Methane activation over Ag-exchanged ZSM-5 zeolites: A theoretical study

Methane activation catalyzed over Ag-exchanged ZSM-5 zeolites was investigated by using the density functional theory (DFT) with a cluster model. Two different pathways were taken into account in this work: the “alkyl” and the “carbenium” pathways. The activation barriers obtained are 34.09 and 66.63 kcal/mol for the “alkyl” and the “carbenium” pathway, respectively. The calculated results show that the activation barrier of the “alkyl” pathway is smaller than that of “carbenium” pathway. Consequently, the “alkyl” pathway is the preferential reaction pathway. A new mechanism of methane conversion in the presence of ethene was proposed. In the catalytic cycle, the initial step of methane activation proceeds with the “alkyl” pathway and the Ag⁺ cation acts as an acceptor of the methyl group, then ethene reacts with the Ag⁺CH₃⁻ group to form propene. In addition, it is found that the Ag⁺ cations play an important role in the methane activation, compared with the reaction of methane activation over H-ZSM-5.     

Outer curvature and conformal geometry of an imbedding

The differential geometry of an imbedded (e.g. string or membrane world sheet) surface in a higher-dimensional background is shown to be conveniently describable (except in the null limit case) in terms of what are designated as its first, second, and third fundamental tensors, which will have the respective symmetry properties η_μν = η_(μν) as a trivial algebraic identity, K_μν^ρ = K_(μν)^ρ as the “generalised Weingarten identity”, which is the (Frobenius type) integrability condition for the imbedding, and Ξ_λμν^ρ = Ξ_(λμν)^ρ as a “generalised Codazzi equation”, which depends on the background geometry being flat or of constant curvature, needing replacement by a more complicated expression for a generic value of the background curvature B_κλ^μ_ν. The “generalised Gauss equation” expressing the dependence on this background curvature of the internal curvature tensor R_κλ^μ_ν of the imbedded surface is converted into terms of the first and second fundamental tensors, and it is thereby demonstrated that the vanishing of the (conformally invariant) “conformation tensor”, i.e. the trace free part C_μν^ρ of the second fundamental tensor K_μv^ρ, is a sufficient condition for conformal flatness of the imbedded surface (and thus in particular for the vanishing of its (Weyl type) conformal curvature tensor C_κλ^μ_ν) provided the background is itself conformally flat. In a trio of which the first two members are the generalised Gauss and Codazzi equations, the “third” member is shown to give an expression in terms of C_μν^ρ for the (trace free, conformally invariant) “outer curvature” tensor Ω_κλ^μ_ν whose vanishing is the condition for feasibility of the natural generalisation of the Walker frame transportation ansatz. The vanishing of C_μν^ρ is shown to be sufficient in a conformally flat background for the vanishing also of Ω_κλ^μ_ν.     

Magnetic properties of Lu2Co17−xSix single crystals

The Co-sublattice anisotropy in Lu₂Co₁₇ consists of four competitive contributions from Co atoms at crystallographically different sites in the Th₂Ni₁₇-type of crystal structure, which result in the appearance of a spontaneous spin-reorientation transition (SRT) from the easy plane to the easy axis at elevated temperatures. In order to investigate this SRT in detail and to study the influence of Si substitution for Co on the magnetic anisotropy, magnetization measurements were performed on single crystals of Lu₂Co_17−xSi_x (x=0−3.4) grown by the Czochralski method. The SRT in Lu₂Co₁₇ was found to consist of two second-order spin reorientations, “easy-plane”–“easy-cone” at T_SR1≈680 K and “easy-cone”–“easy-axis” at T_SR2≈730 K. Upon Si substitution for Co, both SRTs shift toward the lower temperatures in Lu₂Co₁₆Si (T_SR1≈75 K and T_SR2≈130 K) with the further onset of the uniaxial type of magnetic anisotropy in the whole range of magnetic ordering for Lu₂Co_17−xSi_x compounds with x>1 due to a weakening of the easy-plane contribution from the Co atoms at the 6g and 12k sites to the total anisotropy.     

