Photosensitivity and thermosensitivity of polymers doped with Eu(fod)<Subscript>3</Subscript> molecules

We have studied the photoluminescence (PL) spectra of Eu³⁺ ions and the decay kinetics for the photoluminescence intensity on exposure to temperature and UV radiation in polypropylene and oligo(urethane methacrylate) (OUM) doped with Eu(fod)₃ molecules (fod = 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octadione) by soaking in a supercritical CO₂ solution. We have established that the decay kinetics for the photoluminescence intensity on exposure to UV radiation depends on the temperature of the sample and the concentration of the dopant in it. Based on studies of the spectral characteristics of doped OUM samples, we suggest that this material can be used as a two-color luminescent temperature sensor. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 76, No. 1, pp. 104-111, January-February, 2009.     

Thermal quenching of photoluminescence of Eu3+ ions in an Eu(fod)3 complex

We have studied the photoluminescence (PL) spectra of Eu³⁺ ions in the complex Eu(fod)₃ (fod = 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octadione) and also in polymers doped with Eu(fod)₃ with the help of supercritical carbon dioxide. We have established that in the temperature range 20°C–100°C, we observe thermal quenching of the photoluminescence of Eu³⁺ ions, and this quenching is most efficient in polycrystalline Eu(fod)₃ powder and Eu(fod)₃-doped polypropylene. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 3, pp. 315–319, May–June, 2006.     

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.     

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.     

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.     

Inelastic neutron scattering and lattice dynamics of NaNbO<Subscript>3</Subscript> and Sr<Subscript>0.70</Subscript>Ca<Subscript>0.30</Subscript>TiO<Subscript>3</Subscript>

NaNbO₃ and (Sr,Ca)TiO₃ exhibit an unusual complex sequence of temperature- and pressure-driven structural phase transitions. We have carried out lattice dynamical studies to understand the phonon modes responsible for these phase transitions. Inelastic neutron scattering measurements using powder samples were carried out at the Dhruva reactor, which provide the phonon density of states. Lattice dynamical models have been developed for SrTiO₃ and CaTiO₃ which have been fruitfully employed to study the phonon spectra and vibrational properties of the solid solution (Sr,Ca)TiO₃.      

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.     

Theoretical study of ZnO adsorption and bonding on Al<Subscript>2</Subscript>O<Subscript>3</Subscript> (0001) surface

ZnO adsorption on sapphire (0001) surface is theoretically calculated by using a plane wave ultrasoft pseudo-potential method based onab initio molecular dynamics. The results reveal that the surface relaxation in the first layer Al-O is reduced, even eliminated after the surface adsorption of ZnO, and the chemical bonding energy is 434.3(±38.6) kJ · mol⁻¹. The chemical bond of ZnO (0.185 ± 0.01 nm) has a 30° angle away from the adjacent, Al-O bond, and the stable chemical adsorption position of the Zn is deflected from the surface O-hexagonal symmetry with an angle of about 30°. The analysis of the atomic populations, density of state and bonding electronic density before and after the adsorption indicates that the chemical bond formed by the O²⁻ of the ZnO and the surface Al³⁺ has a strong ionic bonding characteristic, while the chemical bond formed by the Zn²⁺ and the surface O²⁻ has an obvious covalent characteristic, which comes mainly from the hybridization of the Zn 4s and the O 2p and partially from that of the Zn 3d and the O 2p.     

Analysis of hydrogen bonds by the IR spectra of thymine and N<Subscript>1</Subscript>,N<Subscript>3</Subscript>-deuterothymine

Calculations of the frequencies and absolute intensities of the IR bands of plane vibrations of thymine and N₁,N₃-deuterothymine in various phase states have been carried out. It has been shown that in the polycrystalline state thymine forms hydrogen bonds C₂=O₈...HN₁ and C₂=O₈...HN₃, and in an aqueous solution the intermolecular interaction is realized by means of the hydrogen bonds O₈...HO and O...HN₁.__________Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 1, pp. 99–105, January–February, 2005.     

Effect of excess Y<Subscript>2</Subscript>O<Subscript>3</Subscript> addition on the physical properties of melt processed YBCO bulks

The YBCO superconductors with Y₂O₃ addition were prepared by a modified melt textured process and the effects of excess Y₂O₃ addition on the physical properties of melt textured YBCO have been investigated. It is found that the melt temperature of YBCO samples decreases drastically with the increasing Y₂O₃, and the maximum levitation forces are drastically different for samples with different Y₂O₃ addition. It is also found that the optimal Y₂O₃ addition to YBCO is about 10wt%. Considering the microstructure and the starting composition, the results are well discussed and interpreted.     

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.     

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.     

Up-conversion emissions of Er<Superscript>3+</Superscript>-Yb<Superscript>3+</Superscript> codoped Al<Subscript>2</Subscript>O<Subscript>3</Subscript> nanoparticles by the arc discharge synthesis method

The Er³⁺-Yb³⁺ codoped Al₂O₃ nanoparticles with an average particle size of about 50 nm have been synthesized by an arc discharge synthesis method. The green and red up-conversion emissions centered at about 526, 547 and 677 nm, corresponding respectively to the ²H_11/2→⁴I_15/2, ⁴S_3/2→⁴I_15/2 and ⁴F_9/2→⁴I_15/2 transitions of Er³⁺, were detected by a 978-nm semiconductor laser diode excitation. The Annealing has evident effect on the up-conversion emissions of the samples: The red up-conversion emission is noticeable before annealing; however, the green up-conversion emission becomes predominant after annealing. The mixture of (Er,Yb)₃Al₅O₁₂ and α-(Al,Er,Yb)₂O₃ phases is more favorable for green up-conversion emissions due to an enhancement of the ESA (I) of ⁴I_11/2+a photon→⁴F_7/2 and ET (III) of ²F_5/2(Yb³⁺)+⁴I_11/2(Er³⁺)→²F_7/2(Yb³⁺)+⁴F_7/2(Er³⁺) processes. The two-photon absorption up-conversion process is involved in the green and red up-conversion emissions. The results have proved that arc discharge synthesis is a new promising preparation technology for optical materials. Supported by National Natural Science Foundation of China (Grant No. 10804015), the Scientific Research Foundation for Doctor of Liaoning Province (Grant No. 20071095), and the Educational Committee Foundation of Liaoning Province (Grant No. 2008123)     

