Kinetics of the formation of gas bubbles during polarization of copper and graphite electrodes in electrolytic aqueous solutions

The adsorption and kinetic processes of the formation of gas bubbles passivating the surface during polarization of copper and graphite electrodes in 1% aqueous solution of sulfuric acid have been investigated. Three stages of the process related to the recharging of the double electric layer—adsorption accumulation of the gas escaping from the surface, the critical nucleation of the gas bubbles, and their subsequent growth—have been revealed, distinguished, and quantitatively estimated. It has been shown that potential leveling at the steady-state value specified by the Tafel equation is unambiguously associated with achievement of the limiting surface area screened by the gas bubbles for each particular current density. The surface diffusion constants D _H = (1.5–4.4) × 10⁻⁴ and (0.1–3.8) × 10⁻⁵ cm²/s of hydrogen on copper and graphite, respectively, and D _O = (1.8–4.5) × 10⁻⁷ cm²/s of oxygen on graphite during the motion toward the drain (the gas bubbles) have been calculated.     

Investigation on F–B–S tri-doped nano-TiO<Subscript>2</Subscript> films for the photocatalytic degradation of organic dyes

F–B–S tri-doped titanium dioxide thin films on common glass were prepared by a modified sol–gel method, in which tetrabutyl titanate (Ti(OC₄H₉)₄) was chosen as the precursor and boric acid (H₃BO₃), sodium fluoride (NaF), and thiourea (N₂H₄CS) were employed as boron, fluorine, and sulfur sources, respectively. The microstructure and optical property were characterized by X-ray diffraction, high-resolution field emission scanning electron microscopy, N₂ adsorption–desorption isotherms, photoluminescence spectrum, and UV–Vis diffraction reflectance spectroscopy. The photocatalytic performances were evaluated by decomposition of organic dyes in solution. The experimental results revealed that the F–B–S tri-doped TiO₂ thin film was composed of uniform round-like nano-particles with the size range of 5–8 nm. F–B–S tri-doping not only significantly promoted the UV-induced photodecomposition activities of TiO₂ films but also extended the optical response of TiO₂ red shift to visible light region, herein improving the visible light-induced degradation of organic dyes. The improvement mechanism by F–B–S tri-doping was also discussed.     

Synthesis of Novel Eu(III) Luminescent Probe Based on 9- Acridinecarboxylic Acid Skelton for Sensing of ds-DNA

Eu(III)-9-acridinecarboxylate (9-ACA) complex was synthesized and characterized by elemental analysis, conductivity measurement, IR spectroscopy, thermal analysis, mass spectroscopy, ¹H-NMR, fluorescence and ultraviolet spectra. The results indicated that the composition of this complex is [Eu(III)-(9-ACA)₂(NCS)(C₂H₅OH)₂] 2.5 H₂O and the oxygen of the carbonyl group coordinated to Eu(III). The interaction between the complex with nucleotides guanosine 5′- monophosphate (5′-GMP), adenosine 5′-diphosphates (5′-ADP), inosine (5′-IMP) and CT-DNA was studied by fluorescence spectroscopy. The fluorescence intensity of Eu(III)-9-acridinecarboxylate complex was enhanced with the addition of CT-DNA. The effect of pH values on the fluorescence intensity of Eu(III) complex was investigated. Under experimental conditions, the linear range was 9–50 ng mL⁻¹ for calf thymus DNA (CT- DNA) and the corresponding detection limit was 5 ng mL⁻¹. The results showed that Eu(III)-(9-ACA)₂ complex binds to CT-DNA with stability constant of 2.41 × 10⁴ M .     

