Thermo-optic coefficients of monoclinic KLu(WO<Subscript>4</Subscript>)<Subscript>2</Subscript>

The three thermo-optic coefficients of the biaxial laser host KLu(WO₄)₂ are measured at 633 nm by a deflection method. Their values at 300 K amount to ∂ n _g /∂ T=−7.4×10⁻⁶ K⁻¹; ∂ n _m /∂ T=−1.6×10⁻⁶ K⁻¹ and ∂ n _p /∂ T=−10.8×10⁻⁶ K⁻¹. Nearly athermal propagation directions are found for polarizations along the N _m and N _p dielectric axes.     

Spectroscopic properties of Nd<Superscript>3+</Superscript>:CaNb<Subscript>2</Subscript>O<Subscript>6</Subscript> crystal

The absorption spectra, fluorescence spectrum and fluorescence decay curve of Nd³⁺ ions in CaNb₂O₆ crystal were measured at room temperature. The peak absorption cross section was calculated to be 6.202×10⁻²⁰ cm² with a broad FWHM of 7 nm at 808 nm for E//a light polarization. The spectroscopic parameters of Nd³⁺ ions in CaNb₂O₆ crystal have been investigated based on Judd-Ofelt theory. The parameters of the line strengths Ω _t are Ω ₂=5.321×10⁻²⁰ cm²,Ω ₄=1.734×10⁻²⁰ cm²,Ω ₆=2.889×10⁻²⁰ cm². The radiative lifetime, the fluorescence lifetime and the quantum efficiency are 167 μs, 152 μs and 91%, respectively. The fluorescence branch ratios are calculated to be β ₁=36.03%,β ₂=52.29%,β ₃=11.15%,β ₄=0.533%. The emission cross section at 1062 nm is 9.87×10⁻²⁰ cm².     

Spectroscopic Properties and Energy Transfer Analysis of Tm<Superscript>3+</Superscript>-Doped BaF<Subscript>2</Subscript>-Ga<Subscript>2</Subscript>O<Subscript>3</Subscript>-GeO<Subscript>2</Subscript>-La<Subscript>2</Subscript>O<Subscript>3</Subscript> Glass

This paper reports on the spectroscopic properties and energy transfer analysis of Tm³⁺-doped BaF₂-Ga₂O₃-GeO₂-La₂O₃ glasses with different Tm₂O₃ doping concentrations (0.2, 0.5, 2.0, 2.5, 3.0, 3.5, 3.5, 4.0 wt%). Mid-IR fluorescence intensities in the range of 1,300 nm−2,200 nm have been measured when excited under an 808 nm LD for all the samples with the same pump power. Energy level structure and Judd-Ofelt parameters have been calculated based on the absorption spectra of Tm³⁺, cross-relaxation rates and multi-phonon relaxation rates have been estimated with different Tm₂O₃ doping concentrations. The maximum fluorescence intensity at around 1.8 μm has been obtained in Tm₂O₃-3 wt% sample and the maximum value of calculated stimulated emission cross-section of Tm³⁺ in this sample is about 0.48 × 10⁻²⁰ cm² at 1,793 nm, and there is not any crystallization peak in the DSC curve of this sample, which indicate the potential utility of Tm³⁺-doped BaF₂-Ga₂O₃-GeO₂- La₂O₃ glass for 2.0-μm optical fiber laser.     

Silver Nanoparticle-Enhanced Chemiluminescence Method for Determining Naproxen Based on Europium(III)-Sensitized Ce(IV)-Na<Subscript>2</Subscript>S<Subscript>2</Subscript>O<Subscript>4</Subscript> Reaction

A simple and sensitive chemiluminescence (CL) method coupled with flow-injection technique is proposed to determine naproxen (NAP). The method is based upon the enhancement of the weak CL signal arising from the reaction of Ce(IV) and Na₂S₂O₄ with Eu³⁺ to form the Eu³⁺-Ce(IV)-Na₂S₂O₄ system. The CL intensity was significantly increased by the introduction of NAP into this system in the presence of silver nanoparticles (Ag NPs). Examination of the recorded UV–vis spectra and fluorescence spectra indicated that the energy of the intermediate SO₂*, which originated from the redox reaction of Ce(IV) and Na₂S₂O₄, was transferred to Eu³⁺ via NAP and that the process was accelerated by Ag NPs due to their catalytic activity. Under the optimum conditions, the CL intensity was increased with increasing NAP concentration and the correlation was linear (r = 0.9992) over the NAP concentration range of 1–420 ng mL⁻¹. The limit of detection (LOD) was 0.11 ng mL⁻¹ with a relative standard deviation (RSD) of 1.15% for 5 replicate determinations of 200 ng mL⁻¹ NAP. The method was successfully applied to determine NAP in pharmaceutical and biological samples.     