Surface morphology of PrBa<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>7-δ</Subscript> single crystals after the long-lasting high-temperature reduction

The results of the detailed scanning electron microscopy study of PrBa₂Cu₃O_7-δ single crystals after the long-lasting high-temperature post-growth treatment are reported. The presence of the unstable decomposition products on the crystal surface indicates that the onset of superconductivity must be related to the structural transformations in the bulk (approximately 20% of the total volume of the examined crystals). The time-dependent character of the superconductivity in the Pr-123 crystals could be attributed to the migration of defects in the Pr−Ba sublattice from the bulk toward the surface.     

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     

Antisite defect types and temporal evolution characteristics of D0<Subscript>22</Subscript>-Ni<Subscript>3</Subscript>V structure: Studied by the microscopic phase field

Microscopic phase field simulation is performed to study antisite defect type and temporal evolution characteristic of D0₂₂-Ni₃V structure in Ni₇₅Al _x V_25−x ternary system. The result demonstrates that two types of antisite defect V_Ni and Ni_V coexist in D0₂₂ structure; however, the amount of Ni_V is far greater than V_Ni; when precipitates transform from D0₂₂ singe phase to two phases mixture of D0₂₂ and L1₂ with enhanced Al:V ratio, the amount of V_Ni has no evident response to the secondary L1₂ phase, while Ni_V exhibits a definitely contrary variation tendency: Ni_V rises without L1₂ structure precipitating from matrix but declines with it; temporal evolution characteristic and temperature dependent antisite defect V_Ni, Ni_V are also studied in this paper: The concentrations of the both defects decline from high antistructure state to equilibrium level with elapsed time but rise with elevated temperature; the ternary alloying element aluminium atom occupies both α and β sublattices of D0₂₂ structure with a strong site preference of substituting α site. Supported by the National Natural Science Foundation of China (Grant Nos. 50671084 and 50875217), the Doctorate Foundation of Northwestern Polytechnical University of China (Grant No. CX200806), the China Postdoctoral Science Foundation Funded Project (Grant No. 20070420218), and the Natural Science Foundation of Shaanxi Province of China     

VUV luminescence of Er<Superscript>3+</Superscript> ions in LiYF<Subscript>4</Subscript> and BaY<Subscript>2</Subscript>F<Subscript>8</Subscript> crystals

Vacuum ultraviolet luminescence of Er³⁺ ions in LiYF4 and BaY₂F₈ crystals has been investigated. It is revealed that under excitation by 193 nm radiation from an ArF excimer laser the interconfigurational 5d–4f radiative transitions in Er³⁺ ions are observed. It is shown that from the LiYF₄:Er crystal only the spin-forbidden luminescence (λ = 165 nm) is detected, whereas both the spin-forbidden (λ = 169 nm) and spin-allowed (λ = 160.5 nm) components are observed from the BaY₂F₈:Er crystal.     

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.     

Large influence of the synthesis conditions on the physico-chemical properties of nanostructured Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>

Magnetite synthesized via three different synthesis routes (coprecipitation process in aqueous media, electrochemical synthesis in presence of complexing agents and solid state reaction at high temperature) has been characterized by X-Ray diffraction, scanning electron microscopy, thermal analysis (TGA), FT-IR and Mössbauer spectroscopies. Although each procedure gave homogeneous magnetite powders, many differences could be seen in the physico-chemical properties of the samples mostly depending on the synthesis conditions. For instance, at least two factors seem to have a huge impact onto the Fe₃O₄ behaviour: the presence of hydration water molecules and the particle size of the powders since a superparamagnetic behaviour was observed with the thinnest particles, at room temperature, on the Mössbauer spectra via the appearance of line broadening and a pronounced central doublet.     

Spectroscopic Characterization of Eu(III) Complexes with New Monophosphorus Acid Derivatives of H<Subscript>4</Subscript>dota

The luminescence lifetimes of europium(III) complexes with new monophosphorus acid derivatives of H₄dota were measured by means of time-resolved laser-induced luminescence spectroscopy in H₂O and D₂O. The hydration numbers of these complexes were estimated using different empirical equations [Horrocks and Sudnick (1979) J. Am. Chem. Soc. 101 (1979) 334; Choppin and Barthelemy(1989) Inorg. Chem. 28, 3354–3357; Choppin and Bünzli Lanthanide probes in life, chemical and earth sciences. Theory and practice (1989); Kimura and Kato J. Alloys Comp. 275–277 (1998) 806; Parker (1999) J. Chem. Soc., Perkin Trans. 2, 493–503; Supkowski and Horroks (2002) Inorg. Chim. Acta. 340, 44–48]. It was shown that all the relationships gave similar results with a satisfactory precision. The hydration numbers of complexes of H₃do3a and H₄dota agreed with the literature values. One water molecule is coordinated in complexes of the new ligands. The results showed that the Choppin formula based on measurements only in H₂O can be satisfactorily used for estimation of the hydration numbers.