Complexation between variable-valency uranium and organic ligands in solutions,their photostability and spectral identification

We discuss possible directions for searching for prospective materials based on low-valency uranium (III–V) as detection media for hard electromagnetic radiation. We have studied the processes of formation of tetravalent and pentavalent uranium complexes from UO₂(NO₃)₃·6H₂O and UO₂Cl₂·H₂O in DMF and with addition of CCl₄, including when the systems are exposed to radiation in the visible range (400–450 nm). In the first case (UO₂(NO₃)₃·6H₂O solutions in DMF), upon irradiation we observe stable complexes of pentavalent uranium, and when CCl₄ is added to the solution we observe complexes of tetravalent uranium. In the system UO₂Cl₂·3H₂O in DMF, we do not observe the appearance of new forms of uranium; but when CCl₄ is added, then complexes of tetravalent uranium are formed. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 2, pp. 184–187, March–April, 2007.     

Vibrational spectra of thin eulytine films

This is a study of IR reflection spectra of systems of a thin Bi₄X₃O₁₂(X=Si, Ge) film and a substrate of fused quartz v-SiO₂ in the range 400–1600 cm⁻¹ at T=295 K. Bands assigned to Bi₄X₃O₁₂ are interpreted. It is found that single-photon processes are exhibited in the range 400–800 cm⁻¹, while biphonon processes, in the range 800–1600 cm⁻¹. I. Franko State University of Lvov, 50 Dragomanov St., 290005, Lvov, Ukraine. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 4, pp. 494–498, July–August, 1997.     

Molecular structures and stratification in a 2-butanol—water system

The results of investigation of the spectra of 2-butanol in CCl₄, pure 2-butanol, and a 2-butanol— water mixture in the region of the second overtone of the stretching O—H vibration are presented. The assignment of the bands of the overtones is performed. The role of various associates in the processes of stratification in the 2-butanol—water system is discussed. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 6, pp. 837–839, November–December, 2005.     

Microhydration of the methylene blue cation in an electrospray ion source

Microhydrated methylene blue cations, MB⁺(H₂O) _n , are produced in an electrospray ion source and their size-distributions are measured as a function of the source temperature. A series of MB⁺(H₂O) _n ions is observed up to n ≃ 60. A striking feature observed in the mass spectra is that the series of hydrated ions starts at n = 4; intensities of n = 1–3 are extremely suppressed. The absence of n = 1–3 ions is well explained by the energetics concerning evaporation processes of water molecules, based on stable structures and the binding energies of MB⁺(H₂O) _n ions calculated by DFT calculations up to n = 5. MB⁺(H₂O) _n ions for n > 4 evaporate a single water molecule sequentially, while MB⁺(H₂O)₄ tends to fragment into MB⁺ and (H₂O)₄ rather than MB⁺(H₂O)₃ and an H₂O molecule. We have observed a clear magic peak at n = 24, which strongly suggests that the MB⁺(H₂O)₂₄ ion is formed by attaching a neutral (H₂O)₂₀ cage onto an MB⁺(H₂O)₄ ion.     

Structure of zinc-borate low-melting glasses derived from IR spectroscopy data

The IR spectra of glasses of the ZnO—SrO—B₂O₃ system with constant additions of PbO, Al₂O₃, and Li₂O (20 mol. % in sum) were studied. It is established that on replacement of B₂O₃ by ZnO, the structure of the glasses is characterized by the presence of groupings with the bridge bonds B^III— O—B^III, B^III—O—B^IV, B^IV—O—B^IV and end groups B^III— O⁻; ZnO practically exerts no influence on the coordination transition [BO₃] → [BO₄]. At a high content of ZnO, zinc ions are present in both a six-and a four-coordinated state. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 6, pp. 778–781, November–December, 2005.     

Vibrational analysis of NaM2OH(H2O)(MoO4)2/D2O [M=Ni,Zn]

The infrared and Raman spectra of NaNi₂OH(H₂O)(MoO₄)₂ and NaZn₂OH (H₂O)(MoO₄)₂ and their partially deuterated analogues are recorded and analysed on the basis of vibrations of MoO ₄ ²⁻ tetrahedra and H₂O molecules. The MoO ₄ ²⁻ groups are found to be more distorted in NaNi₂OH(H₂O)(MoO₄)₂ than in the other compound. Bands indicating the presence of H₃O⁺ ions are not observed in NaZn₂OH(H₂O)(MoO₄)₂ ruling out the possibility of the formulation of NaZn₂OHO(MoO₃OH)₂. Hydrogen bonds of medium strength are present in both the compounds.     

