Investigation of Composition of Endometallofullerene Extracts

Gases evolved upon heating endometallofullerene (EMF) extracts with La or Y have been investigated. It has been shown that solvent molecules used to release EMF are observed in extracts up to high temperatures. It has been found that in the dimethylformamide (DMF) extract the EMF molecules are present mainly as the [EMF]^- anions, which were observed in electrospray mass spectra. The treatment of such extracts with iodine results in the anion reduction to neutral molecules.     

Aggregation of Endometallofullerene Y@C82 in Polar Solvents

Abstract

Having studied the optical absorption, fluorescence spectra and dynamic light scattering (DLS) of solutions of Y‐EMF in polar solvents, we demonstrated for the first time that the endohedral metallofullerenes (EMF) forms nanoparticles, the mean size of which ranges up to 100 nm.     

Polarization Effect in ESR of Co Doped CuGeO<Subscript>3</Subscript>

Electron spin resonance of a single crystal of CuGeO₃ doped with 2% of Co has been studied at f = 99 GHz in temperature range 1.8–50 K. Contributions to ESR absorption from Cu²⁺ chains and from Co²⁺ ions were derived. It is found that functions obtained for ESR integrated intensities: Curie-Weiss for Cu²⁺ (χCu ∼ C _Cu/(T + Θ), with Θ = 92 K) and Curie for Co²⁺ (χCo ∼ C _Co/T) are well consistent with temperature dependence of static magnetic susceptibility. Strong dependence of ESR absorption on polarization of oscillating magnetic field was discovered for Co²⁺ contribution. Polarization effect was studied for magnetic field applied along a, b and c directions. Values of g-factors of resonance lines are presented.     

Spin‐Transparency of the Fullerene Shell of Endometallofullerene La@C82

Abstract

For La@C₈₂ embedded into the polycarbonate film, an intensive ¹H‐electron‐nuclear double resonance (ENDOR) has been revealed. Since La‐EMF does not contain hydrogen atoms, it evidences for the electron spin density on the matrix protons. Furthermore, for the solutions of La‐EMF in hexamethylphosphoramide (HMPA), the paramagnetic shift of the ³¹P NMR signal of bulk solvent molecules has been revealed. These findings testify the partial localization of unpaired electron outside the fullerene cage. The “transparency” of the fullerene shell to the electron spin density may serve the important factor in designing the fullerene‐based materials.     

A study of uv preionization pulsed tea CO2 laser

Abstract

A uniform volumetric discharge was obtained by means of an auxiliary UV preionization in a home‐made TEA CO₂ laser. The maximum output pulse energy of this laser system was about 12J per pulse with a pulse duration of 80 ns. The ratio of electric field to neutral particle density (E/N) in this laser was 7.6×10^‐16 V cm². The peak power and pulse shape of the laser were studied. The time delay between the predischarge and the maindischarge during the stable operation of this laser system has also been studied. It was observed that the laser was operating with uniform glow discharges when the time delayed between the predischarge and the maindischarge was in the range of 1.0 μs to 6.0 μs. The spark array used as a preionizer for producing the UV radiation in this system is new, simple, durable, and can be easily fabricated.     

Assembly of Fe3O4 nanoparticles on SiO2 monodisperse spheres

The assembly of superparamagnetic Fe₃O₄ nanoparticles on submicroscopic SiO₂ spheres have been prepared by an in situ reaction using different molar ratios of Fe³⁺/Fe²⁺ (50–200%). It has been observed that morphology of the assembly and properties of these hybrid materials composed of SiO₂ as core and Fe₃O₄ nanoparticles as shell depend on the molar ratio of Fe³⁺/Fe²⁺.     

Mossbauer study of the effect of oxygen stoichiometry on the highTc superconductor Y1Ba2(Cu0.97Fe0.03)3O7?x

The Mossbauer effect of oxygen-depleted YBa₂Cu₃O_7-x and PrBa₂Cu₃O_7-x doped with 3%⁵⁷Fe has been investigated at room temperature. A manifold of quadrupole-split spectra has been found, whose parameters are in general agreement with those found by other workers. In addition, the Mossbauer spectra show that a fraction of the Fe sites develop magnetic order at room temperature when the oxygen content is reduced. It is demonstrated that the observed asymmetries in the Mossbauer spectra can be the result of a preferential alignment of the platelike crystallites that arises during the normal sample preparation process. The tendency to bond with the oxygen atoms is presumed to be responsible for the discreteness of the Mossbauer spectra as a function of oxygen depletion.     

New Molecular Complex of Fullerene C60 with Porphyrin Dimer [FeTPP]2O: Synthesis and Crystal Structure

Abstract

New molecular complex of C₆₀ with covalently linked (Fe^IIITPP)₂O · C₆₀ dimer has been obtained. The complex has isolated packing of fullerenes in which fullerene molecule is embraced in a pocket built by porphyrins. (Fe^IIITPP)₂O preserves its initial geometry in the complex. The Fe···C(C₆₀) contacts are in the 3.239–3.513 Å range indicating the absence of Fe–C₆₀ coordination. This results in the similarity of the EPR spectra of the complex and parent (Fe^IIITPP)₂O.     

Use of oxygen isotope to study the transport mechanism during high temperature oxide scale growth

Abstract

The examination of high temperature (HT) oxide scale growth mechanisms was performed using secondary ion mass spectrometry (SIMS) and secondary neutral mass spectrometry (SNMS), in conjunction with ¹⁶O₂/¹⁸O₂ HT oxidation experiments. Cr₂O₃, NiO, ZrO₂ and Al₂O₃ were studied because they constitute excellent representative thermally grown oxide scales: they grow by cationic diffusion (Cr₂O₃, NiO), anionic diffusion (ZrO₂) or mixed anionic-cationic diffusion (Al₂O₃). The oxidation tests were performed first in ¹⁶O₂ and subsequently in ¹⁸O₂ at several temperatures (600–1000°C for NiO, 600°C for ZrO₂, 1000°C for Cr₂O₃ and 1100°C for Al₂O₃). The oxygen isotope distribution observed by SIMS and SNMS profiles are discussed and related with the HT oxidation mechanisms proposed in the literature.     