Nuclear track radiography of “Hot” aerosol particles

Nuclear track radiography was applied to identify aerosol “hot” particles which contain elements of nuclear fuel and fallout after Chernobyl NPP accident. For the determination of the content of transuranium elements in radioactive aerosols the measurement of the -activity of “hot” particles by SSNTD was used in this work, as well as radiography of fission fragments formed as a result of the reactions (n,f) and (γ,f) in the irradiation of aerosol filters by thermal neutrons and high energy gamma quanta. The technique allowed the sizes and alpha-activity of “hot” particles to be determined without extracting them from the filter, as well as the determination of the uranium content and its enrichment by ²³⁵U, ²³⁹Pu and ²⁴¹Pu isotopes. Sensitivity of determination of alpha activity by fission method is 5×10⁻⁶ Bq per particle. The software for the system of image analysis was created. It ensured the identification of track clusters on an optical image of the SSNTD surface obtained through a video camera and the determination of size and activity of “hot” particles.     

Functional Characteristics of a New Electrolarynx “Evada” Having a Force Sensing Resistor Sensor

Electrolarynxes have been used as one of the rehabilitation methods for laryngectomees. Earlier electrolarynxes could not alter frequency and intensity simultaneously during conversation. Recently, we developed an electrolarynx named “Evada” (prototype so far) using a force sensing resistor (FSR) sensor that can control both frequency and intensity simultaneously during conversation. Employing three types of electrolarynxes (Evada, Servox-inton, Nu-vois), this study was undertaken to examine the functional characteristics of Evada for the normal control group and for laryngectomess. Five laryngectomees and five normal adults were asked to express three sentences (declarative sentence, “You stay here.”, interrogative sentence, “You stay here?”, and imperative sentence, “You! Stay here.”) using three types of electrolarynxes. Frequency and intensity changes between the first and last vowels in the three sentences were calculated and analyzed statistically by paired t test. The frequency changes in the interrogative and imperative sentences were more prominent in Evada than in Servox-inton and Nu-vois. The intensity changes in the interrogative and imperative sentences were also more prominent in Evada than in Servox-inton and Nu-vois. Evada controls frequency and/or intensity by having the subject press the control button(s). Therefore, Evada appears to be better at producing intonation and contrastive stress than Nu-vois and Servox-inton.     

H double-quantum filtered MR imaging of joints tissues: bound water specific imaging of tendons, ligaments and cartilage

The ¹H double-quantum filtered (DQF) NMR and DQF MRI is applied to the joint tissues of rabbits for selective visualization of tendons, menisci and articular cartilage. The ¹H DQF NMR selectively filters double-quantum coherence arising from the ¹H dipolar interaction of the “bound” water in these tissues. The double-quantum creation time dependency of the DQF signal intensity is determined by the molecular environment of the “bound” water. Therefore, each tissue has a unique creation time at which the DQF signal reaches its maximum intensity, τ_max (Achilles tendon: 0.46 ± 0.02 ms, patella: 0.55 ± 0.8 ms, anterior cruciate ligament: 0.60 ± 0.05 ms, meniscus: 0.78 ± 0.02 ms, skin: 0.81 ± 0.07 ms). We have presented the creation-time-contrasted DQF images of the meniscus, patella, foot, and knee joint. Compared with conventional T₂*-weighted gradient-echo (GRE) MR images, tendons, ligaments, menisci, and articular cartilage were more clearly seen in the DQF MR images. All these tissues were distinctly discriminated from each other by their creation times. DQF MR images of foot and knee joints can selectively demonstrated tendons, ligaments, and cartilage, which make it easier to understand the complicated anatomic structure of joints. Because the DQF NMR signal intensity and τ_max are sensitive to the order structure of the “bound” water, it might be possible to introduce the creation-time dependent-contrast of ¹H DQF MR images as a new tool for analyzing the changes in the ordered structure of the tissue.     

