Study of structural phase transitions in YBa<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>6+δ</Subscript> by x-ray photoelectron spectroscopy

We have used x-ray photoelectron spectroscopy to investigate the charge state of oxygen found in the basal structural plane of YBa₂Cu₃O₆+γ.. We have observed a change in this state after thermal treatment, with a transition to the adjacent structural phase region. We have shown that changes in the charge state of oxygen can be used as an indicator of structural changes occurring in YBa₂Cu₃O₆+δ.. We have found that the rate of structural relaxation yttrium barium cuprate depends on the amount of structural water it contains. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 2, pp. 195–198, March–April, 2007.     

Anomalous absorption in H<Subscript>2</Subscript>CN and CH<Subscript>2</Subscript>CN molecules

Structures of H₂CN and CH₂CN molecules are similar to that of H₂CO molecule. The H₂CO has shown anomalous absorption for its transition 1₁₁–1₁₀ at 4.8 GHz in a number of cool molecular clouds. Though the molecules H₂CN and CH₂CN have been identified in TMC-1 and Sgr B2 through some transitions in ortho as well as in para species, here we have investigated the condition under which transitions 1₁₁–1₁₀ and 2₁₂–2₁₁ of these molecules may show anomalous absorption. For the present investigation, we have calculated energy levels and radiative transition probabilities. However, we have used scaled values for collisional rate coefficients. We found that relative values of collisional rate coefficients can produce the required anom-alous absorption in 1₁₁–1₁₀ and 2₁₂–2₁₁ transitions in the molecules.      

Absorption by CS<Subscript>2</Subscript> molecules on “hot” band emission lines from a TEA CO<Subscript>2</Subscript> laser

We have measured absorption of emission from a TEA CO₂ laser, lasing on hot band lines, in pure CS₂ and a mixture of CS₂ with air, and we have determined the optimal lines for optical excitation. Numerical modeling has shown that as the peak intensity of the pump radiation is increased, we observe absorption saturation, the extent of which decreases as the pressure increases. The major factor responsible for absorption saturation is the “rotational bottleneck” effect. Depending on the peak intensity of the radiation, addition of a buffer gas can lead to an increase or decrease in the absorption. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 1, pp. 61–66, January–February, 2007.     

Hyperfine structure in EPR spectra of the catalytic system TiCl<Subscript>4</Subscript> + Al(i-C<Subscript>4</Subscript>H<Subscript>9</Subscript>)<Subscript>3</Subscript>

In an EPR study of the catalytic system TiCl₄ + Al(i-C₄H₉)₃ in toluene and isopentane in TiCl₄/oligopiperylene + Al(i-C₄H₉)₃ in toluene, we have observed a dependence of the linewidth of the hyperfine structure on the mobility of the complex in solution. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 2, pp. 174–177, March–April, 2007.     

Spectral and kinetic characteristics of CdI<Subscript>2</Subscript> and CdI<Subscript>2</Subscript>:Pb scintillators

We have studied the effect of lead dopant on the optical absorption, photoluminescence, and x-ray luminescence spectra, and the scintillation characteristics of CdI₂ at room temperature. The crystals for the study were grown by the Stockbarger-Bridgman method. Activation of CdI₂ from the melt by the compound PbI₂ leads to the appearance in the absorption spectra in the near-edge region of an activator band at 395–405 nm, which is interpreted as an A band connected with electronic transitions from the ¹S₀ state to the ³P₁ levels in the Pb²⁺ ion. For x-ray excitation, CdI₂:Pb²⁺ crystals with optimal dopant concentration (∼1.0 mol%) are characterized by a light yield with maximum in the 570–580 nm region that is an order of magnitude higher than for CdI₂ crystals in the 490–500 nm band. For α excitation, the radioluminescence kinetics for cadmium iodide is characterized by a very short (∼0.3 nsec) rise time and fast decay of luminescence, with τ₁ ≈ 4 nsec and τ₂ = 10–76 nsec. Depending on the conditions under which the crystals were obtained, the fast component fraction is 95%–99%. The crystal is characterized by a similar scintillation pulse in the case of excitation by x-ray pulses. The radioluminescence pulse shape for CdI₂:Pb in the decay stage is predominantly exponential, with luminescence decay time constants τ₁ ≈ 10 nsec and τ₂ = 200–250 nsec. This system is characterized by low afterglow, at the level for the Bi₄G₃O₁₂ scintillator. We have demonstrated the feasibility of using CdI₂:Pb as a scintillator for detecting α particles. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 6, pp. 825–830, November–December, 2008.     

