found on activation.
To quantify the catalytic effect of the copper particles on the activation process an estimate was made of the activation
energy of the catalysed and uncatalysed reactions. The work gives valuable information on the processes involved in the preparation
of a new range of metal-carbon catalysts.
In celebration of the 60th birthday of Dr. Andrew K. Galwey 相似文献
32.
Piotr Dobrzynski 《Journal of polymer science. Part A, Polymer chemistry》2004,42(8):1886-1900
Lactide polymerization using zirconium(IV) acetylacetonate [Zr(acac)4] as an initiator was investigated. In the reaction between Zr(acac)4 and the monomer molecule, lactide deprotonation and the release of acetylacetone occurred. The structures of the obtained complexes were analyzed with high‐resolution NMR spectroscopy. A computational method was used to calculate the hypothetical structures. The role of the obtained complexes in the initiation of polymerization and the reaction of chain growth was proposed. The influence of the reaction temperature on the structures of the complexes was investigated. Polylactide chain growth proceeded by an insertion‐coordination mechanism. The polymer chain grew on one ligand, which was formed in advance from a deprotonated lactide. The molecular masses of the obtained polymers were the same as the theoretical masses and were directly proportional to the reaction conversion. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1886–1900, 2004 相似文献
33.
Reduction of tetranuclear heterometallic complex Mo2Mg2 was simulated using the B3LYP and PBE density functional methods. The results of geometry calculations of the initial complex
[MoVIO2Mg(MeOH)2(OMe)4]2 and a partially reduced MoV complex are in good agreement with experimental data. The reduced MoIII complex is characterized by a decrease in the binding energy of aqua ligands. Structural rearrangement of the complex with
release of a coordination position at the Mo atoms requires small energy expenditure. One can assume that the reduction of
the polynuclear complex causes overcrowding of its coordination sphere, which favors formation of dinitrogen complexes.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 441–457, March, 2008. 相似文献
34.
The interfacial dynamics‐based cavitation model, developed in Part‐1, is further employed for unsteady flow computations. The pressure‐based operator‐splitting algorithm (PISO) is extended to handle the time‐dependent cavitating flows with particular focus on the coupling of the cavitation and turbulence models, and the large density ratio associated with cavitation. Furthermore, the compressibility effect is important for unsteady cavitating flows because in a water–vapour mixture, depending on the composition, the speed of sound inside the cavity can vary by an order of magnitude. The implications of the issue of the speed of the sound are assessed with alternative modelling approaches. Depending on the geometric confinement of the nozzle, compressibility model and cavitation numbers, either auto‐oscillation or quasi‐steady behaviour is observed. The adverse pressure gradient in the closure region is stronger at the maximum cavity size. One can also observe that the mass transfer process contributes to the cavitation dynamics. Compared to the steady flow computations, the velocity and vapour volume fraction distributions within the cavity are noticeably improved with time‐dependent computations. Copyright © 2004 John Wiley & Sons, Ltd. 相似文献
35.
This paper presents the applications of digital image correlation technique to the mesoscopic damage and fracture study of
some granular based composite materials including steelfiber reinforced concrete, sandstone and crystal-polymer composite.
The deformation fields of the composite materials resulted from stress localization were obtained by the correlation computation
of the surface images with loading steps and thus the related damage prediction and fracture parameters were evaluated. The
correlation searching could be performed either directly based on the gray levels of the digital images or from the wavelet
transform (WT) coefficients of the transform spectrum. The latter was developed by the authors and showed higher resolution
and sensitivity to the singularity detection. Because the displacement components came from the rough surfaces of the composite
materials without any coats of gratings or fringes of optical interferometry, both surface profiles and the deformation fields
of the composites were visualized which was helpful to compare each other to analyze the damage of those heterogeneous materials.
The project supported by the National Natural Science Foundation of China (10125211 and 10072002), the Scientific Committee
of Yunnan Province for the Program of Steel Fiber Reinforced Concrete, and the Institute of Chemical Materials, CAEP at Mianyang 相似文献
36.
Perdigón-Melón J. A. Auroux A. Bonnetot B. 《Journal of Thermal Analysis and Calorimetry》2003,72(2):443-451
As supported palladium oxide catalysts present the best performances in methane combustion in lean conditions, microcalorimetric
studies of the interaction between methane and palladium oxide or metallic palladium supported on Al2O3, ZrO2 and BN have been performed at 673 K. At this temperature methane reduced the palladium oxide, and the heat of reduction of
palladium oxide was shown to depend on the dispersion and on the support. The lowest heats of reduction corresponded to the
highest rates of methane combustion. Moreover methane reforming occurred on metallic palladium, producing hydrogen, and again
methane decomposition was shown to depend on the support.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
37.
38.
In many Italian archaeological sites dated between the sixth and third centuries BC, unworked lumps of Cu-based materials are sometimes found, the so called Aes Rude, which according to archaeological considerations were appreciated as currency, as a medium of exchange and as a form of saving. The microchemical investigation of these ancient artefacts discloses their nature as apparently not usable for any functional applications or possible use. Indeed, Aes Rude resemble ordinary copper material, but microchemical results indicate that they are constituted by highly ferruginous leaded copper, making them useless for producing other metal objects by means of casting or hot and cold working. Notwithstanding this intrinsic negative feature, the production of these intractable Cu-based alloys was deliberately carried out to maximise the process yield in terms of produced metal from an impure and unselected metal ore by tailoring the smelting process parameters. With these considerations in mind, the microchemical investigation of these ancient iron–copper alloys gives evidence of the passage from the acceptance of an artefact value based on its true nature or potential use to the acceptance of the value based only on its appearance or form irrespective of its present or future use. This information could contribute to a better understanding of the evolution of human thought and economic and social interactions. 相似文献
39.
40.
Abhimanyu O. Patil Stephen Zushma Robert T. Stibrany Steven P. Rucker Louise M. Wheeler 《Journal of polymer science. Part A, Polymer chemistry》2003,41(13):2095-2106
Novel nickel(II) bisbenzimidazole complexes were prepared via a three‐step synthetic procedure consisting of aniline/diacid condensation, ligand N‐alkylation, and metal complexation. The complexes were characterized by X‐ray crystallography and found to possess a pseudotetrahedral geometry. Upon activation with methylaluminoxane, these nickel bisbenzimidazoles did not polymerize simple olefins (e.g., ethylene, propylene, and 1‐butene) but were found to carry out the rapid and efficient polymerization of norbornene. The polynorbornene products were characterized by gel permeation chromatography/light scattering, 13C NMR, and IR, and their Mark–Houwink and dn/dc parameters were determined. The molecular weights of the polynorbornenes were very high (weight‐average molecular weight = 587,000–797,000 g/mol). 13C NMR suggested that the polymerization occurred via vinyl addition (i.e., a 2,3‐linked polymer); no ring‐opened product was observed. Thermogravimetric analysis indicated that the polynorbornenes were stable up to 400 °C under nitrogen. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2095–2106, 2003 相似文献