Sonoluminescence of elementary sulfur melt

The sonoluminescence of liquid sulfur has been observed for temperatures of 120–180°C. The sonoluminescence intensity of the sulfur melt is 10⁹ photons/s at 120°C. As the temperature increases, the luminescence intensity decreases nonmonotonically, a maximum is observed at 160–175°C, and cavitation and luminescence cease at 180°C. The dependence obtained correlates with the temperature dependence of the viscosity of the sulfur melt. The sonoluminescence spectrum obtained with a resolution of 10 nm for 130–150°C contains one band with λ_max = 560 nm, the emitter of which is likely an (S⁺)* ion. When the melt is saturated with argon, the sonoluminescence intensity increases by an order of magnitude; in this case, the spectral band shape changes only slightly. The results confirm the “electric” theory of multibubble sonoluminescence. In the process of the sonolysis of the sulfur melt, biradical fragments are formed in cavitation bubbles consisting of sulfur molecules, which initially have the form of cyclooctasulfur S₈. These fragments can enter into the melts and can be involved in various chemical reactions. This circumstance makes it possible to recommend ultrasonic activation for reactions of sulfurization of hydrocarbons.     

Sonochemiluminescence in an aqueous solution of Ru(bpy)3Cl2

The sonochemiluminescence spectra of electron-excited ions ^*[Ru(bpy)₃]²⁺ was registered for the first time during sonolysis of argon saturated aqueous solutions of Ru(bpy)₃Cl₂ with low concentration. At single-bubble sonolysis, the luminescence band of ruthenium is recorded at a concentration of Ru(bpy)₃Cl₂ from 10⁻⁶ M, and at multibubble from 10⁻⁵ M. Possible mechanisms for the appearance of the band of a tris-bipyridyl ruthenium(II) complex on the background of an structureless continuum of water in the spectra of sonoluminescence are analyzed. Based on the results of the comparison of the sonoluminescence spectra of Ru(bpy)₃Cl₂ aqueous solutions with the sonoluminescence spectra of aqueous solutions of rhodamine B (which has a high quantum yield of photoluminescence) it was established that a possible mechanism of sonophotoluminescence does not play a decisive role in ruthenium sonoluminescence. The effect of radical acceptors (O₂, C₂H₅OH, Cd²⁺, I⁻) on ruthenium sonoluminescence is analyzed. The most significant mechanism for the formation of electron-excited ions ^*[Ru(bpy)₃]²⁺ during sonolysis is the sonochemiluminescence in oxidation-reduction reactions involving [Ru(bpy)₃]²⁺ ions and radical products of sonolysis of water (OH, H, e⁻_aq) in the solution volume.     

Luminescence of Tb3+ and Gd3+ ions in sonolysis under the conditions of a single bubble moving in aqueous solutions of TbCl3 and GdCl3

Luminescence bands of Tb³⁺ and Gd³⁺ ions are detected during sonolysis in the regime of a moving single bubble in aqueous solutions of TbCl₃ and GdCl₃ salts with concentration 1–2 mol/L. Saturation with argon, low temperatures of solutions (?5°C), and a high concentration of salts are the factors facilitating sonoluminescence of the metal. Comparison with the characteristics of sonoluminescence of lanthanide ions studied earlier in the regimes of multibubble and single-bubble sonolysis with a stationary bubble shows that the electron excitation of metal ions in the given case is associated with translational displacements of the bubble. Our results confirm the validity of the sonochemical model of microdroplet injection, which explains the penetration of nonvolatile salts into cavitation bubbles as a result of their deformation during intense movements.     

Multibubble sonoluminescence as a tool to study the mechanism of formic acid sonolysis

Sonoluminescence spectra collected from 0.1 to 3.0 M aqueous solutions of formic acid sparged with argon show the OH(A²Σ⁺−X²Π_i) and C₂(d³Π_g → a³Π_u) emission bands and a broad continuum typical for multibubble sonoluminescence. The overall intensity of sonoluminescence and the sonochemical yield of HCOOH degradation vary in opposite directions: the sonoluminescence is quenched while the sonochemical yield increases with HCOOH concentration. By contrast, the concentration of formic acid has a relatively small effect on the intensity of C₂ Swan band. It is concluded that C₂ emission originates from CO produced by HCOOH degradation rather than from direct sonochemical degradation of HCOOH. The intensity of C₂ band is much stronger at high ultrasonic frequency compared to 20 kHz ultrasound which is in line with higher yields of CO at high frequency. Another product of HCOOH sonolysis, carbon dioxide, strongly quenches sonoluminescence, most probably via collisional non-radiative mechanism.     

