A study of the acidic and catalytic properties of pure and sulfated zirconia–titania and zirconia–silica mixed oxides

Protonated pyridine (PyH⁺) was not found on ZrO₂ (Z) or ZrO₂–TiO₂ (ZT), but was detected on sulfated oxides (ZS, ZTS) by IR spectroscopy. In contrast, ZrO₂–SiO₂ samples containing about 30–80 mol% ZrO₂ showed Brønsted acidity both in nonsulfated (ZS) and sulfated (ZSS) forms. The total acidity was determined by NH₃TPD. Introduction of sulfate ions increased the sitespecific catalytic activity (TOF) in the conversion of cyclopropane or nhexane. The effect of sulfate ions was more significant on samples rich in zirconia. Results suggest that Zr is homogeneously distributed in ZS samples rich in silica. Zirconiabound dimeric sulfate, generating strong acidity, could not be formed in these preparations due to the absence of fairly large ZrO₂ domains.     

Mechanism of Upper Temperature Limits in a Wave of Filtration Combustion of Gases

A physical mechanism is established, responsible for the experimentally observed strong deceleration of the growth rate of the maximum skeleton temperature in a wave of filtration combustion of gases with increasing flow rate. The maximum temperatures of the gas and skeleton become commensurable, and the length of the thermalrelaxation zone becomes much shorter. A classification of regimes based on the temperatureheterogeneity criterion ₁ is proposed. Explicit analytical solutions are obtained for the wave for ₁1 and ₁1. A correction to reverse reactions in combustion products is considered. The effect of composition on wave behavior is studied by means of numerical calculations with a detailed kinetic scheme. The activation energy for ultrarich and ultralean methane–air mixtures is evaluated. It is concluded that the limiting efficiency of the heatrecuperation cycle in the wave is reached as ₁1; methods for maximizing the efficiency are suggested.     

Heterogeneous asymmetric reactions. 23. Enantioselective hydrogenation of ethyl pyruvate over cinchonine- and α-isocinchonine-modified platinum catalysts

The enantioselective hydrogenation of ethyl pyruvate to (S)-ethyl lactate over cinchonine- and -isocinchonine-modified Pt/Al₂O₃ catalysts was studied as a function of modifier concentration and reaction temperature. The maximum enantioselectivities obtained under the applied mild conditions were 89% ee using cinchonine (0.014 mmoldm^–3, 1 bar H₂, 23°C, 6% AcOH in toluene), and 76% ee in the case of -isocinchonine (0.14 mmoldm^–3, 1 bar H₂, –10°C, 6% AcOH in toluene). Since -isocinchonine of rigid structure exists only in anti-open conformation these data provide additional experimental evidence to support the former suggestion concerning the dominating role of anti-open conformation in these cinchona-modified enantioselective hydrogenations.     

Localization of Deformation in Copper Single Crystals During Explosive Collapse

It is established that highrate axisymmetric loading of single crystals by the method of explosive collapse of a hollow thickwalled cylinder causes deformation that involves all active closepacked slip systems. The spatial distribution of macroscopic sites of strain localization is determined by the crystallography of the active systems in singlecrystalline samples. The established correlation between the observed shear bands in the microstructure of copper single crystals and {111} active slip <110> systems of facecentered cubic (FCC) crystals and their symmetric arrangement show that deformation at a rate of 5 · 10⁴ sec^-1 occurs according to the crystalline structure of the materials.     

Location of Mn in MnAPO‐11: influence of synthesis from aqueous and non‐aqueous media

MnAPO11 samples were synthesized from aqueous (MnAPO11(A)) and ethylene glycol (MnAPO11(NA)) media. The crystallinity of the samples was more when the synthesis was carried out in ethylene glycol. Chemical and thermogravimetric analyses reveal greater incorporation of Mn in the framework of MnAPO11(NA) than in MnAPO11(A). At least five different types of Mn(II) species are detected in the samples by ESR. The studies suggest that Mn is more homogeneously distributed in MnAPO11(NA) than in MnAPO11(A).     