Investigation on structural characteristics of PVDF–AgCF<Subscript>3</Subscript>SO<Subscript>3</Subscript>–Al<Subscript>2</Subscript>O<Subscript>3</Subscript> nanocomposite solid polymer electrolyte system

There has been an increasing interest towards the incorporation of nanosize ceramic fillers in polymer electrolytes. Solid polymer electrolytes based on polyvinylidene fluoride (PVDF), silver triflate (AgCF₃SO₃), and x wt% of aluminum oxide (Al₂O₃) nanopowders (where x = 1, 3, 5, and 10, respectively) have been prepared using solution casting technique. The structural characteristics of these thin film specimens were studied using Fourier transform infrared (FTIR) and X-ray diffraction (XRD) patterns at room temperature. The appearance of new absorption bands and gradual shifts observed in some characteristic peaks confirmed the complex formation between polyvinylidene fluoride and silver triflate. Furthermore, the addition of nanosized filler Al₂O₃ has also indicated the interaction of the filler with the polymer salt complex. The XRD patterns obtained for all these samples in the 2θ range 10° to 70° showed the amorphous nature of these samples. Paper presented at the Third International Conference on Ionic Devices (ICID 2006), Chennai, Tamilnadu, India, December 7–9, 2006.     

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.     

Preparation of TiO<Subscript>2</Subscript>-coated LiCo<Subscript>1/3</Subscript>Ni<Subscript>1/3</Subscript>Mn<Subscript>1/3</Subscript>O<Subscript>2</Subscript> by electrostatic self-assembly method and its properties

A precursor of TiO₂–LiCo_1/3Ni_1/3Mn_1/3O₂ was prepared by electrostatic self-assembly method. The final product was obtained by heating the precursor at 400–450 °C for 4–6 h in air. X-ray diffraction (XRD), scanning electron microscope (SEM), X-ray photoelectron spectroscopy (XPS), and electrochemical tests were used to examine the structural, morphology, elementary valence, and electrochemical characteristics. XRD indicated that the TiO₂-coated material can be indexed by α-NaFeO₂ layered structure, which belongs to hexagonal-type space group R3m. XPS results confirmed the existence of TiO₂ compound on the surface of the coated sample. The SEM image showed that the material had spherically porous morphology with the uniform size about 6 μm. The initial charge–discharge capacity of the TiO₂-coated LiCo_1/3Ni_1/3Mn_1/3O₂ material was 168.8/160.0 mAh/g. After 60 cycles, the discharge capacity of the TiO₂-coated LiCo_1/3Ni_1/3Mn_1/3O₂ sample was 147.0 mAh/g, and the coulombic efficiency was 94.0%. Compared with the uncoated sample, the electrochemical performance of TiO₂-coated LiCo_1/3Ni_1/3Mn_1/3O₂ was improved.     

Tunable optical parametric oscillator based on a KTP crystal,pumped by a pulsed Ti<Superscript>3+</Superscript>:Al<Subscript>2</Subscript>O<Subscript>3</Subscript> laser

We present the characteristics of an optical parametric oscillator based on a KTP crystal, pumped with noncritical phase matching by a pulsed Ti³⁺:Al₂O₃ laser, tunable in the range 677–970 nm. Tunable generation of signal and idler waves is obtained in the ranges 1030–1390 nm and 2690–3050 nm respectively. The efficiency of conversion of the pump to the signal wave is ≈23%, which for pulses of duration ≈8 nsec ensures an energy in the range 1.0–11.5 mJ. The width of the emission spectrum for the signal wave is within the range 0.8–1.8 nm and is predominantly determined by the linewidth of the Ti³⁺:Al₂O₃ pump laser. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 3, pp. 351–356, May–June, 2007.     