Preparation of MnO<Subscript>2</Subscript>/WMNT composite and MnO<Subscript>2</Subscript>/AB composite by redox deposition method and its comparative study as supercapacitive materials

The manganese oxide/multi-walled carbon nanotube (MnO₂/MWNT) composite and the manganese oxide/acetylene black (MnO₂/AB) composite were prepared by translating potassium permanganate into MnO₂ which formed the above composite with residual carbon material using the redox deposition method and carbon as a reducer. The products were characterized by X-ray diffraction, Fourier transform infrared, and scanning electron microscope. Electrochemical properties of both the MnO₂/MWNT and MnO₂/AB electrodes were studied by using cyclic voltammetry, electrochemical impedance measurement, and galvanostatic charge/discharge tests. The results show that the MnO₂/MWNT electrode has better electrochemical capacitance performance than the MnO₂/AB electrode. The charge–discharge test showed the specific capacitance of 182.3 F·g⁻¹ for the MnO₂/MWNT electrode, and the specific capacitance of 127.2 F·g⁻¹ for the MnO₂/AB electrode had obtained, within potential range of 0–1 V at a charge/discharge current density of 200 mA·g⁻¹ in 0.5 mol·L⁻¹ potassium sulfate electrolyte solution in the first cycle. The specific capacitance of both the MnO₂/MWNT and MnO₂/AB electrodes were 141.2 F·g⁻¹ and 78.5 F·g⁻¹ after 1,200 cycles, respectively. The MnO₂/MWNT electrode has better cycling performance. The effect of different morphologies was investigated for both MnO₂/MWNT and MnO₂/AB composites.     

Structural and electrical properties of pure and H<Subscript>2</Subscript>SO<Subscript>4</Subscript> doped (PVA)<Subscript>0.7</Subscript>(NaI)<Subscript>0.3</Subscript> solid polymer electrolyte

Solid polymer electrolytes (SPE) based on poly-(vinyl alcohol) (PVA)_0.7 and sodium iodide (NaI)_0.3 complexed with sulfuric acid (SA) at different concentrations were prepared using solution casting technique. The structural properties of these electrolyte films were examined by X-ray diffraction (XRD) studies. The XRD data revealed that sulfuric acid disrupt the semi-crystalline nature of (PVA)_0.7(NaI)_0.3 and convert it into an amorphous phase. The proton conductivity and impedance of the electrolyte were studied with changing sulfuric acid concentration from 0 to 5.1 mol/liter (M). The highest conductivity of (PVA)_0.7(NaI)_0.3 matrix at room temperature was 10⁻⁵ S cm⁻¹ and this increased to 10⁻³ S cm⁻¹ with doping by 5.1 M sulfuric acid. The electrical conductivity (σ) and dielectric permittivity (ε′) of the solid polymer electrolyte in frequency range (500 Hz–1 MHz) and temperature range (300–400) K were carried out. The electrolyte with the highest electrical conductivity was used in the fabrication of a sodium battery with the configuration Na/SPE/MnO₂. The fabricated cells give open circuit voltage of 3.34 V and have an internal resistance of 4.5 kΩ.     

Near-infrared broadband luminescence in Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>-GeO<Subscript>2</Subscript> binary glass system

Near-infrared broadband luminescence from 1100 to 1600 nm was observed in Bi₂O₃-GeO₂ binary glasses. The strongest emission can be observed with 30 mol % Bi₂O₃ when pumped at 808 nm. The lifetimes of all samples are longer than 200 μs. The glass network was studied by Raman spectra and Bi⁺ ions are proposed as the infrared luminescence centers in this glass system. Thermal treatment in air results in partly oxidation of Bi⁺ to Bi²⁺.     

