Excess energy in the electroexplosive nanopowders

Research on Chemical Intermediates - The electroexplosive route for nanopowders production is a rapidly occurring nonequilibrium process under the action of high power density energy. The...     

Oxidation of copper nanopowders on heating in air

The morphology and structure of copper nanopowders produced by electrical explosion of conductors are considered. The regularities of nanopowder oxidation in air were studied during linear and isothermal heating. The characteristics of initial powders in relation to the kinetic oxidation parameters were determined and the dependence of phase composition of the products of nanopowder oxidation on the heating conditions and dispersity of initial powders was found.     

Effect of heating rates on TG-DTA results of aluminum nanopowders prepared by laser heating evaporation

Aluminum (Al) nanopowders with mean diameter of about 50 nm and passivated by alumina (Al₂O₃) coatings were prepared by an evaporation route: laser heating evaporation. Thermal properties of the nanopowders were investigated by simultaneous thermogravimetric-differential thermal analysis (TG-DTA) in dry oxygen environment, using a series of heating rates (5, 10, 20, 30, 50 and 90°C min⁻¹) from room temperature to 1200°C. With the heating rates rise, the onset and peak temperatures of the oxidation rise, and the conversion degree of Al to Al₂O₃ varies. However, the specific heat release keeps relatively invariant and has an average value of 18.1 kJ g⁻¹. So the specific heat release is the intrinsic characteristic of Al nanopowders, which can represent the ability of energy release.     

Fundamental aspects of oxidation of electroexplosive nickel nanopowder

Fundamental aspects of the process in which a nickel nanopowder produced by an electric explosion of conductors is oxidized under heating in air at a linearly increasing temperature and in the isothermal mode were studied. It is shown that the dispersion composition of the powder, structure of the metallic core of nickel particles, and characteristics of the oxide shell affect the kinetic parameters of the process. An explanation is suggested for specific features of the macrokinetic reaction mode caused by the joint influence exerted by the relative amounts of fractions of different-size particles in the powder and by the characteristic of the oxide layer. The reaction kinetics is simulated, with the size distribution function of nickel particles taken into account.     

Oxidation and melting of aluminum nanopowders

Recently, nanometer-sized aluminum powders became available commercially, and their use as potential additives to propellants, explosives, and pyrotechnics has attracted significant interest. It has been suggested that very low melting temperatures are expected for nanosized aluminum powders and that such low melting temperatures could accelerate oxidation and trigger ignition much earlier than for regular, micron-sized aluminum powders. The objective of this work was to investigate experimentally the melting and oxidation behavior of nanosized aluminum powders. Powder samples with three different nominal sizes of 44, 80, and 121 nm were provided by Nanotechnologies Inc. The particle size distributions were measured using small-angle X-ray scattering. Melting was studied by differential scanning calorimetry where the powders were heated from room temperature to 750 degrees C in an argon environment. Thermogravimetric analysis was used to measure the mass increase indicative of oxidation while the powders were heated in an oxygen-argon gas mixture. The measured melting curves were compared to those computed using the experimental particle size distributions and thermodynamic models describing the melting temperature and enthalpy as functions of the particle size. The melting behavior predicted by different models correlated with the experimental observations only qualitatively. Characteristic stepwise oxidation was observed for all studied nanopowders. The observed oxidation behavior was well interpreted considering the recently established kinetics of oxidation of micron-sized aluminum powders. No correlation was found between the melting and oxidation of aluminum nanopowders.     

The oxidation of isopropylbenzene in the presence of copper nanopowders

The oxidation of isopropylbenzene with oxygen in the presence of copper nanopowders prepared under various wireelectrical explosion conditions was studied. The oxidative conversion of isopropylbenzene was observed only for nanopowders with a linear function of oxygen absorption. Holding copper nanopowders in a vacuum stimulated their initiating activity. A lower initial temperature of the oxidation of nanopowders in air corresponded to a higher rate of oxygen absorption by isopropylbenzene. The amount of absorbed oxygen was not equivalent to the conversion of isopropylbenzene.     