Divisors on elliptic Calabi-Yau 4-folds and the superpotential in F-theory — I

Each smooth elliptic Calabi-Yau 4-fold determines both a three-dimensional physical theory (a compactification of “M-theory”) and a four-dimensional physical theory (using the “F-theory” construction). A key issue in both theories is the calculation of the “superpotential” of the theory, which by a result of Witten is determined by the divisors D on the 4-fold satisfying X( _D = 1. We propose a systematic approach to identify these divisors, and derive some criteria to determine whether a given divisor indeed contributes. We then apply our techniques in explicit examples, in particular, when the base B of the elliptic fibration is a toric variety or a Fano 3-fold.

When B is Fano, we show how divisors contributing to the superpotential are always “exceptional” (in some sense) for the Calabi-Yau 4-fold X. This naturally leads to certain transitions of X, i.e., birational tranformations to a singular model (where the image of D no longer contributes) as well as certain smoothings of the singular model. The singularities which occur are “canonical”, the same type of singularities of a (singular) Weierstrass model. We work out the transitions. If a smoothing exists, then the Hodge numbers change.

We speculate that divisors contributing to the superpotential are always “exceptional” (in some sense) for X, also in M-theory. In fact we show that this is a consequence of the (log)-minimal model algorithm in dimension 4, which is still conjectural in its generality, but it has been worked out in various cases, among which are toric varieties.     

Scattering-controlled recombination of Δ2-light-hole indirect excitons and apparently enhanced quantum confined Stark effect in tensilely strained Si1−yCy/Si (0 0 1) quantum wells

Anomalies are found in the near-band-edge luminescence properties of Δ₂-light-hole indirect excitons in Si_1−yC_y-based tensilely strained quantum wells (QWs). The experimental spectra exhibit a clear signature of phonon-assisted transitions on the lower energy side of the “no-phonon” transition, which indicates the relevance of “virtual” indirect valleys and in-plane k-dispersion, as opposed to the theoretical prediction that the zone-centered Δ₂ valleys take over the conduction band edge. Intervalley scattering between [0 0 1]-Δ₂ valleys and in-plane Δ₄ valleys is suggested as the underlying mechanism. On the other hand, the experimental evidence was found for “apparently enhanced” quantum-confined Stark red shifts for Si_1−yC_y-based QWs. However, quantitative estimates are in conflict with the experimental results and predict a blue shift due to exciton weakening which masks the Stark effect as in the case of Δ₄-heavy hole excitons in Si_1−xGe_x-based QWs.     

Magnetic instabilities in the rare earth-3d compounds

Due to the evolution of the band structure through the series, the rare earth R-3d metal compounds form outstanding tools for the study of the 3d and/or 4f magnetic instabilities. Such instabilities are illustrated in this paper for three types of systems: i) the Y-Ni system with a special emphasis on the “thermal spontaneous magnetization” observed in Y₂Ni₇, ii) the R-Co system where “collective electron metamagnetism” and Co antiferromagnetism are observed in the RCo₂ (as in ThCo₅), and in La₂Co_1.7 and La₂Co₃, respectively; iii) the Ce-Ni system where the 4f instability is quite characteristic in the CeNi intermediate valence compound in which large magnetovolume effects were determined.     

Structural and transport properties of the triple-layer compounds Ba4(Pb1−xBix)3O10 (0≤ x<0.3)

A series of new compounds Ba₄(Pb_1−xBi_x)₃O₁₀ with 0≤x<0.3 has been prepared and characterized by X-ray and electron diffraction. The d.c. resistivity vs. temperature data for different x values are presented and structural features are compared to those of the superconducting phase Ba(Pb_1−xBi_x)O₃. The “mother-compound” Ba₄Pb₃O₁₀ is tetragonal, with lattice constants A=0.4280(1) and C=3.017(1) nm. Its structure can be regarded as a stacking of Ba(PbBi)O₃ triple-layers, separated by single BaO layers. Electron diffraction reveals the presence of a weak superstructure with the a-axis related to that of the perovskite by a=√2a_p. Frequent intergrowth of this phase with the perovskite structure is observed. The conductivity of the samples Ba₄Pb₃O₁₀ is nearly independent of temperature, while Bi-doped samples exhibit semiconductor-like behaviour at low temperature. No superconducting transition is observed down to 2K.     