One-step synthesis of colloidal Mn<Subscript>3</Subscript>O<Subscript>4</Subscript> and γ-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> nanoparticles at room temperature

A facile room-temperature synthesis has been developed to prepare colloidal Mn₃O₄ and γ-Fe₂O₃ nanoparticles (5 to 25 nm) by an ultrasonic-assisted method in the absence of any additional nucleation and surfactant. The morphology of the as-prepared samples was observed by transmission electron microscopy. High-resolution transmission electron microscopy observations revealed that the as-synthesized nanoparticles were single crystals. The magnetic properties of the samples were investigated with a superconducting quantum interference device magnetometer. The possible formation process has been proposed.     

Structural,thermal and ion transport studies on nanocomposite polymer electrolyte-{(PEO + SiO<Subscript>2</Subscript>):NH<Subscript>4</Subscript>SCN} system

Development and characterisation of polyethylene oxide (PEO)-based nanocomposite polymer electrolytes comprising of (PEO-SiO₂): NH₄SCN is reported. For synthesis of the said electrolyte, polyethylene oxide has been taken as polymer host and NH₄SCN as an ionic charge supplier. Sol–gel-derived silica powder of nano dimension has been used as ceramic filler for development of nanocomposite electrolytes. The maximum conductivity of electrolyte ∼2.0 × 10⁻⁶ S/cm is observed for samples containing 30 wt.% silica. The temperature dependence of conductivity seems to follow an Arrhenius-type, thermally activated process over a limited temperature range.     

Preparation of nanosized Bi<Subscript>2</Subscript>WO<Subscript>6</Subscript> using different content of starting materials and their photoactivities

A series of nanosized Bi₂WO₆ catalysts was synthesized using various starting materials, and they were characterized by X-ray diffractometry, transmission electron microscopy, and diffuse reflectance spectroscopy. Rhodamine-B (RhB) photodegradation in aqueous medium was employed as a probe reaction to test the photoactivity of the as-prepared samples. Dependence of the photocatalytic activities on different contents of the starting materials was examined under visible irradiation (λ > 400 nm). The sample prepared in the following conditions: reaction time 24 h, the pH of the solution 7, the Bi³⁺ amount in the start precipitates 5 mmol — exhibited the highest photochemical activity when the hydrothermal temperature was settled at 180°C. Published in Zhurnal Prikladnoi Spektroskopii, Vol. 76, No. 2, pp. 243–249, Martch–April, 2009.     

Ultrasound-assisted dispersion of SrFe<Subscript>12</Subscript>O<Subscript>19</Subscript> nanoparticles in organic solvents and the use of the dispersion as magnetic cosmetics

A new method of dispersing the aggregated strontium hexaferrite (SrFe₁₂O₁₉) magnetic nanoparticles in organic solvents such as propylene glycol monomethyl ether acetate (PGMEA), propylene glycol (PG), and glycerol, by an ultrasonic bath is reported herein. The particles size of SrFe₁₂O₁₉ after treatment with the PGMEA is in the range 70–100 nm. The structure of dispersed SrFe₁₂O₁₉ was characterized using transmission electron microscopy (TEM), high resolution scanning electron microscopy (HR SEM) and thermo gravimetric analysis (TGA). This dispersed material was used for the preparation of a topical magnetic cosmetic product as follows: The dispersion of SrFe₁₂O₁₉ in PG was mixed with “Dermud-Ahava Body Cream”, an ‘oil in water’ emulsion of a Dead Sea mineral cosmetic, “AHAVA”, and the magnetic properties of the created composite were determined. The ferrimagnetic behavior of the composite has been demonstrated as being very similar to the behavior of strontium hexaferrite itself.     