The formation of nanosheets of aluminum oxyhydroxides from electroexposive nanopowders

Products formed at various stages of the hydrolysis of aluminum nanopowder prepared by electrical explosion in the atmosphere of nitrogen were isolated and characterized. Particles formed in hydrolysis were shown to have the morphology of nanosheets 5–10 nm thick agglomerated into 0.5–3.0 μm volume structures. The phase composition of hydrolysis products was determined.     

The kinetics of coal oxidation

Seven coals from across Canada were oxidized, and a kinetic analysis made from the data obtained. It was established that the equation¹,

is a valid rate of sorption of oxygen in the temperature range 110 to 170°C.     

Chemical and structural transformations in manganese aluminum spinel of the composition Mn1.5Al1.5O4 during heating and cooling in air

Single phase cubic spinel of the composition Mn_1.5Al_1.5O₄ is synthesized. Its crystal structure refinement shows that 0.4Mn+0.6Al are in the octahedral sites and 0.7Mn+0.3Al are in the tetrahedral sites. High temperature X-ray diffraction is used to analyze Mn_1.5Al_1.5O₄ behavior during heating and cooling in air. In a temperature range of 600°C to 700°C, initial spinel splits into layers, and the sample represents a twophase system: cubic spinel Mn_0.4Al_2.4O₄ and a phase based on β-Mn₃O₄. Above 900°C the sample again turns into single phase cubic spinel. The role of oxidizing processes in the decomposition of Mn_1.5Al_1.5O₄ caused by oxygenation and partial oxidation of Mn²⁺ to Mn³⁺ is shown. A scheme of structural transformations of manganese aluminum spinel during heating from room temperature and cooling from 950°C is proposed.     

The kinetics of polyolefin oxidation in aqueous media

The thermal oxidation, at 75–92°C, of antioxidant-free low-density polyethylene (LDPE) is faster in most aqueous environments than in air. The accelerative environments include water, solutions of sodium salts, and a basic buffer. However, an acidic buffer retards oxidation. Transition metal salts are not examined here since their catalytic effect is wellknown. The acceleration is predominantly a surface phenomenon, and so is most obvious in thin polymer films. For antioxidant-containing polyolefins, complications arise because of the possibility of extraction of stabilizers, but the trend in oxidative lifetime is similar to that of the antioxidant-free specimens, and the antioxidants are observed to react chemically during the aging process. For example, a commercial crosslinked polyethylene (XLPE) shows a reduction in thermo-oxidative lifetime of at least a factor of two in aqueous environments compared to air. High-density polyethylene (HDPE) and polypropylene (PP) show similar behavior, but the magnitude of the effect of aqueous environments is less. This phenomenon is discussed in terms of nucleophilic attack by peroxy anions on hydroperoxides.     

Particle size effects on the oxidation of tungsten carbide nanopowders

The oxidation of tungsten carbide (WC) powders with the average particle size 〈D〉 from 20 to 6000 nm was studied by differential thermal and differential thermogravimetric analyses. WC powders are oxidized, irrespective of their dispersity, to higher oxide WO₃. The conclusion was drawn that at smaller particle sizes of WC powder, the oxidation rate increases, and the temperature of the peak of the exo effect decreases. The functional dependences of the temperature of the peak and the activation energy of oxidation on the particle size were determined.     

The kinetics of pentoxyl oxidation by hypochlorite ions

The kinetics of pentoxyl (I) oxidation in aqueous media under the action of hypochlorite ions was studied at pH 8.8 and 273–298 K. The order of the reaction with respect to both participants was found to be one. The temperature dependence of the reaction rate obeyed the Arrhenius law. The reaction activation parameters were found to be E _a=11.08 kJ/mol, ΔH ^≠=8.73 kJ/mol, ΔS ^≠=?200.70 J/(mol K), and ΔG ^≠=66.88 kJ/mol. Reaction stoichiometry was studied, the chemical characteristics of the process considered, and a mechanism of the oxidative transformation of I under the action of OCl^? suggested.     

