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71.
采用密度泛函理论计算和实验研究形貌可控制备氧化铁作为高效载氧体用于化学链燃烧的可行性. 首先从理论上对比分析Fe2O3高指数晶面[104]和低指数晶面[001]的反应活性及深层还原反应机理. 表面反应结果显示, Fe2O3[104]氧化CO的反应活性远高于Fe2O3[001], Fe2O3[104]被还原成为低价的铁氧化物或单质, 这些低价的铁氧化物或单质可被O2氧化再生. 载氧体和CO深层反应结果显示Fe2O3[104]可被CO彻底还原成Fe单质, Fe2O3[104]释放氧能力强, 反应活性高; 而Fe2O3[001]还原到一定程度后反应能垒高, 抑制表面进一步还原, 释放氧能力有限. 最后, 实验结果进一步证明了Fe2O3[104]作为载氧体用于化学链燃烧的高反应活性及稳定性. 相似文献
72.
Xiaofeng Peng 《Applied Surface Science》2009,255(8):4384-4388
A novel approach is presented for nanohole 3D-size tailoring. The process starts with a monolayer of polystyrene (PS) beads spun coat on silicon wafer as a template. The holes can be directly prepared through combustion of PS beads by oxygen plasma during metal or oxide thin film deposition. The incoming particles are prevented from adhering on PS beads by H2O and CO2 generated from the combustion of the PS beads. The hole depth generally depends on the film thickness. The hole diameter can be tailored by the PS bead size, film deposition rate, and also the combustion speed of the PS beads. In this work, a series of holes with depth of 4-24 nm and diameter of 10-36 nm has been successfully prepared. The hole wall materials can be selected from metals such as Au or Pt and oxides such as SiO2 or Al2O3. These templates could be suitable for the preparation and characterization of novel nanodevices based on single quantum dots or single molecules, and could be extended to the studies of a wide range of coating materials and substrates with controlled hole depth and diameters. 相似文献
73.
G.M. Dutro R.A. Yetter G.A. Risha S.F. Son 《Proceedings of the Combustion Institute》2009,32(2):1921-1928
The effect of stoichiometry on the combustion behavior of the nanoscale aluminum molybdenum trioxide (nAl/MoO3) thermite was studied in a burn tube experiment by characterizing the propagation velocity and pressure output of the reaction. Changing the stoichiometry affects the combustion through changes in the product temperature, phase, and composition. The mixture ratios of the composites were varied over an extremely wide range (5% nAl (95% MoO3)–90% nAl (10% MoO3)). Results revealed three separate combustion regimes: a steady high speed propagation (100 to 1000 m/s) from approximately 10% to 65% nAl, an oscillating and accelerating wave near 70% nAl, and a steady-slow speed propagation (0.1–1 m/s) from approximately 75% to 85% nAl. Propagation was observed to fail both <10% nAl and >85% nAl. This is the first known observation of such limits for a nanoscale thermite in a tube geometry. The instrumented tube tests revealed peak pressures over 8 MPa near stoichiometric conditions in the steady high speed propagation region, no measurable pressure rise at low speed propagation, and building pressures for accelerating waves. The results suggest the propagation mode to be a supersonic convective wave for near stoichiometric mixtures and a conductive deflagration for extremely fuel-rich mixtures. The implications of these results for microscale combustion applications are discussed. 相似文献
74.
Vijay Singh R.P.S. Chakradhar Isabelle Ledoux-Rak Laurent Badie Fabienne Pelle Svetlana Ivanova 《Journal of luminescence》2009,129(11):1375-1380
New near-infrared luminescent, monoclinic CaAl2O4:Er3+ phosphor was prepared by using the combustion route at furnace temperatures as low as 500 °C in a few minutes. Combustion synthesized phosphor has been well characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy-dispersive analysis of X-ray (EDAX) mapping studies. The luminescence spectra of Er3+-doped calcium aluminate were studied at UV (380 nm), vis (488 nm) and IR (980 nm) excitation. Upon UV and vis excitation, the CaAl2O4:Er3+ phosphor exhibits emission bands at ~523 nm and at ~547 nm, corresponding to transitions from the 2H11/2 and 4S3/2 erbium levels to the 4I15/2 ground state. A strong luminescence at 1.55 μm in the infrared (IR) region due to 4I13/2→4I15/2 transition has been observed in CaAl2O4:Er3+ phosphor upon 980 nm CW pumping. In the spectrum of IR-excited up-conversion luminescence, green (~523 and ~547 nm) and red (662 nm) luminescence bands were present, the latter associated with the 4F9/2→4I15/2 transitions of Er3+ ions. Both excited state absorption and energy transfer may be proposed as processes responsible for the population of the 4S3/2 and 4F9/2 erbium levels upon IR excitation. The mechanisms responsible for the up-conversion luminescence are discussed. 相似文献
75.
76.
Combustion properties and thermal degradation behavior of polylactide with an effective intumescent flame retardant 总被引:6,自引:0,他引:6
An intumescent flame retardant spirocyclic pentaerythritol bisphosphorate disphosphoryl melamine (SPDPM) has been synthesized and its structure was characterized by Fourier transformed infrared spectrometry (FTIR), 1H and 31P nuclear magnetic resonances (NMR). A series of polylactide (PLA)-based flame retardant composites containing SPDPM were prepared by melt blending method. The combustion properties of PLA/SPDPM composites were evaluated through UL-94, limiting oxygen index (LOI) tests and microscale combustion calorimetry (MCC) experiments. It is found that SPDPM integrating acid, char and gas sources significantly improved the flame retardancy and anti-dripping performance of PLA. When 25 wt% flame retardant was added, the composites achieved UL-94 V0, and the LOI value was increased to 38. Thermogravimetric analysis (TGA) showed that the weight loss rate of PLA was decreased by introduction of SPDPM. In addition, the thermal degradation process and possible flame retardant mechanism of PLA composites with SPDPM were analyzed by in situ FTIR. 相似文献
77.
