Reactions of poly(hexafluoropropylene oxide) perfluoroisopropyl ketone with various amines

The reaction of poly(hexafluoropropylene oxide) perfluoroisopropyl ketone, perfluoroethyl perfluoroisopropyl, or bis-perfluoroisopropyl ketone with various amines has been studied and the products identified. A comparison of the reactivity of the ketones with different amines is made and identified by mass spectroscopy. The reaction of diethyl amine with all three ketones leads to two unexpected products and the mechanism of their formation is considered.     

Preparation and properties of polyurethane networks based on α,ω-difunctional poly(hexafluoropropylene oxide)

Poly(hexafluoropropylene oxide), poly(HFPO), networks were prepared from functional polymers by end linking via urethane groups. The prepolymers were characterized by NMR spectroscopy and GPC. The networks were characterized by determination of the number of network chains from the shear modulus, and were snown to contain both trifunctional crosslinks and difunctional links. The properties of the networks were investigated by a range of techniques. Compared with fully-fluorinated networks formed via triazine cross-links, investigated previously, the urethane-linked networks were more readily prepared but were poorer elastomers, were less thermally stable, and were less resistant to swelling by common polar solvents. © 1995 John Wiley & Sons, Inc.     

Understanding the influence of hydrocarbon insulators in fluorinated amines: Reactivity of poly(hexafluoropropylene oxide) amine containing methylene spacers

Although reactions involving hydrocarbon amines have been thoroughly investigated, very little is currently known about reactions of corresponding fluorinated amines containing a methylene spacer group. Furthermore, such reactions involving the poly(hexafluoropropylene oxide) (herein, polyHFPO) amine have been completely unexplored. The addition of acyl, sulfonyl and alkyl halides, isocyanates, aldehydes, anhydrides and esters to polyHFPO amine has been accomplished. The results of these reactions, including reaction mechanisms, yields, byproducts, etc. are discussed.     

Decomposition of nitrous oxide on AlFe-PILC catalyst

Summary Two AlFe-PILC catalysts were prepared with different OH/metal ratio and applied in nitrous oxide (N₂O) decomposition reactions. The 100% conversion of N₂O with NH₃into N₂and H₂O was achieved below 500^oC with both applied catalysts. However, the activity of catalysts in direct conversion of N₂O into N₂and O₂did not exceed 40 % below 500^oC. In this reaction the activity of AlFe-PILC catalyst synthesized at higher OH/metal ratio (4) is higher compared to the activity of AlFe-PILC catalyst with OH/metal ratio (2). Free FeO·Fe₂O₃particles were registered in the AlFe-PILC catalyst with higher OH/metal ratio (4).     

碳酸二甲酯在锌铝复合氧化物上分解行为的红外研究

采用尿素热分解法制备锌铝水滑石,1 073 K下煅烧得到相应的锌铝复合氧化物催化剂。通过XRD谱图确定锌铝复合氧化物ZAO-3(1 073 K)催化剂的组分为ZnO相和ZnAl2O4尖晶石相。NH3(CO2)-TPD结果表明,当向ZnO中引入Al后,催化剂的酸碱性位和酸碱性强度都发生改变。采用原位红外(in-situ FT-IR)手段,研究了碳酸二甲酯(DMC)分别在ZAO-3(1 073 K)、ZnAl2O4、ZnO上随着温度变化的分解行为。结果表明,ZAO-3(1 073 K)催化剂上大量的弱酸碱性位协同稳定DMC,抑制DMC的分解。     

高比表面积介孔氧化镍制备及表征

采用硝酸镍和草酸为原料,采用固态热分解法制备得到高比表面积的介孔Ni O纳米粒子,考察了原料的用量,热处理的温度,热处理的时间对孔结构的影响。用X射线衍射、透射电镜、扫描电镜和N2吸附-脱附技术对材料的物化性质进行了表征。结果表明:硝酸镍和草酸1∶1混合均匀、400℃灼烧4 h得到的介孔Ni O粒子的孔结构为最发达的蠕虫状介孔结构,比表面积和孔容分别达到236 m2·g-1和0.42 cm3·g-1。     

硝酸酯的热分解性能

分别在B3LYP/6-31G*和MP2/6-31G*的理论水平下,计算得到硝酸正丙酯、硝酸异丙酯、硝酸异辛酯和二缩三乙二醇二硝酸酯4种硝酸酯的O-NO2键离解能(BDE)。 采用常压DSC和高压DSC实验方法,研究了4种硝酸酯的热分解过程,获得热分解反应动力学参数。 常压下4种物质的热分解反应发生在气相区,当压力增大至2 MPa时,4种物质直接发生液相分解反应。 4种硝酸酯的O-NO2键离解能在很大程度上符合由实验分析得到的活化能,表明4种硝酸酯的热分解反应只是单分子O-NO2键的均裂反应。     