Luminescence of silver chloride microcrystals upon photoexcitation by different methods

The luminescence spectra of AgCl microcrystals were measured in two different regimes: in the regime of excitation of stationary luminescence and in the regime of photostimulated burst of luminescence. Differences between the spectra of stationary luminescence and the spectra of photostimulated-luminescence burst in the range between 430 and 590 nm have been found. The luminescence spectra are complex; the ratio of intensities for elementary components changes with the technique of excitation. Differences in the form and composition of complex luminescence bands obtained under different conditions of registration are attributed to the recombination interaction of the luminescence centers. It is shown that analysis of the dependences of intensity ratios for the elementary components of a complex luminescence band on the exciting-radiation intensity allows one to evaluate the mechanism of recombination in elementary bands provided that the mechanism is known for at least one luminescence band.__________Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 1, pp. 85–89. January–February, 2005.     

Single-bubble sonoluminescence of aqueous solutions of lanthanide chlorides and models of the sonochemistry of nonvolatile metal salts

The single-bubble sonoluminescence of d-f (Ce³⁺, Pr³⁺) and f-f (Tb³⁺) ions is detected in aqueous solutions of LnCl₃. It has been shown that the luminescence of these ions is sonophotoluminescence, i.e., the reemission of the absorbed short-wavelength part of the radiation spectrum of a blackbody, which appears in a bubble levitating in the field of a standing ultrasonic wave, in the bulk of the solution. In view of the revealed inefficiency of reemission in GdCl₃, the single-bubble sonoluminescence of Gd³⁺ has not been observed. The results indicate the low probability of the penetration of nonvolatile metal ions into the bubble in the hot shell model, which would be valid in single-bubble sonolysis and thereby confirm the validity of the injected droplet model, which explains the penetration to the bubble, electronic excitation, and luminescence of f-f ions Gd³⁺ and Tb³⁺ in multibubble sonolysis with an intensity much higher than the yield of their sonophotoluminescence.     

Luminescence and thermally stimulated recombination processes in Li<Subscript>6</Subscript>Gd(BO<Subscript>3</Subscript>)<Subscript>3</Subscript>:Ce<Superscript>3+</Superscript> crystals

The luminescence and thermally stimulated recombination processes in lithium borate crystals Li₆Gd(BO₃)₃ and Li₆Gd(BO₃)₃:Ce have been studied. The steady-state luminescence spectra under X-ray excitation (X-ray luminescence), temperature dependences of the intensity of steady-state X-ray luminescence (XL), and thermally stimulated luminescence (TSL) spectra of these compounds have been investigated in the temperature range of 90–500 K. The intrinsic-luminescence 312-nm band, which is due to the ⁶ P _J → ⁸ S _7/2 transitions in Gd³⁺ matrix ions, dominates in the X-ray luminescence spectra of these crystals; in addition, there is a wide complex band at 400–420 nm, which is due to the d → f transitions in Ce³⁺ impurity ions. It is found that the steady-state XL intensity in these bands increases several times upon heating from 100 to 400 K. The possible mechanisms of the observed temperature dependence of the steady-state XL intensity and their correlation with the features of electronic-excitation energy transfer in these crystals are discussed. The main complex TSL peak at 110–160 K and a number of minor peaks, whose composition and structure depend on the crystal type, have been found in all crystals studied. The nature of the shallow traps that are responsible for TSL at temperatures below room temperature and their relation with defects in the lithium cation sublattice are discussed.     