Structural and dehydriding properties of Ca(BH<Subscript>4</Subscript>)<Subscript>2</Subscript>

We have investigated the structural and dehydriding properties of Ca(BH₄)₂. It was found that Ca(BH₄)₂ undergoes a structural phase transformation from an orthorhombic low-temperature (LT) modification into a tetragonal high-temperature (HT) modification between 433 K and 523 K. The amount of hydrogen desorbed from Ca(BH₄)₂ during the pressure–composition (p–c) isotherm measurement was 5.9 mass%. This hydrogen desorption is caused by the partial dehydrogenation of Ca(BH₄)₂ accompanied by the formation of CaH₂ and orthorhombic intermediate phases.     

Characterization of Y<Subscript>2</Subscript>BaCuO<Subscript>5</Subscript> nanoparticles synthesized by nano-emulsion method

Nanoscale yttrium–barium–copper oxide (Y₂BaCuO₅, Y211) particles were synthesized using the emulsion method and the solution method. The basic water-in-oil (w/o) emulsion system consisted of n-octane (continuous oil phase), cetyltrimethylammonium bromide (cationic surfactant), butanol (cosurfactant) and water. The composition of the emulsion system was varied and characterized by measuring the conductivity of the solutions and droplet size. The droplet size of emulsion was determined by using the dynamic light scattering method. The water content, cosurfactant content, and surfactant/n-octane ratio affected the droplet size which was in the range of 3–8 nm, and hence the w/o emulsion system was referred to as a nano-emulsion system. A model was used to verify the droplet size. The influence of salt (Y₂(NO₃)₃) content on the droplet size was investigated and the addition of salt reduced the droplet size. The effects of reaction time and temperature on the Y211 particle sizes were also investigated. The particles were characterized using the TEM, SEM, and XRD. Nanoparticles produced by the nano-emulsion method were calcined at 850°C to form the Y211 phase as compared to solid state processing temperature of 1050°C. Based on the TEM analysis, the average diameter of the Y211 particles produced using the nano-emulsion method was in the range of 30–100 nm. The effect of adding 15% Y211 nanoparticles to the superconductor YBCO-123 as flux pinning centers, was investigated, and the transition temperature was reduced by 3 K.     

Luminescence of CaGa<Subscript>2</Subscript>Se<Subscript>4</Subscript>:Eu crystals

We have studied photoluminescence and thermoluminescence (PL and TL) in CaGa₂Se₄:Eu crystals in the temperature range 77–400 K. We have established that broadband photoluminescence with maximum at 571 nm is due to intracenter transitions 4f⁶ 5d–4f⁷ (⁸S_7/2) of the Eu²⁺ ions. From the temperature dependence of the intensity (log I–10³/T), we determined the activation energy (E _a = 0.04 eV) for thermal quenching of photoluminescence. From the thermoluminescence spectra, we determined the trap depths: 0.31, 0.44, 0.53, 0.59 eV. The lifetime of the excited state 4f6 5d of the Eu²⁺ ions in the CaGa₂Se₄ crystal found from the luminescence decay kinetics is 3.8 μsec. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 76, No. 1, pp. 112–116, January–February, 2009.     

Accuracy in determination of the temperature and partial pressure of CO<Subscript>2</Subscript> in CO<Subscript>2</Subscript>:N<Subscript>2</Subscript>:H<Subscript>2</Subscript>O:NO<Subscript>2</Subscript> mixtures by multiple-frequency laser probing

We present the results of analysis of the errors introduced by hot-band transitions 11¹0-01¹1, 03¹0-01¹1, 12⁰0-12⁰1 of the CO₂ molecule and the absorption lines of the H₂O and NO₂ molecules in determination of the temperature and partial pressure of CO₂, included in the gas mixture CO₂: N₂:H₂O: NO₂ at atmospheric pressure, by multiple-frequency laser probing using a CO₂ laser tunable over the lines of the 00⁰1-[10⁰0,02⁰0]_I,II ground-state laser transitions. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 6, pp. 810–815, November–December, 2007.     