Fast ionic conduction in cubic hafnium garnet Li<Subscript>7</Subscript>La<Subscript>3</Subscript>Hf<Subscript>2</Subscript>O<Subscript>12</Subscript>

A new member of the family of garnets with fast lithium ion conduction has been found with the composition Li₇La₃Hf₂O₁₂. The anion arrangement corresponds to the oxygen framework in garnets, e.g., in Ca₃Fe₂Si₃O₁₂. Hafnium is coordinated octahedrally while the lanthanum environment can be described as a distorted cube. Lithium occupies a large number of positions with tetrahedral, trigonal planar, and metaprismatic coordination. Li₇La₃Hf₂O₁₂ shows a lithium bulk ion conductivity of 2.4 × 10⁻⁴ Ω⁻¹ cm⁻¹ at room temperature with an activation energy of 0.29 eV.     

Infrared absorption spectra of pure and doped YAl<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript> single crystals

Several weak absorption bands have been observed in the optical absorption spectra of pure and rare-earth-doped YAl₃(BO₃)₄ single crystals in the 3350– 3650 cm⁻¹ wave number region. Two of them, peaking at about 3377 cm⁻¹ and 3580 cm⁻¹ in the 8 K spectra, appear in most of the samples. They are tentatively attributed to the stretching mode of OH⁻ ions incorporated in the crystal during the growth. An additional absorption band at about 5250 cm⁻¹ at 8 K has also been detected in almost all samples. The temperature and polarization dependences of these bands, and their possible origin, are discussed.     

Magnetic properties of LiNi<Subscript>0.5</Subscript>Mn<Subscript>0.47</Subscript>Al<Subscript>0.03</Subscript>O<Subscript>2</Subscript> as positive electrode for Li-ion batteries

The layered LiNi_0.5Mn_0.47Al_0.03O₂ was synthesized by wet chemical method and characterized by X-ray diffraction and analysis of magnetic measurements. The powders adopted the α-NaFeO₂ structure. This substitution of Al for Mn promotes the formation of Li(Ni_0.47²⁺Ni_0.03³⁺Mn_0.47⁴⁺Al_0.03³⁺)O₂ structures and induces an increase in the average oxidation state of Ni, thereby leading to the shrinkage of the lattice unit cell. The concentration of antisite defects in which Ni²⁺ occupies the (3a) Li lattice sites in the Wyckoff notation has been estimated from the ferromagnetic Ni²⁺(3a)–Mn⁴⁺(3b) pairing observed below 140 K. The substitution of 3% Al for Mn reduces the amount of antisite defects from 7% to 6.4–6.5%. The analysis of the magnetic properties in the paramagnetic phase in the framework of the Curie–Weiss law agrees well with the combination of Ni²⁺ (S = 1), Ni³⁺ (S = 1/2) and Mn⁴⁺ (S = 3/2) spin-only values. Delithiation has been made by the use of K₂S₂O₈. According to this process, known to be softer than the electrochemical one, the nickel ions in the (3b) sites are converted into Ni⁴⁺ in the high spin configuration, while Ni²⁺(3a)–Mn⁴⁺(3b) ferromagnetic pairs remain, as the Li⁺(3b) ions linked to the Ni²⁺(3a) ions in the antisite defects are not removed. The results show that the antisite defect is surrounded by Mn⁴⁺ ions, implying the nonuniform distribution of the cations in agreement with previous NMR and neutron experiments.     

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.     

Influence of carbon additive on the properties of spherical Li<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>12</Subscript> and LiFePO<Subscript>4</Subscript> materials for lithium-ion batteries

Preparing spherical particles with carbon additive is considered as one effective way to improve both high rate performance and tap density of Li₄Ti₅O₁₂ and LiFePO₄ materials. Spherical Li₄Ti₅O₁₂/C and LiFePO₄/C composites are prepared by spray-drying–solid-state reaction method and controlled crystallization–carbothermal reduction method, respectively. The X-ray diffraction characterization, scanning electron microscope, Brunauer–Emmett–Teller, alternating current impedance analyzing, tap density testing, and electrochemical property measurements are investigated. After hybridizing carbon with a proper quantity, the crystal grain size of active materials is remarkably decreased and the electrochemical properties are obviously improved. The Li₄Ti₅O₁₂/C and LiFePO₄/C composites prepared in this work are spherical. The tap density and the specific surface area are as high as 1.71 g cm⁻³ and 8.26 m² g⁻¹ for spherical Li₄Ti₅O₁₂/C, which are 1.35 g cm⁻³ and 18.86 m² g⁻¹ for spherical LiFePO₄/C powders. Between 1.0 and 3.0 V versus Li, the reversible specific capacity of the Li₄Ti₅O₁₂/C is more than 150 mAh g⁻¹ at 1.0-C rate. Between 2.5 and 4.2 V versus Li, the reversible capacity of the LiFePO₄/C is close to 140 mAh g⁻¹ at 1.0-C rate.     