Molybdenum nitride for the direct decomposition of NO

The physico-chemical properties of passivated -Mo₂N have been investigated. The material showed high activities for NO direct decomposition: nearly 100% NO conversion and 95% N₂ selectivity were achieved at 450C. The amount of O₂ taken up by -Mo₂N increased with temperature rise and reached 3133.9 molg^–1 at 450C; we conclude that there formation of Mo₂O_xN_y occurred. This oxygen-saturated -Mo₂N material was catalytically active: NO conversion and N₂ selectivity were 89 and 92% at 450C. We found that by means of H₂ reduction at 450C, Mo₂O_xN_y could be reduced back to -Mo₂N and the oxidation/reduction cycle is repeatable; such a behaviour and the high oxygen capacity (3133.9 molg^–1) of -Mo₂N suggest that -Mo₂N is a promising catalytic material for automobile exhaust purification.     

Anisotropic oxidation of crystallites of vanadyl pyrophosphate

Anisotropic oxidation of crystallites of vanadyl pyrophosphate ((VO)₂P₂O₇) has been demonstrated by Raman spectroscopy with samples having different microstructures. Oxidation of these samples by O₂ produced X₁ phase,- and-VOPO₄ phases. The relative peak intensity of the X₁ phase to the other phases correlated well with the ratio of the (100) plane to the side planes (surface area-basis). This correlation showed that the (100) plane was oxidized to X₁ phase and the side planes to- and-VOPO₄. For example, thin plate-like (VO)₂P₂O₇, of which the (100) fraction is 98%, was oxidized almost exclusively to X₁ phase. But when it was fractured into small plates to increase the side planes and then oxidized,- and-VOPO₄ were detected in addition to the X₁ phase. These results are consistent with our previous conclusion that the (100) plane of (VO)₂P₂O₇ is selective, but side planes are non-selective for catalytic oxidation ofn-butane.     

Electrochemical behaviour of viologen-cyclodextrin inclusion complexes. The case of non-alkyl group substituted viologen

The electrochemical behavior of non-alkyl substituted viologen, 4,4-dibenzyl bipyridinium (BzV), 4,4-dicyanophenyl bipyridinium (CyV) and -,-,-cyclodextrin (, , -CD) was studied using cyclic voltammetry and a spectroelectrochemical method. It was found that BzV and Fe(CN) ₆ ^4– formed a charge-transfer (CT) complex with a ratio of 21 and the colour of the solution faded with the addition of an electrolyte. This behaviour is the same as in then-heptyl viologen and ferrocyanide system [1]. BzV, -CD and -CD formed an inclusion complex only in the reduced state, whilst BzV and -CD formed an inclusion complex in both the oxidized and the reduced state. An EC scheme in which a chemical reaction follows an electrochemical reaction was considered to predominate in the BzV and -, -CD systems, while a CE scheme in which a chemical reaction preceded an electrochemical reaction predominated in the BzV and -CD system. On the other hand, CyV was found to form an inclusion complex with -, -, -CD in both the oxidized and the reduced states. therefore a CE scheme was considered to predominate in the CyV--, -, -CD systems.     

A miscibility study of ternary blends of polystyrene,tetramethylbisphenol-A polycarbonate,and poly(2,6-dimethyl-1,4-phenylene oxide)

Phase behaviorof ternary blends of polystyrene (PS), tetramethylbisphenol-A polycarbonate (TMPC), and poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) at two different temperatures (i.e., 210 and 300 °C, respectively) was studied by means of differential scanning calorimetry. Miscibility of the ternary blends at either temperature was found restricted to limited compositions, in agreement with simulated spinodal curves based on published values of interaction parameters. The limited ability of PS, which is separately miscible with TMPC and PPO at 210 °C, to act as a common solvent for the immiscible TMPC/PPO pair at this temperature was explained in terms of the disparity in PS/TMPC and PS/PPO pair interactions (i.e., the 'X effect).     

