Effect of dissolved gases on sonochemical oxidation in a 20 kHz probe system: Continuous monitoring of dissolved oxygen concentration and sonochemical oxidation activity

Dissolved gases have a substantial influence on acoustic cavitation and sonochemical oxidation reactions. Little research on the changes in dissolved gases and the resultant changes in sonochemical oxidation has been reported, and most studies have focused only on the initial dissolved gas conditions. In this study, the dissolved oxygen (DO) concentration was measured continuously during ultrasonic irradiation using an optical sensor in different gas modes (saturation/open, saturation/closed, and sparging/closed modes). Simultaneously, the resulting changes in sonochemical oxidation were quantified using KI dosimetry. In the saturation/open mode using five gas conditions of Ar and O₂, the DO concentration decreased rapidly when O₂ was present because of active gas exchange with the atmosphere, and the DO concentration increased when 100% Ar was used. As a result, the order of the zero-order reaction constant for the first 10 min (k_0-10) decreased in the order Ar:O₂ (75:25) > 100% Ar ≈ Ar:O₂ (50:50) > Ar:O₂ (25:75) > 100% O₂, whereas that during the last 10 min (k_20-30) when the DO concentration was relatively stable, decreased in the order 100% Ar > Ar:O₂ (75:25) > Ar:O₂ (50:50) ≈ Ar:O₂ (20:75) > 100% O₂. In the saturation/closed mode, the DO concentration decreased to approximately 70–80% of the initial level because of ultrasonic degassing, and there was no influence of gases other than Ar and O₂. Consequently, k_0-10 and k_20-30 decreased in the order Ar:O₂ (75:25) > Ar:O₂ (50:50) > Ar:O₂ (25:75) > 100% Ar > 100% O₂. In the sparging/closed mode, the DO concentration was maintained at approximately 90% of the initial level because of the more active gas adsorption induced by gas sparging, and the values of k_0-10 and k_20-30 were almost the same as those in the saturation/closed mode. In the saturation/open and sparging/closed modes, the Ar:O₂ (75:25) condition was most favorable for enhancing sonochemical oxidation. However, a comparison of k_0-10 and k_20-30 indicated that there would be an optimal dissolved gas condition that was different from the initial gas condition. In addition, the mass-transfer and ultrasonic-degassing coefficients were calculated using changes in the DO concentration in the three modes.     

Second upper-bound on the three-phonon resistivity in Ge

Contributions of different allowed three-phonon resistances in Ge have been presented in the second upper-bound W^>₁. It is found that the deviation of W^>₁ from W^>₀, the first upper-bound, is markable. As a matter of fact W^>₁ is shown to be less than W^>₀ by about 14% at 100°K and about 5% at 300°K.     

Inverse scattering with non-overdetermined data

Let A(β,α,k) be the scattering amplitude corresponding to a real-valued potential which vanishes outside of a bounded domain D⊂R³. The unit vector α is the direction of the incident plane wave, the unit vector β is the direction of the scattered wave, k>0 is the wave number. The governing equation for the waves is [∇²+k²−q(x)]u=0 in R³. For a suitable class M of potentials it is proved that if Aq₁(−β,β,k)=Aq₂(−β,β,k),∀β∈S², ∀k∈(k₀,k₁), and q₁, q₂∈M, then q₁=q₂. This is a uniqueness theorem for the solution to the inverse scattering problem with backscattering data. It is also proved for this class of potentials that if , ∀k∈(k₀,k₁), and q₁, q₂∈M, then q₁=q₂. Here is an arbitrarily small open subset of S², and |k₀−k₁|>0 is arbitrarily small.     

Excitation intensity dependence of shallow donor bound exciton luminescence in n-GaAs