Long-time correlation tails in crystals

Nonequilibrium thermodynamics and the Onsager hypothesis are utilized to demonstrate that long-time correlation “tails”, decaying as t^−3/2, should be expected in the velocity autocorrelation function of crystals. In the simplest situation, this behavior is due to the non-propagating (Rayleigh) mode. In the general case, it is argued that “diffusive” modes decaying in wavevector space as exp (−tK²), where is a constant, should lead to the same behavior.     

Chiral symmetry and the A1 contribution to the nucleon-nucleon interaction

The contribution of A₁ exchange to the nucleon-nucleon potential is studied in a broken chiral symmetric model. The A₁ is treated as a finite-width resonance in the πρ s-wave. Connections between pseudoscalar and pseudovector pion-nucleon coupling in the underlying model lagrangian are studied in detail. It is found that large terms in the NN interaction arising from πρ exchange with pseudoscalar coupling are suppressed by interference with a₁ exchange. With pseudovector coupling there is a suppression of the A₁ exchange by the so-called “seagull” terms in πρ exchange which arise from gauge invariance. The suppression becomes an exact cancellation in the limit of infinite ρ and a₁ masses and exact chiral symmetry. We found that inclusion of the a₁ decay into the πρ state strongly modifies the a₁] exchange potential, suppressing the tensor part but leaving the spin-spin part almost unchanged.     

Yb (Ba, Sr)2Cu4O8: a “124” phase superconductor with a reduced unit cell volume

Yb(Ba_1−xSr_x)₂Cu₄O₈ (0.1x0.3) superconductors of the YBa₂Cu₄O₈(“124”) structure were successfully synthesized using an O₂-hot-isostaticc-pressing (HIP) technique. The samples were characterized with respect to the crystal structure and superconducting properties. The lattice parameters of the samples decreased as the substitution of Sr for Ba proceeded. The superconducting transition temperatures of all the Yb-“124” samples were more or less the same, being around 80 K.     

Pseudo-billiards

A new class of Hamiltonian dynamical systems with two degrees of freedom and kinetic energy of the form T = c₁|p₁| + c₂|p₂| (called “pseudo-billiards”) is studied. For any kind of interaction, the canonical equations can always be integrated on sequential time intervals; i.e. in principle all the trajectories can be found explicitly.

Depending on the potential, a dynamical system of this class can either be completely integrable or behave just as a usual non-integrable Hamiltonian system with two degrees of freedom: in its phase space there exist invariant tori, stochastic layers, domains of global chaos, etc. Pseudo-billiard models of both the types are considered.

If a potential of a pseudo-billiard system has critical points (equilibria), then trajectories close to these points (“loops”) can exist; they can be treated as images of self-localized objects with finite duration. Such a model (with quartic potential) is also studied.     

Veiled assonance between geodesics on ellipsoid and billiard in its focal ellipse

We introduce new special ellipsoidal confocal coordinates in ⁿ (n ≥ 3) and apply them to the geodesic problem on a triaxial ellipsoid in ³ as well as the billiard problem in its focal ellipse.

Using such appropriate coordinates we show that these different dynamical systems have the same common analytic first integral. This fact is not evident because there exists a geometrical spatial gap between the geodesic and billiard flows under consideration, and this separating gap just “veils” the resemblance of the two systems.

In short, a geodesic on the ellipsoid and a billiard trajectory inside its focal ellipse are in a “veiled assonance”—under the same initial data they will be tangent to the same confocal hyperboloid. But this assonance is rather incomplete: the dynamical systems in question differ by their intrinsic action angle-variables, thereby the different dynamics arise on the same phase space (i.e. the same phase curves in the same phase space bear quite different rotation numbers).