Synthesis, Characterization and Thermal Decomposition of Hydroxylammonium Uranyl Acetate

The synthesis of hydroxylammonium uranyl acetate is described. The identity of the synthesized compound was confirmed by chemical and infrared analysis. The intermediates and final products of the thermal decomposition were identified by means of thermogravimetric analysis, differential thermal analysis and X-ray diffraction. The thermal decomposition of hydroxylammonium uranyl acetate involves several steps. Two of them are due to decomposition of this compound to UO₂ via UO₂(CH₃COO)₂, and the third to the partial oxidation of UO₂ to UO₃ and the formation of U₂O₈ in the solid state at higher temperature.This revised version was published online in November 2005 with corrections to the Cover Date.     

热分解法制备纳米氧化钕

采用热分解法以2-硝基苯甲酸和硝酸钕为原料制备了纳米氧化钕微粉,利用正交设计对合成条件进行了优化,得出了最佳的合成条件,即原料2-硝基苯甲酸与硝酸钕物质的量比2.5∶1,溶液pH值5.5,反应时间3h、干燥时间8 h,在此条件下制得了平均粒径为15 nm的氧化钕微粉,并利用XRD和TEM对制得的纳米微粉进行了结构表征.     

13C separation by IRMPD of CF2HCL molecules with a powerful CO2-TEA laser

The single pulse separation parameters in IRMPD of CF₂HCL molecules have been obtained in relation with the laser fluence, the number of laser pulses, and the gas pressure. The measurements have been carried out using a fixed laser line (9P22) and an ordinary shape of the laser pulses.     

纳米Cu2O的制备及其对高氯酸铵热分解的催化性能

 以Cu(NO3)2和NaOH为原料,以水合肼为还原剂,通过沉淀法在室温下制备了纳米Cu2O. 采用X射线衍射、透射电镜和X射线光电子能谱等手段对产物进行了表征,并用热分析法考察了不同形貌的纳米Cu2O对高氯酸铵热分解的催化作用. 结果表明,通过改变NaOH溶液的加入量可分别得到长针形和多边形的纳米Cu2O. 通过调节反应物浓度可以将纳米Cu2O粒径控制在19～68 nm. 不同形貌的纳米Cu2O均能强烈催化高氯酸铵的热分解,其中分散性良好的多边形纳米Cu2O的催化活性较高,添加2%的多边形纳米Cu2O可使高氯酸铵的高温分解温度降低103 ℃,分解放热量由590 J/g增至1350 J/g.     

Density‐matrix theory of quantum dynamics under a strong external field switched on nonadiabatically

Quantum time‐evolution equations for the density matrix are formulated in the unrestricted Hartree–Fock approximation, with an emphasis on the nonperturbative effect due to a sudden or gradual onset of a strong external field. Numerical simulations are performed for ideal Fermi gas around a square‐well potential which is switched on dynamically. When the switching is fast enough, an oscillatory motion of the particle is induced by a nonadiabatic transition at the Landau–Zener crossing point, which is most clearly seen in a small‐size system. When the switching is sufficiently slow, the simulation corroborates the adiabatic theorem. It is shown that the Anderson's infrared catastrophe in a metal is strongly enhanced by the nonperturbative effect. The Keldysh formula of atomic multiphoton ionization can also be derived from the nonperturbative term in the density‐matrix equation, indicating a wide applicability of the present theory. © 2014 Wiley Periodicals, Inc.     

Kinetics of Thermal Decomposition of Dolomite

The thermal decomposition reactions of calcitic dolomite were investigated. Simultaneous TG/DTG/DTA were applied under non-isothermal conditions. From the recorded curves, the activation energies, pre-exponential factors and thermodynamic parameters of activation were calculated for the two thermal decomposition steps. This revised version was published online in August 2006 with corrections to the Cover Date.     

Fourier grid Hamiltonian‐based multidimensional Floquet propagator method for continuous,pulsed, and bichromatic laser field: Application to the multiphoton dissociation dynamics of HCN molecule

We present a Fourier grid Hamiltonian‐based multidimensional propagator method for multiphoton dissociation dynamics of triatomic molecule in continuous, pulsed, and bichromatic laser field. The method has been successfully applied to the photodissociation dynamics of HCN molecule, i.e., collinear geometry. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007     

Non-isothermal Kinetic Study of the Heterogeneous Thermal Decomposition of a Mannich Compound

The authors present data concerning the evaluation of kinetic parameters of the decomposition of a Mannich compound by using the classical method of constant heating rate thermal analysis and the new one of controlled rate thermal analysis (CRTA). The data processed using the CRTA method allow to obtain more reliable kinetic parameters according to the proposed reaction mechanism. This revised version was published online in July 2006 with corrections to the Cover Date.     