Luminescence measurements were performed on high purity epitaxial n-GaAs $\text{(}\text{1 × 10}{}^{14}\text{cm}{}^3\text{< n <}\text{3 × 10}{}^{15}\text{cm}{}^3\text{)}$ for various excitation intensities I₀ in the range $\text{8 mW}\text{cm}{}^2\text{< I}{}_0\text{<}\text{4 W}\text{cm}{}^2$. The luminescence line corresponding to the radiative decay of the shallow donor bound exciton, (D⁰, X), broadens with increasing I₀ and appears as a doublet for $\text{I}{}_0\text{? 1}\text{W}\text{cm}{}^2$, while the two-electron replica of the (D⁰, X) remains a single narrow line. The doublet structure of the (D⁰, X) at elevated excitation levels is due to missing luminescence intensity in the center of the line as a consequence of low (D⁰, X) concentration in a layer extending 1–2 μm from the sample surface into the bulk. The low concentration of (D⁰, X) is attributed to capture of (D⁰, X) quanta into surface states, extending to lower energies from the Fermi level fixed by the shallow donors. Comparison of the present results with luminescence spectra obtained by various authors reveals, that unexplained spectral features in the (D⁰, X) region of n-GaAs reported in the literature are a consequence of high excitation intensity and correspond to the effect reported here. In partly compensated p-GaAs with donor concentrations as given above, the (D⁰, X) did not transform into a doublet structure even at $\text{W}\text{cm}{}^2$ excitation intensity.     

Theory of light scattering from a system of interacting Brownian particles

Starting from a N-particle diffusion equation for a system of N interacting spherical Brownian particles, a non-linear transport equation for concentration fluctuations δc(r, t) of the particles is derived. This dynamic equation is transformed into a hierarchy of equations for retarded propagators of increasing numbers of concentration fluctuations. A cluster expansion to lowest order in the average concentration results in a set of two coupled equations. The spectrum of light scattered by the interacting particles is in general not a Lorentzian, due to the non-linear term in the transport equation. For small scattering wave vectors k the width is D(ω)k², where ω is the transferred frequency. It is shown that D(0) = D_e, the effective diffusion coefficient. For a hardcore interaction potential the spectrum is Lorentzian and it is found that D_e = D₀(1 + φ), where D₀ is the diffusion constant for independent particles and φ the volume concentration of Brownian particles.     

Effective biaxial modulus and strain energy density of ideally (h k l)-fiber-textured cubic polycrystalline films

The effective biaxial modulus (M_eff) and strain energy density (W) of cubic polycrystalline films with ideally (h k l) fiber textures are estimated using Vook-Witt (VW) grain interaction model and the data are compared with those derived from Voigt, Reuss and Voigt-Reuss-Hill (VRH) models. Numerical results show that the VW average of M_eff for ideally (1 0 0)- or (1 1 1)-fiber-textured films is identical to the VRH average of M_eff. For (1 1 0) and (1 1 2) planes, however, the VW average of M_eff for (1 1 0)-fiber-textured film is larger than that of (1 1 2)-fiber-textured film when the Zener anisotropic factor (A_R) is not equal to 1. Furthermore, M_eff and W exhibit incremental tendencies with the increase of the orientation factor (Γ_h k l) for the [h k l] axis when A_R > 1, implying that M_eff and W have the minimums on the (1 0 0) plane. Reversely, M_eff and W decrease with the increasing Γ_h k l when A_R < 1. This means that M_eff and W on (1 1 1) plane have the minimums.     

High-precision frequency measurements of the ν1 + ν3 combination band of C2H2 in the 1.5 μm region

A pair of 1.5 μm semiconductor laser frequency standards have been developed for optical telecommunications use, stabilised to transitions of ¹²C₂H₂ and ¹³C₂H₂, using cavity-enhanced Doppler-free saturation absorption spectroscopy. The absolute frequencies of 41 lines of the ν₁ + ν₃ band of ¹²C₂H₂, covering the spectral region 1520-1545 nm, have been measured by use of a passive optical frequency comb generator, referenced to ¹³C₂H₂ transitions of known frequency. The mean experimental uncertainties (coverage factor k = 1) of the frequency values are 3.0 kHz (type A) and 10 kHz (type B). Improved values of the band origin ν₀, rotational constants B′ and B″, and centrifugal distortion coefficients D′, D″, H′, and H″ are presented.     

D-dimensional massless particle with extended gauge invariance

We propose the model ofD-dimensional massless particle whose Lagrangian is given by theN-th extrinsic curvature of world-line. The system hasN+1 gauge degrees of freedom constitutingW-like algebra; the classical trajectories of the model are space-like curves which obey the conditionsk _N+a=k_N−a, k_2N =0,a=1, ...,N−1,N≤[(D−2)/2], while the firstN curvaturesk _i remain arbitrary. We show that the model admits consistent formulation on the anti-DeSitter space. The solutions of the system are the massless irreducible representations of Poincaré group withN nonzero helicities, which are equal to each other. Presented at the 9th Colloquium “Quantum Groups and Integrable Systems”, Prague, 22–24 June 2000.     