Some results of this work have been published before in Russian (Tabanov, 1993) and presented to the International Geometrical Colloquium (Moscow, May 10–14, 1993) and the International Symposium on Classical and Quantum Billiards (Ascona, Switzerland, July 25–30, 1994).     

On the origin of 1.5 μm luminescence in porous silicon coated with sol–gel derived erbium-doped Fe2O3 films

Sol–gel derived Fe₂O₃ films containing about 10 wt% of Er₂O₃ were deposited on porous silicon by dipping or by a spin-on technique followed by thermal processing at 1073 K for 15 min. The samples were characterized by means of PL, SEM and X-ray diffraction analyses. They exhibit strong room-temperature luminescence at 1.5 μm related to erbium in the sol–gel derived host. The luminescence intensity increases by a factor of 1000 when the samples are cooled from 300 to 4.2 K. After complete removal of the erbium-doped film by etching and partial etching the porous silicon, the erbium-related luminescence disappears. Following this, luminescence at 1.5 μm originating from optically active dislocations (“D-lines”) in porous silicon was detected. The influence of the conditions of synthesis on luminescence at 1.5 μm is discussed.     

Determination of isotopic composition of plutonium in hot particles of the Chernobyl area

The knowledge of the isotopic composition of man-made transuranium elements (TUE) in the environmental samples is of great interest because, on the basis of these data, statements about the origin of the TUE can be made. One of the most radiotoxic elements released during reactor accidents and nuclear weapons tests was plutonium with the alpha emitters ²³⁸Pu, ²³⁹Pu, ²⁴⁰Pu, ²⁴²Pu and the beta-emitter ²⁴¹Pu which decays into ²⁴¹Am. The determination of plutonium in “hot” particles from the Chernobyl reactor was accomplished by means of solid state nuclear track detectors registering the alpha particles and by alpha spectroscopy after chemical treatment. Furthermore, in order to perform a complete analysis of the isotopic composition one of the “hot” particles has been investigated by resonance ionization mass spectrometry which possesses an excellent sensitivity and a good isotopic resolution.     

Measurement of the cascade time of ∑ in liquid helium

In a study of ∑⁻π⁺ production by stopped K⁻ in liquid helium, (19 ± 6)% of stopped ∑⁻ were observed to decay. This corresponds to a “cascade time” of 28 ± 8 psec.     

Coherent noise, scale invariance and intermittency in large systems

We introduce a new class of models in which a large number of “agents” organize under the influence of an externally imposed coherent noise. The model shows reorganization events whose size distribution closely follows a power law over many decades, even in the case where the agents do not interact with each other. In addition, the system displays “aftershock” events in which large disturbances are followed by a string of others at times which are distributed according to a t⁻¹ law. We also find that the lifetimes of the agents in the system possess a power-law distribution. We explain all these results using an approximate analytic treatment of the dynamics and discuss a number of variations on the basic model relevant to the study of particular physical systems.     

The magnetic anisotropy of samarium-alnico pseudobinary alloys

The anisotropy properties of samarium-Alnico V pseudobinary alloys have been investigated. With alloys containing less than 12.0 mol% samarium, the K₁ values are negative at 77 K and increase with increasing temperature to approximately zero at room temperature. The K₂ values remain positive at all temperatures. We do not find the easy cone that has long been thought to be existed in those alloys with K₁ < 0 and K₂ #62; 0. In alloys with samarium contents between 13.3 and 19.0 mol%, the K₁ and K₂ values are positive at all temperatures. The anisotropy fields are not changed monotonically in the whole range of 10.1 to 19.0 mol% of samarium. It is concluded that the alloys are characteristics in thermodynamically of first-order transition. We have found that the “hard cone” exists in each of those alloys with samarium content more than 16.0 mol% and at temperatures above 77 K. The alloys with samarium less that 13.4 mol% also have “hard cone” under 77 K. However, the observed “hard cone” is different from the well known one in the first-order magnetization process, and it will collapse to the easy axis when the measuring field and temperature increase while under room temperature.