Luminescence mechanism of acoustic and laser-induced cavitation

A new approach is proposed for explaining the experimental data on sonoluminescence of acoustic and laser-induced cavitation bubbles. It is suggested that two different sonoluminescence mechanisms, namely, thermal and electric ones, are possible and that they manifest themselves depending on the bubble dynamics. An intense thermal luminescence occurs as a result of compression of an individual stationary spherical bubble; a weak electric luminescence accompanies the deformation and splitting of the bubble when thermal luminescence is suppressed (for example, in the case of multibubble sonoluminescence). It is shown that, when an individual bubble loses its spherical shape under the effect of different actions (change in the acoustic pressure, artificial deformation, translatory motion, etc.) or when a laser-induced bubble undergoes fragmentation, the sonoluminescence spectrum exhibits specific bands that are similar to the bands in the multibubble sonoluminescence spectrum. The appearance of these bands is attributed to the suppression of the thermal sonoluminescence mechanism and the manifestation of the electric mechanism. It is shown that the maximum temperature T _max characterizing the compression of a laser-induced bubble is primarily determined by the temperature of the plasma at the instant of the laser-induced breakdown, whereas, for an acoustic bubble, T _max is primarily determined by the acoustic and hydrostatic pressures and by the saturation vapor pressure of the liquid.     

Extreme conditions during multibubble cavitation: Sonoluminescence as a spectroscopic probe

We review recent work on the use of sonoluminescence (SL) to probe spectroscopically the conditions created during cavitation, both in clouds of collapsing bubbles (multibubble sonoluminescence, (MBSL)) and in single bubble events. The effective MBSL temperature can be controlled by the vapor pressure of the liquid or the thermal conductivity of the dissolved gas over a range from ～1600 to ～9000K. The effective pressure during MBSL is ～300bar, based on atomic line shifts. Given nanosecond emission times, this means that cooling rates are >10(12)K/s. In sulfuric and phosphoric acid, the low volatility and high solubility of any sonolysis products make bubble collapse more efficient and evidence for an optically opaque plasma core is found.     

A search for sonoluminescence in vivo in the human cheek

In a previous experiment, sonoluminescence was observed in aerated water, especially at the pressure antinodes in the standing-wave field of a physiotherapeutic ultrasound device (Therasonic 1030). Mammalian cells in vitro showed growth inhibition when placed at the pressure antinodes but not at adjacent pressure nodes. In the light of these results, we looked for sonoluminescence in vivo when a similar standing-wave field was set up. To detect luminescence, a light guide was held against the inner surface of the human cheek. This would channel any luminescence photons to a cooled, red-sensitive photomultiplier which would quantify the light. Direct insonation of the cheek produced no detectable luminescence. Similarly when a water bag was placed against the outer surface of the cheek, and the latter was insonated through the bag, no luminescence was detected. Sonoluminescence from the water bag was, however, detected when the bag was placed against the inner surface of the cheek, showing that absorption of sound by the cheek tissue was not preventing cavitation. Further analysis showed that if cavitation had been occurring in the cheek without detection using the system employed, then the resulting sonoluminescence would have to be at most 0.025 times as intense as that produced by an equivalent volume of aerated water.     

Luminescence properties of transparent ceramics Y<Subscript>3</Subscript>Al<Subscript>5</Subscript>O<Subscript>12</Subscript>:Yb

We present the results of studying the luminescence properties of transparent ceramics Y₃Al₅O₁₂:Yb obtained by the vacuum sintering and nanocrystalline technology. In the course of research, we measured the luminescence and luminescence excitation spectra, as well as the temperature and kinetic behavior of luminescence. Our results are analyzed in comparison with the characteristics of corresponding single crystals. We revealed that processes of generation and relaxation of electronic excitations that occur in ceramics, in particular, in the charge transfer state, are similar to processes occurring in crystals. The behavior of two charge-transfer luminescence bands at 340 and 490 nm is studied. In the range 300–600 nm, we revealed a broad emission band of radiation of other type, which is also observed in spectra of undoped ceramics. This broad band is attributed to F⁺ centers. Emission and excitation spectra of charge transfer luminescence at a maximum of the temperature dependence of 100 K are measured for the first time. We found that, upon excitation in the charge transfer band, luminescence in ceramics is more intense than in single crystals with similar concentrations of Yb and has a higher quenching temperature.     