Ammonia synthesis over multi‐promoted iron catalysts obtained by high‐energy ball‐milling

The feasibility of producing ammonia synthesis catalysts from highenergy ballmilling of a simple mixture of the constituent oxides has been investigated. The effect of ballmilling the fused oxidic precursor of the industrial KM1 ammonia synthesis catalyst has also been studied. The results show that highenergy ballmilling offers some interesting possibilities for preparing novel catalytic materials. It is observed that ballmilling of the powder oxides mixture leads to formation of solid solutions and the catalytic activity is significantly higher than that of the starting material. Furthermore, ballmilling of fused oxidic KM1 precursor is seen to give rise to more homogeneous promoter distribution and slightly higher activity. The quite small activity increase observed in this case probably reflects the fact that the fusion process has already resulted in a close to optimal promoter distribution. The choice of atmosphere during ballmilling is also seen to offer possibilities for regulating the phase composition.     

Convective Regime of Filtration Combustion of Energetic Materials in a Cocurrent Flow of Their Combustion Products

The convective regime of filtration combustion of energetic materials in a cocurrent flow of their combustion products is studied using a model with extremely simplified kinetics and heat transfer, which shows instability of the process. It is shown that the more accurate twotemperature model describes a steadystate regime. In this regime, the gas temperature on the hot boundary of the heating zone is well below the combustion temperature, and the solidphase temperature is well below the temperature proposed in recent studies on this topic. It is pointed out that the twotemperature approach is unjustified and intragranular nonisothermicity must be taken into account for convective regimes. It is shown that the threetemperature model, which takes into account this effect, does not give a stable steadystate solution.     

Electrosynthesis of 4,4′-dinitroazobenzene on PbO2 electrodes

Parameters which affect the electrosynthesis of 4,4-dinitroazobenzene from p-nitroaniline on platinum and PbO₂ electrodes were investigated and optimum conditions were determined. Maximum conversion efficiency for electrosynthesis was 95% with a pure -PbO₂ electrode. It was found that the electrocatalytic activity of a PbO₂ electrode depends upon its / ratio and its degree of crystallinity. The effects of the added base and water on the conversion efficiency were also elucidated.     

Phase transitions and dimensional and morphological changes in an “Aluminum Hydroxide-Alumina” system under a shock-wave action

A method is proposed to study the sequence of phase transitions in powdered materials under a shock-wave action. It is shown that the aluminum hydroxide-alumina system has the following sequence of phase transformations under a shock-wave action: bayerite boehmite -Al₂O₃ -Al₂O₃. It is found that there are no transitional high-temperature modifications of alumina. A method is developed for obtaining a submicron alumina powder, which allows obtaining materials with a controlled phase composition, including a thermodynamically stable -modification of Al₂O₃. The specific features of the morphological structure and the phase and structural characteristics of powders after a shock-wave action are considered.Translated from Fizika Goreniya i Vzryva, Vol. 41, No. 1, pp. 110–119, January–February, 2005.     

Acetone conversion to isobutene in high selectivity using zeolite β catalyst

The catalytic activity of the proton forms of zeolite and ZSM-5 are compared for the conversion of acetone. Zeolite demonstrates markedly enhanced selectivity to isobutene and selectivities of >80% can be achieved for conversions up to 65%. In contrast high selectivities to isobutene with ZSM-5 can be attained only at very low conversions (5%).     

Surface of a Titanium Target After Interaction with Shaped‐Charge Jet Particles

Coatings containing WC_1-x and W₂C_1-x tungsten carbides were produced on titanium targets by a shapedcharge explosion. The experiment used conical liners with a cone angle of 30° manufactured from a mixture of fine powders of tungsten, graphite, and ammonium nitrate. A comparative quantitative xray analysis of the top and bottom layers of the coating was performed. For the phase WC_1-x in the bottom layer, the value of the cubic unit cell parameter falls outside the range known in the literature. Microhardness in different segments of the target was studied.     

Factors governing the electrochemical synthesis of α-nickel (ii) hydroxide

The electrodeposition of -nickel hydroxide is promoted by the simultaneous chemical corrosion of the electrode by an acidic nitrate bath. Chemical corrosion results in the formation of a poorly ordered layered phase which is structurally similar to -nickel hydroxide and provides nucleation sites for the deposition of the latter. Therefore under conditions which enhance corrosion rates such as low current density (<1.3 mA cm–2), high temperature (60 C), high nickel nitrate concentration ( 1M) and the resultant low pH (1.7), -nickel hydroxide electrodeposition is observed, while -nickel hydroxide forms under other conditions. Further, -nickel hydroxide deposition is more facile on an iron electrode compared to nickel or platinum.     