A theoretical deduction of the shape and size of nanocarbons suitable for hydrogen storage

We evaluated the adsorption energy of a hydrogen molecule in nanocarbons consisting of graphene sheets. The nanocarbon shapes were a pair of disks with separation 2d, a cylinder with radius d, and a truncated sphere with radius d. We obtained the adsorption energy in the form of a 10–4 Lennard–Jones function with respect to 1/d. The values of the potential depth (D) and equilibrium distance (d _e), respectively, were 94 meV and 2.89 Å for the disk pair, 158 meV and 3.14 Å for the cylinder, and 203 meV and 3.37 Å for the sphere. When d=d _e, the adsorption energy of the disk pair (cylinder) became deeper than ?0.9D, and it approached ?D when the radius (length) increased to more than twice its separation (radius). The adsorption energy of the sphere was increased from ?D to ?0.5D when the radius of the opening increased from 0 to d _e. These results suggest that porous carbon materials can increase the adsorption energy by up to ～200 meV if the carbon atoms are arranged on a spherical-like surface with ～7 Å separation. This may lead to practical hydrogen storage for fuel cells.     

A Boubaker polynomials expansion scheme (BPES)-related protocol for measuring sprayed thin films thermal characteristics

Measurements of In₂S₃ and ZnIn₂S₄ sprayed thin films thermal characteristics have been carried out using the photodetection technique. The thermal conductivity k and diffusivity D were obtained using a new protocol based on photothermal signal parameters analysis. Measured values of k and D were respectively, (15.2 ± 0.85) W m⁻¹K⁻¹ and (69.8 ± 7.1) × 10⁻⁶ m²s⁻¹ for In₂S₃, (7.2 ± 0.7) W m⁻¹K⁻¹ and (32.7 ± 4.3) × 10⁻⁶ m²s⁻¹ for ZnIn₂S₄. These values are extremely important since similar compounds are more and more proposed as Cd-free alternative materials for solar cells buffer layers.     

Far-infrared spectrum of the internal rotation in methylamine

The far-infrared spectra of the Q branches of hindered rotation of CH₃NH₂ were studied in the 80 to 280 cm^?1 spectral region with resolutions up to 0.12 cm^?1. Through the theoretical analysis 11 of the 12 b-type parameters I_a1, I_a2, V₃, V₆, k₁, k₂, k₃, k₄, k₅, k₆, k₇, D_KK are determined using a nonlinear least-squares fit. The agreement between the observed and the final theoretical spectrum is satisfactory considering that only Q-branch lines were studied. Experimentally more lines, especially at low frequencies, were observed which probably belong to P- and R-branch lines of clusters thereof.     

A study of the neutrino production of <Emphasis Type="Italic">φ</Emphasis> and <Emphasis Type="Italic">D</Emphasis><Stack><Subscript><Emphasis Type="Italic">s</Emphasis></Subscript><Superscript>+</Superscript></Stack> mesons

The charged current neutrino production of φ and D _s ⁺ mesons is studied, using the data obtained with the SKAT bubble chamber exposed to the Serpukhov accelerator neutrino beam. It is found that the φ production occurs predominantly in the forward hemisphere of the hadronic c.m.s. (at x _F > 0, x _F being the Feynman variable), with the mean yield strongly exceeding the expected yield of directly produced φ mesons and varying from 〈n _φ(x _F s 0)〉 = (0.92 ± 0.34) × 10^?2 at W > 2 GeV up to (1.23 ± 0.53) × 10^?2 at W > 2.6 GeV and (1.44 ± 0.69) × 10^?2 at W > 2.9 GeV, W being the invariant mass of the hadronic system. For the first time, the inclusive yield of leading D _s ⁺ mesons carrying more than z = 0.85 of the current c-quark energy is estimated: 〈n _{D s} ⁺ (z > 0.85, W > 2.9 GeV)〉 = (6.64 ± 1.91) × 10^?2. It is shown that the shape of measured φ meson differential spectrum on xF is reproduced by that expected from the D _s ⁺ → φX decays. An indication was obtained that this expected spectrum underestimates the measured φ yield.     