Decomposition of aliphatic α-fluorodinitro compounds in the liquid phase

The decomposition of compounds Y[CH₂C(NO₂)₂X]₂ (X=NO₂ and F; Y=CH₂C(O)O and OCH₂O) in the liquid phase (melt, solution) was found to proceedvia the same mechanism (homolytic cleavage of the C−N bond) as in the gas phase. Some stabilizing effects of the O_β atom and independence of the gas evolution rate constant (measured by the yield of final products) on the number of the −C(NO₂)₂X groups were found and interpreted. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2455–2458, December, 1998.     

A study of chromic oxide decomposition in an RF argon plasma

Vapor-phase thermal decomposition of chromic oxide in an rf argon plasma was studied using a new experimental system. Homogeneous and heterogeneous modes of reaction were compared, the overall process efficiency being substantially higher for the process carried out entirely in the vapor phase. Reaction products were collected along the reactor wall and studied by chemical methods as well as SEM, X-ray, and IR absorption. The collected powder was highly reactive, fine-grained, and of semiamorphous nature, the average particle size being well below 100 nm. Temperature profiles recorded below the coupling coil by spectroscopic methods were typical of an rf plasma, showing maxima slightly exceeding 5000 K, with the presence of off-axis peaks. Local Cr contents and concentration ratio (Cr)/(Cr₂O₃) in the plasma were determined from the deposition data obtained. A diffusion process was assumed for the wall-deposit buildup. The results obtained confirmed the advantages of using plasma vapor-phase systems, these being higher-efficiency processes and more reliable models than those obtained in the case of gas-solid plasma reactors, where solid particles are injected into the plasma. The thermal decomposition conversion of Cr₂O₃ into Cr was about 8 times higher in the homogeneous gas phase than in the plasma solid phase, all other conditions being equal.Nomenclature c velocity of light, cm × s^–1 - C _Cr ^m metallic Cr content, % by wt. - C _Cr ^t total Cr content, % by wt. - D species diffusivity, cm² · s^–1 - E energy of excited level, eV - f oscillator strength - F rate of species deposition, mol · cm^–2 · s^–1 - g statistical weight - h Planck's constant, J · s^–1 - I radial emission intensity for a given spectral line at a given radius in the plasma, W · sr^–1 · cm^–3 - k Boltzmann's constant, J · K^–1 - l length of collected deposit, cm - m mass of collected deposit, g - M molar weight of Cr - M _Ar ^a molar flow of axial argon, mmol · s^–1 - M _Ar ^p molar flow of peripheral argon, mmol · s^–1 - M _{Cr 2}O₃ molar flow of evaporated Cr₂O₃, mmol · s^–1 - Cr(I) concentration, cm^–3 - Q _T partition function at temperatureT - r reaction radius, cm - R radius of quartz tube, cm - t duration of deposition, s - T temperature, K - total extent of Cr₂O₃ decomposition into Cr, % - Z position of a plane normal to the plasma axis downward the lower turn of rf coil, cm Greek Letters molar ratio of Cr and Cr₂O₃ in deposit - wavelength, nm - species concentration, mol · cm^–3     

Influence of the Heating Rate in the Thermal Decomposition of HMX

This work refers to a study of the thermal decomposition of octahydro-1,3,5,7-tetranitro-1,3,5,7 tetrazocine (HMX) by differential scanning calorimetry (DSC) in non-isothermal conditions, with heating rates from1 to 25°C min⁻¹. The influence of the heating rate, the particle and the sample size were verified. The activation energy was calculated using the peak temperature shift method, proposed by Ozawa and a significant variation in the results was observed according to the range of the used heating rates. As the heating rate was increased, different conversions and self-heating effects were observed at the respective DSC peaks, indicating that the use of this method was inadequate and it may lead to incorrect results, which, in turn, could explain the wide range of activation energy values published in literature. At lower heating rates HMX decomposition occurs on the solid state and at higher ones decomposition occurs after melting practically at the same temperature, which does not depend on the heating rate. This revised version was published online in July 2006 with corrections to the Cover Date.     

Thermal Decomposition of Axinite

The thermal decomposition of axinite was studied by means of thermal, FTIR and X-ray methods. Dehydroxylation takes place in a rather narrow temperature range, the maximum of the corresponding peak being at ca. 900°C. The decomposition products are anorthite, rankinite and probably also small amounts of other, partly amorphous phases. This revised version was published online in July 2006 with corrections to the Cover Date.