ICP-AES analysis of aluminum isopropoxide,yttrium, and neodymium oxide nanopowders

A technique has been developed for analysis of impurities in precursors of the optic ceramics: aluminum isopropoxide, yttrium and neodium oxide nanopowders (weight fraction of Nd ≤5%) by atomic-emission spectroscopy with inductively coupled plasma. In the case of aluminum isopropoxide, the effect of matrix is compensated by applying Bi as an internal standard. The detection limits of impurities were found to be 10^?5–10^–6 wt.%.     

Interaction of compact samples made of pyrophoric iron nanopowders with air

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Kinetics of the growth of the oxide layer during anodic oxidation of aluminum

Experimental plots of anode current density against time obtained for various electrolytes over a temperature range from 5 to 60°C have been compared with a theoretical model which describes the kinetics of the growth of the oxide film during anodic oxidation of aluminum. It is concluded from differences in the kinetic parameters for ammonium benzoate and ammonium adipate that the oxidative destruction of the corresponding carboxylate anion is involved in a rate determining step of the process. V. I. Vernadskii Institute of General and Inorganic Chemistry, Ukraine Academy of Sciences, 32/34 Academician Palladin Prosp., 252680 Kiev-142, Ukraine. Translated from Teoreticheskiya i éksperimental’naya Khimii, Vol. 33, No. 1, pp. 58–61, January–February, 1997.     

The kinetics of the chromic acid oxidation of diphenylmethane

The kinetics of the chromic acid oxidation of diphenylmethane in aqueous acetic acid solution has been studied. The rate law is v = k[φCH₂φ][CrO₃]h₀ a kinetic isotope effect, k_H/k_D = 6·4 at 30°, was noted, and electron releasing groups were found to moderately facilitate the reaction (⁺ = −1·17). These, and related data, suggest that the initial reaction is the abstraction of a hydrogen atom forming a benzhydryl radical. The latter may then be further oxidized to give the product, benzphenone. It is noted that the chromic acid oxidations which must involve hydrogen abstraction all show a kinetic dependence on the total chromium (VI) concentration, whereas those which are believed to proceed via an ester mechanism have a kinetic dependence on only the acid chromate ion. This difference is suggested as a possible method of distinguishing between these two mechanisms. The effect of the water content of the solvent on the rate of the reaction is discussed, and a tentative, relative, H₋ scale for some of these solutions is suggested. This may permit one to determine the number of molecules of water which are involved in a reaction.     

Criteria for the dilatometric analysis to determine the transformation kinetics during continuous heating

Journal of Thermal Analysis and Calorimetry - A method was established to determine the amount of austenite formed, by stages, in a low-carbon steel through dilatometric analysis. Based on length...     

空气氧化Fe2+动力学及含铁污水处理技术研究

从动力学角度研究空气氧化Fe~(2+)离子的化学反应机理,主要探究溶液矿化度、pH和曝气方式对Fe~(2+)氧化速率的影响,在40℃实验温度下建立动力学模型.实验表明,pH对处理含铁污水有重要作用.并通过模拟高含铁(c(Fe~(2+))≥100 mg/L)和含铁含HCO■两种常见油田酸性污水并做处理研究,得到处理含铁污水的可行方法.处理结果表明,对于高含铁污水可通过加碱方法改性,pH提高到9时Fe~(2+)含量接近0;含铁含HCO■污水可通过定量曝气比V_(G/L)方法将pH提高到预期范围,并利用溶解氧延迟氧化Fe~(2+),该氧化模式为二级动力学反应.     

The kinetics of oxidation of bilirubin and ascorbic acid in solution

The results of a comparative study of the oxidation of bilirubin, ascorbic acid, and their mixture in aqueous solutions under the action of air oxygen and hydrogen peroxide are presented. The observed and true rate constants for the oxidation reactions were determined. It was shown that the oxidation of tetrapyrrole pigment occurred under these conditions bypassing the stage of biliverdin formation to monopyrrole products. Simultaneous oxidation of bilirubin and ascorbic acid was shown to be accompanied by the inhibition of ascorbic acid oxidation by bilirubin, whereas ascorbic acid itself activated the oxidation of bilirubin.