Growing networks with preferential deletion and addition of edges

A preferential attachment model for a growing network incorporating the deletion of edges is studied and the expected asymptotic degree distribution is analyzed. At each time step t=1,2,…, with probability π₁>0 a new vertex with one edge attached to it is added to the network and the edge is connected to an existing vertex chosen proportionally to its degree, with probability π₂ a vertex is chosen proportionally to its degree and an edge is added between this vertex and a randomly chosen other vertex, and with probability π₃=1−π₁−π₂<1/2 a vertex is chosen proportionally to its degree and a random edge of this vertex is deleted. The model is intended to capture a situation where high-degree vertices are more dynamic than low-degree vertices in the sense that their connections tend to be changing. A recursion formula is derived for the expected asymptotic fraction p_k of vertices with degree k, and solving this recursion reveals that, for π₃<1/3, we have p_k∼k^{−(3−7π₃)/(1−3π₃)}, while, for π₃>1/3, the fraction p_k decays exponentially at rate (π₁+π₂)/2π₃. There is hence a non-trivial upper bound for how much deletion the network can incorporate without losing the power-law behavior of the degree distribution. The analytical results are supported by simulations.     

Forbidden rotational spectra of polyatomic molecules

Some of the pure rotational transitions of polyatomic molecules that are forbidden according to the rigid rotor selection rules may acquire intensity by a centrifugal distortion mechanism, in which the intensity depends on the dipole derivatives and on the displacements in the normal coordinates produced by centrifugal distortion. The structures of the predicted spectra are discussed for nonpolar molecules belonging to the point groups D_3h, D_n (n > 2), D_2d, and T_d. Some of the calculated R-branch lines of methane are stronger than some of the lines of HD already observed in the same frequency range. For polar molecules extra contributions to the intensity must be considered and are exemplified for the Δk = ±3 transitions of C_3v molecules. These forbidden rotational transitions may have some astrophysical importance.     

Segregation during crystal growth from melt and absorption cross section determination by optical absorption method

Segregation during crystal growth from melt under two conditions is studied by using crystal mass, which can be measured easily, as an independent variable, and a method to determine the effective segregation coefficient and absorption cross section of optical dopant is given. When the segregated solute disperses into the whole or just a part of melt homogenously, the concentration C _s in solid interface will change by different formulas. If the crystal growth interface is conical and segregated solute disperses into melt in total or part, the solute concentration at r = 2/3R, where r is the distance from the growth cross section center and R the crystal radius, is independent on the shape of the crystal growth interface, and its variation at r = 2/3R can be regarded as the result from crystal growth in flat interface. With C _s variation formula in solid and absorption cross section σ for optical dopant, the absorption coefficients along the crystal growth direction can be calculated, and the corresponding experimental value can be obtained through the crystal optical absorption spectra. By minimizing the half sum, whose independent variables are k, ΔW or σ, of the difference square between the calculated and experimental absorption coefficients from one or more absorption peaks along the crystal growth direction, k and σ, or k and ΔW, can be determined at the same time through the Levenberg-Marquardt iteration method. Finally, the effective segregation coefficient k, ΔW and absorption cross sections of Nd:GGG were determined, the results fitted by two formula gave more closed effective segregation coefficient, and the value ΔW also indicates that the segregated dopant had nearly dispersed into the whole melt. Experimental results show that the method to determine effective segregation coefficient k, ΔW and absorption cross sections σ is convenient and reliable, and the two segregation formulas can describe the segregation during the crystal growth from melt relatively commendably. Supported by the National Natural Science Foundation of China (Grant No. 50772112)     

2D-isothermal compressibility of deposited gold layer on Au(1 1 1) surface

Based on thermodynamic arguments, a simple formula is derived that relates the 2D-isothermal compressibility, κ_2D, directly to (∂L_D/∂E)_T and (∂L_D/∂N)_T, where L_D is the stripe separation of the Au(1 1 1) surface, E is the applied electrode potential and N is the surface concentration of deposit. It accounts for the deposition-induced compression of the top most Au(1 1 1) surface layer during gold deposition. Furthermore, the value of κ_2D for the deposited gold layer on Au(1 1 1) surface has been experimentally determined. The results reveal that the κ_2Dvalue for gold does not match the reported trend for other metals.     