Sulfide passivation of a textured interface of a gallium arsenide surface-barrier photovoltaic cell

A comparative study is made of the influence of sulfide passivation in an aqueous Na₂S·9H₂O solution on the photoconversion parameters of solar radiation in Au-GaAs barrier structures as a function of the character of the microrelief and the pretreatment of the GaAs surface. A quasigrating and a dendritic surface microrelief were produced by anisotropic chemical etching. It is shown that this type of GaAs surface treatment is potentially useful for enhancing the efficiency of a photovoltaic cell stored for several years. A possible mechanism is discussed for the processes leading to changes in the structure parameters. Zh. Tekh. Fiz. 69, 132–134 (June 1999)     

Modification of the optical spectra of mixed K2CoxNi1–x(SO4)2?6H2O crystals

We propose a new method for obtaining K₂Co _x Ni_1–x (SO₄)₂⋅6H₂O (x = 0, 0.4, 0.8, 1) crystals, involving the use of the chlorides (CoCl₂⋅6H₂O and NiCl₂⋅6H₂O) in an aqueous solution instead of the widely used sulfates. We have studied the transmission spectra of the grown single crystals in the range λ = 200–900 nm and the IR reflectance spectra in the 2.5–20 μm region. We have observed a change in the position and intensity of the absorption bands as a function of the composition of the crystals. Based on the Tanabe–Sugano diagrams, we determined the crystal field splitting (D_q) and its dependence on the nickel concentration. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 76, No. 1, pp. 126–130, January–February, 2009.     

Photoinduced self-limited low-temperature growth of ultra-thin silicon-oxide films with water vapor

The growth of ultra-thin (<2 nm) silicon-oxide films was investigated on Si(100):H, Si(111):H, and a-Si:H surfaces in a pure water atmosphere (0.1–10 Pa) at low temperatures of 30–250 °C. Oxidation was induced photochemically by pulsed F₂-laser radiation at 157 nm. The thickness and composition of the growing oxide films were monitored in real time by spectroscopic ellipsometry in the photon energy range of 1.15–4.75 eV. The mechanism of laser-induced silicon oxidation in a H₂O atmosphere is shown to differ fundamentally from the classical Deal–Grove mechanism of thermal oxidation at 900–1200 °C, as well as from the photoinduced low-temperature oxidation in an O₂ atmosphere. In particular, the film thickness essentially does not depend on temperature below 250 °C. A kinetic model is developed for low-temperature silicon oxidation in a H₂O atmosphere. According to this model, the growth is limited at small thicknesses by the oxidation reaction and at larger thicknesses by reactions of the diffusing oxidizing species in the oxide layer. Very good agreement is established between this kinetic model and the ellipsometric measurements and the temperature and pressure dependence of the water oxidation process. PACS 82.65.+r; 07.60.Fs; 81.65.Mq; 82.50.Hp     

Synthesis, Crystal Structure and Luminescent Property of Complex [Tb0.1Gd0.9(TPTZ)(H2O)6]Cl3·3H2O

The complex [Tb_0.1Gd_0.9(TPTZ)(H₂O)₆]Cl₃·3H₂O was prepared through the reaction of 2,4,6-tris-(2-pyridyl)-1,3,5-triazine (TPTZ) with TbCl₃:GdCl₃ (0.1:0.9) in absolute ethanol at room temperature. Single crystal X-ray diffraction revealed that the metal atom is nine-coordinated with three nitrogen atoms from one TPTZ ligand and six oxygen atoms from six water molecules. The complex emits intense green fluorescence under ultraviolet light. The luminescence peaks correspond to the characteristic emission ⁵D₄→⁷F_J (J = 3–6) transitions of the Tb³⁺ ion.     