Wave mixing in nominally undoped Sn<Subscript>2</Subscript>P<Subscript>2</Subscript>S<Subscript>6</Subscript> at high light intensities

The intensity dependence of the photorefractive response of Sn₂P₂S₆ is studied for the Kr⁺-laser wavelength of 647 nm and pump-beam intensities of up to 10 W/cm². A considerable enhancement of the two-beam coupling gain factor with increasing intensity at a grating spacing of ≃1 μm is attributed to a light-induced increase of the effective trap density. The large gain reached at high intensities is applied for the build up of a double phase conjugate mirror with a sub-millisecond switch-on time.     

Photoluminescence of nanoparticles of (Ga<Subscript>2</Subscript>S<Subscript>3</Subscript>)<Subscript>0.95</Subscript>(Eu<Subscript>2</Subscript>O<Subscript>3</Subscript>)<Subscript>0.05</Subscript> solid solution

We have ground bulk samples to obtain nanoparticles of (Ga₂S₃)_1–x (Eu₂O₃) _x solid solutions, the sizes of which were determined using an atomic force microscope. The photoluminescence spectra of the nanoparticles were studied in the temperature interval 77–300 K. We have established the mechanisms for emission and transfer of energy from the matrix to the rare-earth ion, and we determined the Stokes shift (ΔS = 0.7 eV), the Huang–Rhys parameter (S = 16), and the optical phonon energy (ħ−ω = 23 meV).     

Magnetic properties and large cryogenic low-field magnetocaloric effect of HoCo<Subscript>2</Subscript> nanoparticles without core/shell structure

The HoCo₂ nanoparticles are found to be stable in air without any shell protection. The HoCo₂ nanoparticles display superparamagnetic properties between their blocking temperature of 40 K and Curie temperature of 78 K. The magnetic-entropy change increases with decreasing temperature at a certain magnetic-field change, which is ascribed to the competition between the Zeeman energy and thermal-agitation energy at low temperatures. A large magnetic-entropy change of 19.4 J kg⁻¹ K⁻¹ was found at 7.5 K in an applied-field change from 1 to 7 T, while 6.1 J kg⁻¹ K⁻¹ was achieved in a low field change of 1 T. HoCo₂ nanoparticles are useful for application of magnetic refrigeration at low temperatures.     

Structure,thermal properties,conductivity and electrochemical stability of di-urethanesil hybrids doped with LiCF<Subscript>3</Subscript>SO<Subscript>3</Subscript>

Variable chain length di-urethane cross-linked poly(oxyethylene) (POE)/siloxane hybrid networks were prepared by application of a sol-gel strategy. These materials, designated as di-urethanesils (represented as d-Ut(Y′), where Y′ indicates the average molecular weight of the polymer segment), were doped with lithium triflate (LiCF₃SO₃). The two host hybrid matrices used, d-Ut(300) and d-Ut(600), incorporate POE chains with approximately 6 and 13 (OCH₂CH₂) repeat units, respectively. All the samples studied, with compositions ∞ > n ≥ 1 (where n is the molar ratio of (OCH₂CH₂) repeat units per Li⁺), are entirely amorphous. The di-urethanesils are thermally stable up to at least 200 °C. At room temperature the conductivity maxima of the d-Ut(300)- and d-Ut(600)-based di-urethanesil families are located at n = 1 (approximately 2.0 × 10⁻⁶ and 7.4 × 10⁻⁵ Scm⁻¹, respectively). At about 100 °C, both these samples also exhibit the highest conductivity of the two electrolyte systems (approximately 1.6 × 10⁻⁴ and 1.0 × 10⁻³ Scm⁻¹, respectively). The d-Ut(600)-based xerogel with n = 1 displays excellent redox stability.     