有机溶液中圆锥泡声致发光

在U形管声致发光装置的基础上建立了一套新型的声致发光装置——直管圆锥泡声致发光装置. 利用此装置以有机溶液为液体介质得到了超强的发光脉冲并测量得到了其发光光谱. 结果表明发光光谱为一从紫外光至可见光波长范围的连续谱,上面叠加有C₂的d³Π_g→d³Π_u跃迁形成的五个序列谱带,分别对应于Δv=-2,Δv=-1,Δv=0,Δv< 关键词： 声致发光 光谱 斯旺带 振动温度     

Anti-stokes luminescence of solid AgCl<Subscript>0.95</Subscript>I<Subscript>0.05</Subscript> solutions

An anti-Stokes luminescence band with λ_max = 515 nm of microcrystals of solid AgCl_0.95I_0.05 solutions excited by a radiation flux of density 10¹³–10¹⁵ quanta/cm²·sec in the range 600–800 nm at 77 K was detected. It is shown that the intensity of this luminescence and the frequency of its excitation depend on the prior UV-irradiation of samples. Analysis of the stimulated-photoluminescence spectra and the anti-Stokes luminescence excitation spectra of the indicated microcrystals has shown that to the centers of anti-Stokes luminescence excitation correspond local levels in the forbidden band of the crystals. These states are apparently due to the atomic and molecular disperse silver particles that can be inherent in character or formed as a result of a low-temperature photochemical process. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 6, pp. 738–742, November–December, 2005.     

Optical characterization of sol gel TiO<Subscript>2</Subscript> monoliths doped with Brilliant Green

Amorphous titanium dioxide monoliths doped with brilliant green (BG) were synthesized by the sol-gel process. The optical properties of the monoliths were characterized by Photoacoustic Spectroscopy and Photoluminescence Spectroscopy. The absorption spectra for the BG-doped TiO₂ monoliths exhibited two well defined absorption regions: a band below 400 nm corresponding to TiO₂ absorption and three absorption bands centered at 424 nm, 588 nm, and 632 nm due to brilliant green. While the undoped TiO₂ monoliths showed no luminescence, the doped samples showed a strong luminescence band at 673 nm, which increased its intensity for increasing organic dye doping.     

Sonoluminescence intensity and ultrasonic cavitation temperature in organic solvents: Effects of generated radicals

Ultrasonic cavitation in organic solvents remains poorly understood in contrast with aqueous systems, largely because of complexities related to solvent decomposition. In this study, we sonicated different types of organic solvents (i.e. linear alkanes, aliphatic alcohols, aromatic alcohols, and acetate esters) under argon saturation. The average temperature of the cavitation bubbles was estimated using the methyl radical recombination method. We also discuss the effects of the physical properties of the solvents, such as vapor pressure and viscosity, on the cavitation temperature. The average cavitation bubble temperature and sonoluminescence intensity were higher in organic solvents with lower vapor pressure; for aromatic alcohols, these values were particularly high. It was found that the specific high sonoluminescence intensities and average cavitation temperatures exhibited in aromatic alcohols are caused by the highly resonance-stable generated radicals. The results obtained in this study are very useful for acceleration of sonochemical reaction in organic solvents, which are indispensable for organic synthesis and material synthesis.     

Multibubble sonoluminescence spectra of water which resemble single-bubble sonoluminescence

Multibubble sonoluminescence (MBSL) spectra of water from cavitation clouds were collected in the presence of different noble gases and at different acoustic intensities. Results show that at high acoustic intensity and with xenon as a dissolved gas the emission of the OH* radical becomes indiscernible from the continuum. These spectra resemble single-bubble sonoluminescence (SBSL) spectra. It is concluded that the source of emission in MBSL and SBSL can be the same, the difference in spectra is due to the higher temperature inside the bubble during SBSL.     