Spectroscopic investigation of the plasma of a high-current diffuse discharge in He/Ar/CF2Cl2(CCl4) mixtures

Survey emission spectra in the region of 190–600 nm and time and service-life characteristics of a transverse nanosecond discharge in He/Ar/CF₂Cl₂(CCl₄) mixtures at a pressure of 10–100 kPa are investigated. In the emission spectra, excited products of the decomposition of freons—C₂(A−X), CN(B−X), Cl ₂ ^* , C^*, Cl^*, and Cl^+*— and the emission of ArF at λ=193 nm are revealed. The emissions of Cl ₂ ^* at λ=258 nm and ArF at λ=193 nm were the most intense. The discharge in the He/Ar/CF₂Cl₂ mixture is a multiwave emission source with λ=258 nm Cl ₂ ^* 193 nm ArF, and probably, 175 nm Arcl. It is of interest for applications in UV-VUV-range pulse photometry. The duration of the emission on Cl ₂ ^* , ArF, ArI, ClI, and ClII transitions in the discharge in the Ar/CF₂Cl₂ mixture (P=10–20 kPa) was 200–300 nsec. With adding He and increasing pressure to 100 kPa the duration of the emission decreased by a factor of 1.5–2. The basic mechanisms of the formation of Cl₂, ArF, and CN(B) molecules in the transverse-discharge plasma are considered. Uzhgorod State University, 46, Pidgirna Str., Uzhgorod, 294000, Ukraine. Translated from Zhurnal. Prikladnoi Spektroskopii, Vol. 66, No. 2, pp. 241–246, March–April, 1999.     

Evaluation and use of the Pd | SrCe0.95Yb0.05O3| Pd electrochemical reactor for equilibrium-limited hydrogenation reactions

The current — overpotential characteristics of the H₂ - Pd - SCY interphase have been studied at atmospheric total pressure and temparatures between 400 – 550 °C in the single chamber reactor — cell: Pd | SCY | Pd. The results of I−η measurements indicate that the apparent anodic and cathodic charge tranfer coefficients are equal to: α_a=α_c=0.5. The present results are compared to those obtained with the single — chamber reactor cell: Ag | SCY | Ag. A solid state proton (H⁺) conducting reactor — cell with Pd electrodes was tested for the ammonia synthesis from its elements at atmospheric pressure. At 570 °C, over 75% of the ectrochemically supplied hydrogen was converted into NH₃. The thermodynamic requirement for a high pressure process was eliminated. Paper presented at the 5th Euroconference on Solid State Ionics, Benalmádena, Spain, Sept. 13–20, 1998.     

Near-infrared diode laser absorption sensor for rapid measurements of temperature and water vapor in a shock tube

A fast-response (100 kHz) tunable diode laser absorption sensor is developed for measurements of temperature and H₂O concentration in shock tubes, e.g. for studies of combustion chemistry. Gas temperature is determined from the ratio of fixed-wavelength laser absorption of two H₂O transitions near 7185.60 cm^-1 and 7154.35 cm^-1, which are selected using design rules for the target temperature range of 1000–2000 K and pressure range of 1–2 atm. Wavelength modulation spectroscopy is employed with second-harmonic detection (WMS-2f) to improve the sensor sensitivity and accuracy. Normalization of the second-harmonic signal by the first-harmonic signal is used to remove the need for calibration and minimize interference from emission, scattering, beam steering, and window fouling. The laser modulation depth for each H₂O transition is optimized to maximize the WMS-2f signal for the target test conditions. The WMS-2f sensor is first validated in mixtures of H₂O and Ar in a heated cell for the temperature range of 500–1200 K (P=1 atm), yielding an accuracy of 1.9% for temperature and 1.4% for H₂O concentration measurements. Shock wave tests with non-reactive H₂O–Ar mixtures are then conducted to demonstrate the sensor accuracy (1.5% for temperature and 1.4% for H₂O concentration) and response time at higher temperatures (1200–1700 K, P=1.3–1.6 atm). PACS 42.62.Fi; 42.55.Px; 42.60.Fc; 07.35.+k     