Photoacoustic spectroscopy of thin films of As<Subscript>2</Subscript>S<Subscript>3</Subscript>, As<Subscript>2</Subscript>Se<Subscript>3</Subscript> and GeSe<Subscript>2</Subscript>

Photoacoustic spectroscopy (PAS) is one of the important branches of spectroscopy, which enables one to detect light-induced heat production following the absorption of pulsed radiation by the sample. As₂S₃, As₂Se₃ and GeSe₂ exhibit a wide variety of photo-induced phenomena that enable them to be used as optical imaging or storage medium and various electronic devices, including electro-optic information storage devices and optical mass memories. Therefore, accurate measurement of thermal properties of semiconducting films is necessary to study the memory density. The thermal conductivity of thin films of As₂S₃ (thickness 100 μm and 80 μm), As₂Se₃ (thickness 100 μm and 80 μm) and GeSe₂ (thickness 120 μm and 100 μm) has been measured using PAS technique. Our result shows that the thermal conductivity of thicker films is larger than the thinner films. This can be explained by the thermal resistance effect between the film and the surface of the substrate.      

Electrical characterization of the [N(CH<Subscript>3</Subscript>)<Subscript>4</Subscript>][N(C<Subscript>2</Subscript>H<Subscript>5</Subscript>)<Subscript>4</Subscript>]ZnCl<Subscript>4</Subscript> compound

The [N(CH₃)₄][N(C₂H₅)₄]ZnCl₄ compound has been synthesized by a solution-based chemical method. The X-ray diffraction study at room temperature revealed an orthorhombic system with P2₁2₁2 space group. The complex impedance has been investigated in the temperature and frequency ranges 420–520 K and 200 Hz–5 MHz, respectively. The grain interior and grain boundary contribution to the electrical response in the material have been identified. Dielectric data were analyzed using the complex electrical modulus M ^* for the sample at various temperature. The modulus plots can be characterized by full width at half height or in terms of a non-exponential decay function ϕ(t) = exp[(−t/τ) ^β ]. The detailed conductivity study indicated that the electrical conduction in the material is a thermally activated process. The variation of the AC conductivity with frequency at different temperatures obeys the Almond and West universal law.     

Large optical nonlinearity in CaCu<Subscript>3</Subscript>Ti<Subscript>4</Subscript>O<Subscript>12</Subscript> thin films

CaCu₃Ti₄O₁₂ (CCTO) thin films were successfully prepared on LaAlO₃ substrates by pulsed laser deposition technique. We measured the nonlinear optical susceptibility of the thin films using Z-scan method at a wavelength of 532 nm with pulse durations of 25 ps and 7 ns. The large values of the third-order nonlinear optical susceptibility, χ ⁽³⁾, of the CCTO film were obtained to be 2.79×10⁻⁸ esu and 3.30×10⁻⁶ esu in picosecond and nanosecond time regimes, respectively, which are among the best results of some representative nonlinear optical materials. The origin of optical nonlinearity of CCTO films was discussed. The results indicate that the CCTO films on LaAlO₃ substrates are promising candidate materials for applications in nonlinear optical devices.     

Magnetic properties of nanoparticle La<Subscript>0.7</Subscript>Ca<Subscript>0.3</Subscript>MnO<Subscript>3</Subscript> under applied hydrostatic pressure

Pressure effects on magnetic properties of two La_0.7Ca_0.3MnO₃ nanoparticle samples with different mean particle sizes were investigated. Both the samples were prepared by the glycine-nitrate method: sample S—as-prepared (10 nm), and sample S₉₀₀—subsequently annealed at 900 °C for 2 h (50 nm). Magnetization measurements revealed remarkable differences in magnetic properties with the applied pressure up to 0.75 GPa: (i) for S sample, both transition temperatures, para-to-ferromagnetic T _C = 120 K and spin-glass-like transition T _f = 102 K, decrease with the pressure with the respective pressure coefficients dT _C/dP = −2.9 K/GPa and dT _f/dP = −4.4 K/GPa; (ii) for S₉₀₀ sample, para-to-ferromagnetic transition temperature T _C = 261 K increases with pressure with the pressure coefficient dT _C/dP = 14.8 K/GPa. At the same time, saturation magnetization M _S recorded at 10 K decreases/increases with pressure for S/S₉₀₀ sample, respectively. Explanation of these unusual pressure effects on the magnetism of sample S is proposed within the scenario of the combined contributions of two types of disorders present in the system: surface disorder introduced by the particle shell, and structural disorder of the particle core caused by the prominent Jahn–Teller distortion. Both disorders tend to vanish with the annealing of the system (i.e., with the nanoparticle growth), and so the behavior of the sample S₉₀₀ is similar to that previously observed for the bulk counterpart.