丙三醇溶液声致发光中的黑体辐射谱

利用U型管圆锥泡声致发光装置,测量到了丙三醇溶液中圆锥泡声致发光的光谱和光脉冲。结果表明,测量得到的发光光谱为光滑的连续谱,且与理论模拟得到的黑体辐射谱相吻合,拟合温度分布于2 600～3 500 K范围内。文章从空间和时间两方面分析了圆锥泡空化发光中存在黑体辐射的原因：较大的气泡体积(气泡塌缩半径为1.4 cm)与较长的发光时间(几十微秒)。另外,实验研究表明随着发光波长的增长,光脉冲宽度变宽,从而进一步证明了圆锥泡声致发光中的黑体辐射机制。最后,利用测量得到的发光光谱和脉冲计算得到了发光光强为0.18 J,远远高于其他方式得到的声致发光光强。     

Anomalous isotopic effect in multibubble sonoluminescence of aqueous solutions of terbium chloride

An anomalously low isotope effect has been discovered in 20-kHz sonoluminescence of terbium chloride solutions in H₂O-D₂O mixtures. The intensity of luminescence in the characteristic 488-and 545-nm lines of the Tb³⁺ ion, which are observed against the solvent continuum (230–700 nm), increases with the content of D₂O to a maximum value of 4.0 ± 0.4, whereas the isotope effect in photoluminescence of the same solutions reaches 10 ± 1.0. The result is explained using the model of nonexponential decay of sonoluminescence of Tb³⁺ ions. These ions, which are formed in an excited state in cavitation bubbles, first undergo radiative and radiationless deactivation in the gas phase. However, some excited ions enter the solution bulk, because the excitation lifetime is longer than the average bubble lifetime. At the first stage, the isotope effect is small, because the density of the gas phase is low and quenching by solvent molecules is weak. At the second stage, the isotope effect coincides with the effect in usual photoluminescence in the solution. The total decrease in the effect in sonoluminescence depends on the weight of the “gas” stage of deactivation of excited Tb³⁺ ions.     

The role of vapour pressure in multibubble sonoluminescence from organic solvents

The action of high intensity cavitation on several liquid halocarbons (C(2)Cl(4) CCl(4), CHCl(3), C(2)H(2)Br(4)) and other organic solvents (acetone, benzene and their mixtures) was investigated by recording multibubble sonoluminescence UV-Vis spectra over the temperature range between 246 and 298 K. The temperature induced variation of some thermophysical properties of the solvents Favours the interpretations of their role in determining the salient characteristics of the recorded spectra. We observed that high volatility does not necessarily quench sonoluminescence emission and that argon flow plays a key role in the appearance of radical emission lines. While for each investigated substance the intensity of C*(2) emission lines was clearly correlated to temperature, a comparative test between different halocarbons did not show a clear correlation with vapour pressure. Following recently reported results which evidenced the formation of dynamically differentiated populations of emitting bubbles in sulphuric acid, we performed MBSL experiments in liquid mixtures of halocarbons and sulphuric acid to investigate the correlation between the production of emitting species and the halocarbon volatility.     

Luminescence of CsBr:Eu films grown by liquid-phase epitaxy

By liquid-phase epitaxy from an aqueous alcoholic solution, we have obtained films of the well-known storage phospor CsBr:Eu, and we have studied their cathodoluminescence and photoluminescence (PL) spectra compared with the undoped CsBr films. We have established that the structure of the photoluminescence centers of the CsBr:Eu films when excited by laser radiation in the absorption band of the Eu²⁺ ions (λ = 337 nm) includes Eu²⁺-V_Cs isolated dipole centers and CsEuBr₃ aggregate centers, and also luminescence centers based on inclusions of hydroxyl group OH⁻ with the corresponding emission bands in the 440 nm, 520 nm, and 600 nm regions. We have studied the dependence of the spectra and the intensity of the photoluminescence for CsBr:Eu films on annealing temperature in air at 423–483 K, compared with analogous dependences for CsBr:Eu single crystals obtained from the melt. We have shown that annealing the films at T = 423–463 K leads to rapid formation of CsEuBr3 aggregate luminescence centers, while for T > 473 K thermal degradation of these centers occurs. We conclude that the observed differences between the photoluminescence spectra of CsBr:Eu films and CsBr:Eu single crystals may be due to additional doping of the films with OH⁻ ions. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 2, pp. 191–194, March–April, 2006.