Frequency response analysis of ionically conducting mixed system (1-x)CuI - xAg2MoO4 (0.15 ≤ x ≤ 0.55)

A systematic analysis of the electrical response of the mixed system (1-x)CuI — xAg₂MoO₄ (0.15≤x≤0.55) over the temperature range 297 – 447 K in the 20 Hz — 1 MHz frequency domain has been reported. Relaxation processes associated with individual compositions of this heterogeneous mixture of polycrystalline samples have been identified through a combined analysis of modulus and impedance spectral formalisms. The detailed analysis of these relaxation processes has indicated that AgI and Ag₂MoO₄ phases are the predominant sources of electric conduction in the case of samples in the composition region 0.33≤x≤0.55 whereas in those samples having x<0.33, the presence of Cu₂MoO₄ phase in the mixture is found to make a definite contribution to their effective electric conduction.     

Backscattering of low-energy (0–8 eV) electrons by a silicon surface

An experimental apparatus and method for investigating elastic and inelastic backscattering (180°) of low-energy (0–8 eV) monoenergetic electrons by a solid surface are described and the first results are presented for the reflection of electrons by samples of pure single-crystalline silicon with a polished surface (Si), doped p-type single-crystalline silicon with a porous surface (Si-p) as well as H₂O and H₂O₂ passivated porous samples, Si-p + H₂O and Si-p + H₂O₂. A structure due to the excitation of surface plasmons has been observed for the first time in the loss spectra. Features corresponding to a resonance excited state of molecular nitrogen adsorbed on the surface of porous silicon have been observed in the constant residual energy spectra. Zh. Tekh. Fiz. 67, 103–108 (May 1997)     

Infrared-to-visible up-conversion emissions and thermometric applications of Er 3+-doped Al 2 O 3

Er³⁺-doped Al₂O₃ has been prepared by a sol–gel method, using aluminium isopropoxide [Al(OC₃H₇)₃]-derived Al₂O₃ sols with addition of erbium nitrate [Er(NO₃)₃·5H₂O]. The phase structure of θ-(Al,Er)₂O₃ phase was obtained for the 0.1 mol. % Er³⁺-doped Al₂O₃ at the sintering temperature of 1273 K. The green and red up-conversion emissions centered at about 523, 545 and 660 nm, corresponding respectively to the ² H _11/2, ⁴ S _3/2→⁴ I _15/2 and ⁴ F _9/2→⁴ I _15/2 transitions of Er³⁺, were detected by a 978-nm semiconductor laser diode excitation. The temperature dependence of green up-conversion emissions was studied over a wide temperature range of 295–725 K, and reasonable agreement between the calculated temperatures obtained by the fluorescence intensity ratio theory and the measured temperature was obtained, which proved that Er³⁺-doped Al₂O₃ has a good potential for the development of high-temperature sensors. It has some advantages compared to glasses due to its higher thermal and mechanical resistance and allows measurements in a large temperature range. PACS 78.55.Hx; 81.40.Tv     

Effect of lanthanides on the spectral-luminescence properties and photoresistance of organic dyes in silicate sol-gel films

A sol-gel method is used to synthesize silicate films dyed in the sol stage with rhodamine C or methylene blue and further doped with cerium or lanthanum. It is shown that this sort of doping leads to a reduction in the peak intensity and a change in the shape of the S ₁←S ₀ band of the dyes, as well as to a shift in this band in a direction that depends on the H₂O: Si(OC₂H₅)₄ ratio. At the same time, the photoresistance of the rhodamine C molecules increases. The observed spectral changes are explained by the formation of supramolecules that include organic molecules, rare earth ions, and elements from the structural grid of the film, while the enhanced photoresistance is explained mainly by strengthening of the T ₁→S ₀ transitions in the dye. Fiz. Tverd. Tela (St. Petersburg) 41, 1979–1984 (November 1999)