Sergio L. González-Cortés 《Reaction Kinetics and Catalysis Letters》2009,97(1):131-139
The thiophene hydrodesulfurization (HDS) reaction on γ-Al2O3 supported CoMo, NiMo and NiW sulfide catalysts was compared in order to gain insight into the promoter effect on direct desulfurization
(DDS) and hydrogenation (HYD) pathways. Ni-promoted Mo (or W) sulfide catalysts favor the hydrogen transfer reactions relative
to CoMo sulfide catalyst, which facilitates the direct route instead. This different performance and also the dependence of
the apparent Arrhenius parameters with the catalyst formulation were attributed to the major participation of Mo (or W) edge
for the Ni-containing catalysts and S edge for CoMo sulfide catalyst upon the thiophene-HDS reaction. 相似文献
78.
Leo W.Y. Yeung Yuichi Miyake Sachi Taniyasu Keerthi S. Guruge Nobuyoshi Yamashita 《Analytica chimica acta》2009,635(1):108-5513
The widespread occurrence and environmental persistence of perfluorinated compounds (PFCs) received worldwide attention recently. Exhaustive analysis of all fluorinated compounds in an environmental sample can be daunting because of the constraints in the availability of analytical standards and extraction methods. Combustion ion chromatographic technique for trace fluorine analysis was used to assess the concentrations of known PFCs (e.g., PFOS, PFOA) and total fluorine (TF) in the blood of wild rats collected from Japan. The technique was further validated using tissues from PFOA-exposed rats. Six PFCs (PFOS, PFOSA, PFUnDA, PFDA, PFNA, and PFOA) were detected in all of the wild rat blood samples. Concentrations of extractable organic fluorine (EOF) in fraction 1 (Fr1; MTBE extraction) of wild rats ranged 60.9-134 ng F mL−1, while those in fraction 2 (Fr2; hexane) were below LOQ (32 ng F mL−1); TF concentrations in the blood of wild rats ranged from 59.9-192 ng F mL−1. The contribution of known PFCs in EOF-Fr1 (MTBE) varied from 9% to 89% (56% on average), and known PFC concentrations in TF content were less than 25%. In contrast, TF concentrations in the blood of PFOA-exposed rats ranged from 46900 to 111000 ng F mL−1, with PFOA contributing over 90% of TF. A comparison of results from the samples analyzed in this study and the literature revealed three distinct groups with PFOA/known PFC and TF levels (i.e., wild rats and general population, occupationally exposed workers, and PFOA-exposed laboratory rats). The mass balance analysis of the different forms of fluorine in blood suggested the presence of other forms of organic fluorine in addition to known PFCs. 相似文献
79.
Maria das Dores M.C. Ribeiro da Silva Manuel A.V. Ribeiro da Silva Vera L.S. Freitas Maria Victoria Roux Pilar Jiménez Manuel Temprado Juan Z. Dávalos Pilar Cabildo Rosa M. Claramunt José Elguero 《The Journal of chemical thermodynamics》2009,41(12):1400-1407
A thermochemical and thermophysical study has been carried out for crystalline barbital [5,5′-diethylbarbituric acid]. The thermochemical study was made by static bomb combustion calorimetry, from which the standard () molar enthalpy of formation of the crystalline barbital, at T = 298.15 K, was derived as −(753.0 ± 1.8) kJ · mol−1. The thermophysical study was made by differential scanning calorimetry over the temperature interval (265 to 470) K. A solid–solid phase transition was found at T = 413.3 K. The vapour pressures of the crystalline barbital were measured at several temperatures between T = (355 and 377) K, by the Knudsen mass-loss effusion technique, from which the standard molar enthalpy of sublimation, at T = 298.15 K was derived as (117.3 ± 0.6) kJ · mol−1. The combination of the experimental results yielded the standard molar enthalpy of formation of barbital in the gaseous phase, at T = 298.15 K, as −(635.8 ± 1.9) kJ · mol−1. This value is compared and discussed with our theoretical calculations by several methods (Gaussian-n theories G2 and G3, complete basis set CBS-QB3, density functional B3P86 and B3LYP) by means of atomization and isodesmic reaction schemes. 相似文献
80.
Clara C.S. Sousa M. Agostinha R. Matos Victor M.F. Morais 《The Journal of chemical thermodynamics》2009,41(12):1408-1412
In this work, we have determined the experimental standard (p° = 0.1 MPa) molar enthalpies of formation, in gas phase, of flavone and flavanone.These results were obtained by combining the standard molar enthalpies of formation in the condensed phase with the standard molar enthalpies of sublimation. The former values were derived from combustion experiments in oxygen, at T = 298.15 K, in a static bomb calorimeter. The values of the standard molar enthalpies of sublimation were obtained by Calvet microcalorimetry and corrected to T = 298.15 K.High-level density functional theory calculations using the B3LYP hybrid exchange–correlation energy functional with extended basis sets and more accurate correlated computational techniques of the MCCM/3 suite have been performed for the compounds.The obtained results, experimental and computational, for flavone and flavanone were compared with those obtained for chromone and chromanone, respectively. 相似文献