Elastic,piezoelectric and dielectric properties of ZnO and CdS single crystals in a wide range of temperatures

A complete set of elastic, piezoelectric and dielectric constants of ZnO and CdS at room temperature was determined by the method of resonance-antiresonance. Elastic constants s^E₁₁, s^E₁₂, s^E₅₅, c^D₃₃, c^D₅₅, coefficients of electromechanical couplingk₃₁, k₁₅, k_t and dielectric constants ε^T₁₁, ε^T₃₃ of ZnO single crystals were determined in the temperature range 4.2–800 K. Elastic constants s^E₁₁, s^E₁₂, s^D₃₃, s^E₅₅, s^D₃₃, s^D₅₅, coefficients of electromechanical coupling k₃₁, k₃₃, k₁₅, k_t and dielectric constants ε^T₁₁, ε^T₃₃ of CdS single crystals were determined in the temperature range 4.2–300 K.     

Sliding behavior of oil droplets on nanosphere stacking layers with different surface textures

Two facile coating techniques, gravitational sediment and spin coating, were applied for the creation of silica sphere stacking layers with different textures onto glass substrates that display various sliding abilities toward liquid drops with different surface tensions, ranged from 25.6 to 72.3 mN/m. The resulting silica surface exhibits oil repellency, long-period durability > 30 days, and oil sliding capability. The two-tier texture offers a better roll-off ability toward liquid drops with a wide range of γ_L, ranged from 30.2 to 72.3 mN/m, i.e., when the sliding angle (SA) < 15°, the oil droplet start to roll off the surface. This improvement of sliding ability can be ascribed to the fact that the two-tier texture allows for air pockets (i.e., referred to as the Cassie state), thus favoring the self-cleaning ability. Taking Young-Duprè equation into account, a linearity relationship between sine SA and work of adhesion (W_ad) appears to describe the sliding behavior within the W_ad region: 2.20-3.03 mN/m. The smaller W_ad, the easier drop sliding (i.e., the smaller SA value) takes place on the surfaces. The W_ad value ∼3.03 mN/m shows a critical kinetic barrier for drop sliding on the silica surfaces from stationary to movement states. This work proposes a mathematical model to simulate the sliding behavior of oil drops on a nanosphere stacking layer, confirming the anti-oil contamination capability.     

Radiative and radiationless processes of Eu3+ in dimethyl sulfoxide

Solutions of Eu³⁺ in dimethyl sulfoxide (DMSO) exhibit a considerable enhancement in the intensities of bands associated with ?J = 2 both in the absorption and in the emission spectra. This effect is so strong that addition of considerable amounts of either D₂O or H₂O has no effect at all. Contrary to that, addition of very small quantities of DMSO in solutions of Eu³⁺ in D₂O is accompanied by drastic changes in the appropriate transition probabilities. In solutions of Eu³⁺ in DMSO containing relatively small [H₂O] or [D₂O], the primary solvation sphere appears to consist mainly of DMSO. Secondary and primary fluorescence quenching rate constants have been determined such as: k^sec_D2O ? 5.1 M^-1s^-1; k^sec_DMSO ? 20 M^-1s^-1 and k_fl + k^≈_h ? 4.5 × 10²s^-1.     

Distribution of Particles Which Produces a “Smart” Material

If A _q(β, α, k) is the scattering amplitude, corresponding to a potential , where D⊂ℝ³ is a bounded domain, and is the incident plane wave, then we call the radiation pattern the function , where the unit vector α, the incident direction, is fixed, β is the unit vector in the direction of the scattered wave, and k>0, the wavenumber, is fixed. It is shown that any function , where S ² is the unit sphere in ℝ³, can be approximated with any desired accuracy by a radiation pattern: , where ∊ >0 is an arbitrary small fixed number. The potential q, corresponding to A(β), depends on f and ∊, and can be calculated analytically. There is a one-to-one correspondence between the above potential and the density of the number of small acoustically soft particles D _m⊂ D, 1≤ m≤ M, distributed in an a priori given bounded domain D⊂ℝ³. The geometrical shape of a small particle D _m is arbitrary, the boundary S _m of D _m is Lipschitz uniformly with respect to m. The wave number k and the direction α of the incident upon D plane wave are fixed. It is shown that a suitable distribution of the above particles in D can produce the scattering amplitude , at a fixed k>0, arbitrarily close in the norm of L ²(S ²× S ²) to an arbitrary given scattering amplitude f(α ', α), corresponding to a real-valued potential q∊ L ²(D), i.e., corresponding to an arbitrary refraction coefficient in D. MSC: 35J05, 35J10, 70F10, 74J25, 81U40, 81V05, 35R30. PACS: 03.04.Kf.