β-Phellandrene: kairomone for pine engraver,Ips pini (Say) (Coleoptera: Scolytidae)

The responses ofIps pini (Scolytidae) to multiple-funnel traps baited with the pheromone, ipsdienol, and various monoterpenes were determined in stands of lodgepole pine in southern and central British Columbia.Ips pini was attracted to both ipsdienol and -phellandrene, demonstrating that -phellandrene is a kairomone for this species.Lasconotus complex (Colydiidae) and aCorticeus sp. (Tenebrionidae) were attracted to both ipsdienol and -phellandrene. TheCorticeus sp. exhibited a synergistic response to the combination of ipsdienol and -phellandrene; the responses of the other two species to the combination were additive. The predators,Thanasimus undatulus, Enoclerus sphegeus, andE. lecontei (Cleridae), were attracted to ipsdienol-baited traps, whileMonochamus clamator (Cerambycidae) andDendroctonus ponderosae (Scolytidae) were attracted to -phellandrene. Attraction of all eight species increased with increasing release rates of ipsdienol and/or -phellandrene.     

Both Ovarian Fluid and Female Urine Increase Sex Steroid Hormone Levels in Mature Atlantic Salmon (Salmo salar) Male Parr

We compared the ability of urine and ovarian fluid from female Atlantic salmon (Salmo salar) to stimulate increase in plasma concentrations of sex steroid hormones in mature conspecific male parr (priming effect of the stimuli). We also tested the hypothesis that prostaglandin F₂ (PGF₂) may act as a priming pheromone in the tested stimulants. Individual males of salmon parr were exposed to female urine, ovarian fluid, urine–ovarian fluid mix, or PGF₂. Plasma concentrations of the sex steroids of 17,20-dihydroxy-4-pregnen-3-one (17,20-P) were higher in males exposed to urine, ovarian fluids, and PGF₂ compared to control males. PGF₂ and a mixture of urine and ovarian fluid also gave increased concentrations of 11-ketotestosterone (11-KT). Concentrations of PGF₂ were higher in ovarian fluids than in urine. A behavior test with mature male parr in a fluviarium showed neither attraction to nor avoidance of 0.1 nM PGF₂, but plasma levels of 17,20-P were significantly higher in exposed males compared to controls.     

Impact of Structural Factors on Unsteady Combustion Modes of Gasless Systems

Based on the twotemperature, twovelocity timedependent model of gasless combustion, taking into account structural transformations related to the force action of the gas filtering in the pores and vitrification and volume variation of the condensed phase during the chemical transformation, selfoscillatory combustion modes are studied. Structural transformations are shown to have a pronounced effect on the propagation pattern of combustion waves and can either stabilize or destabilize combustion. The major structural parameters appreciably affecting combustionwave stability are the initial porosity, particle size, and pressure.     

Specific features of the phase transformations occurring during the sintering process of the beta-alumina based ceramics and their properties

Conclusions During the sintering process of beta-alumina obtained using the method of plasmochemical synthesis, the structural transformation occurs and it is accompanied by the separation of the excess Na₂O and the formation of an intergranular meltlike phase that is saturated with sodium and is characterized by high dielectric properties.The quantity of the meltlike phase and the magnitude of the /( + ) ratio determine the degree of stabilization (stability) and the final resistivity of the material and depend on the initial chemical composition and the heating rate maintained during the sintering process.It was shown that when the duration of residence of the material in the hot zone of the furnace is increased or when the specimens sintered maintaining high heating rates are subjected to additional heat treatment, one observes the occurrance of the reverse structural transformation that is characterized by an increase of the phase ratio /( + ) 1, a reduction in the quantity of the meltlike phase right up to its complete disappearance, and a decrease of the electrical resistivity of the material.In the materials having a large excess quantity of sodium oxide, the process of crystallization of the intergranular NaAlO₂ phase occurs simultaneously with the second phase transformation.The best ceramic and electrophysical parameters were obtained when sintering the material contained 7.9% Na₂O.Translated from Ogneupory, No. 3, pp. 13–18, March, 1990.