Structural investigation on PEO-based polymer electrolytes dispersed with Al<Subscript>2</Subscript>O<Subscript>3</Subscript> nanoparticles

Thin solid polymer electrolytes based on polyethylene oxide (PEO) and silver triflate (AgCF₃SO₃) dispersed with various concentrations of aluminum oxide (Al₂O₃) nanoparticles have been prepared by solution casting technique. These thin polymer films are found to have thickness of the order of 30 to 100 μm. The X-ray diffraction (XRD) patterns have indicated the amorphous nature of the polymer electrolyte. The differential scanning calorimeter (DSC) traces showed slight change in the glass transition temperature (T _g) whereas the degree of crystallization (X _c) decreases markedly due to the addition of alumina nanoparticles. Fourier transform infrared (FTIR) spectral analysis of all these samples has revealed the presence of absorption bands around 1,000 cm⁻¹; thus indicating the complexation of silver ions with oxygen in PEO. Employing the Wagner’s polarization technique as the standard method, the total ionic transference number for the complexed polymer electrolyte was found to be approximately unity thereby revealing that the significant contribution to electrical conduction was due to ions only. Paper presented at the Third International Conference on Ionic Devices (ICID 2006), Chennai, Tamilnadu, India, December 7–9, 2006     

Synthesis of ZnAl<Subscript>2</Subscript>O<Subscript>4</Subscript>/α-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> complex substrates and growth of GaN films

With the solid phase reaction between pulsed-laser-deposited (PLD) ZnO film and α-Al₂O₃ substrate, ZnAl₂O₄/α-Al₂O₃ complex substrates were synthesized. X-ray diffraction (XRD) spectra show that as the reaction proceeds, ZnAl₂O₄ changes from the initial (111)-oriented single crystal to poly-crystal, and then to inadequate (111) orientation. Corresponding scanning electron microscope (SEM) images indicate that the surface morphology of ZnAl₂O₄ transforms from uniform islands to stick structures, and then to bulgy-line structures. In addition, XRD spectra present that ZnAl₂O₄ prepared at low temperature is unstable at the environment of higher temperature. On the as-obtained ZnAl₂O₄/α-Al₂O₃ substrates, GaN films were grown without any nitride buffer using light-radiation heating low-pressure MOCVD (LRH-LP-MOCVD). XRD spectra indicate that GaN film on this kind of complex substrate changes fromc-axis single crystal to poly-crystal as ZnAl₂O₄ layer is thickened. For the single crystal GaN, its full width at half maximum (FWHM) of X-ray rocking curve is 0.4°. Results indicate that islands on thin ZnAl₂O₄ layer can promote nucleation at initial stage of GaN growth, which leads to the (0001)-oriented GaN film.     

PLD and RF-PLD synthesis of Ba<Subscript>0.6</Subscript>Sr<Subscript>0.4</Subscript>TiO<Subscript>3</Subscript> ferroelectric thin films for electrically controlled devices

Ba_0.6Sr_0.4TiO₃ (BST) bulk ceramic synthesized by solid state reaction was used as target for thin films grown by pulsed laser deposition (PLD) and radiofrequency beam assisted PLD (RF-PLD). The X-ray diffraction patterns indicate that the films exhibit a polycrystalline cubic structure with a distorted unit cell. Scanning Electron Microscopy investigations showed a columnar microstructure with size of spherical grains up to 150 nm. The capacitance–voltage (C–V) characteristics of the BST films were performed by applying a DC voltage up to 5 V. A value of 280 for dielectric constant and 12.5% electrical tunability of the BST capacitor have been measured at room temperature.