Microhardness studies on as-grown faces of NaClO3 and NaBrO3 crystals

Single crystals of NaClO₃ and NaBrO₃ are grown from their aqueous solutions at a constant temperature of 35°C by slow evaporation by using good quality seed crystals. Systematic microhardness studies are made on as-grown faces of these crystals at various loads. Typical cracks are observed at the corners of the impressions in NaClO₃ whereas in addition to the cracks at the corners microcracks also appeared in NaBrO₃ crystals around the impressions. The impressions formed in NaBrO₃ are not very clear as in NaClO₃, a possible mechanism for it is discussed. The work hardening index number(n) for both these crystals is around 1.6 suggesting that these are moderately harder samples. The hardness studies point out that NaBrO₃ is harder than NaClO₃ (ΔH ≈ 100 kg/mm ²,this could be due to strong inter ionic forces acting between Na-Br in NaBrO₃ crystals. Using Gilman’s empirical relation, hardness values are calculated from the values of elastic constants (C ₄₄) and are found to be close to the experimental results.     

Selection of scattering enhancement particles for improving color homogeneity and luminous flux of phosphor-converted LEDs

Abstract

At the present time, color homogeneity and luminous flux are the two essentials utilized to appraise high-quality phosphor-converted LEDs (pcLEDs). In this paper, we present the search for the optimal selection among scattering enhancement particles (SEPs) to apply to improve these essentials for pcLEDs having correlated color temperature of 8500 K. The interested contenders include CaCO₃, CaF₂, SiO₂, and TiO₂. Each of them is added to yellow phosphor compounding (Y₃Al₅O₁₂:Ce³⁺). Firstly, the LightTools program is employed to do the optical simulations. Secondly, the obtained results are verified and analyzed based on Mie scattering theory. The scattering computation of SEPs includes the scattering coefficients, the anisotropic scattering, the reduced scattering and the scattering amplitudes at 455 and 595 nm. It is observed that TiO₂ particles provide the highest color homogeneity among the SEPs but the luminous flux reduces significantly as its concentration increases. By using CaCO₃ particles, the highest luminous flux of 792 lm is obtained. CaCO₃ particles can also reduce the deviation of color correlated temperature to 620 K at 30% concentration. Therefore, CaCO₃ particles should be selected to enhance both color homogeneity and luminous flux.     

Singlet‐Triplet Transition in the C60 2− Dianion

Abstract

The C₆₀ complexes with decamethylcobaltocene: (Cp*₂Co)₂C₆₀(C₆H₄Cl₂, C₆H₅CN)₂ (1) and [K · (18‐crown‐6)]₂ · C₆₀ · (DMF)₄ (2) have been obtained as single crystals by the diffusion method. The IR‐ and UV‐VIS‐NIR‐spectra justify the formation of the C₆₀ ^2? dianions in these salts. EPR measurements show that the low temperature signals of 1 in the 4–140 K range and 2 in the 4–60 K range have intensity corresponding only to 0.4% and 3.5% from total C₆₀. Because of this, most of the complexes are EPR silent, and, consequently, C₆₀ ^2? has a diamagnetic singlet (S = 0) state in these temperature ranges. The appearance of a broad EPR signal in the spectum of 1 above 140 K and 2 above ～60 K is assigned to a thermal population of a close lying excited triplet (S = 1) state. The singlet–triplet energy gap for C₆₀ ^2? in solid 1 and 2 was estimated to be 730 ± 10 and 300 ± 10 cm^?1.     

Magnetic field effects on electric behavior of [Fe(CN)6]3− at bare and membrane-coated electrodes

Abstract

The cyclic voltammetric behavior of [Fe(CN)₆]^3? was investigated under homogeneous magnetic fields perpendicular to the electrode surface in order to determine the effects of magnetic fields on the distribution of an Fe²⁺/Fe³⁺ redox couple. The cathodic current was enhanced much more than the anodic current by a homogeneous magnetic field, suggesting that the concentration gradient of paramagnetic [Fe(CN)₆]^3? and diamagnetic [Fe(CN)₆]^4? formed at an electrode surface may also contribute to the asymmetric current. The apparent diffusion coefficient of the redox couple increased by over 30% in both cathodic and anodic processes upon applying a magnetic field. For a gold electrode coated with dioctadecyldimethylammonium, the application of a magnetic field perpendicular to the surface increased the peak-to-peak separation, and enhanced the asymmetric current. It is inferred that the application of a magnetic field promotes the electron-tunneling process by tilting chain molecules in the barrier membrane.     

Spectroscopic investigations of Cu2+ in Li2O-Na2O-B2O3-Bi2O3 glasses

Pure and copper doped glasses with composition,x Li ₂ O-(40-x)Na ₂ O-50B ₂ O ₃-10Bi ₂ O ₃,have been prepared over the range 0 ≤ x ≤ 40. The electron paramagnetic resonance (EPR) spectra of Cu²⁺ ions of these glasses have been recorded in the X-band at room temperature. Spin Hamiltonian parameters have been calculated. The molecular bonding coefficients, α² and β², have been calculated by recording the optical absorption spectra in the wavelength range 200–1200 nm. It has been observed that the site symmetry around Cu²⁺ ions is tetragonally distorted octahedral. The density and glass transition temperature variation with alkali content shows non-linear behaviour. The IR studies show that the glassy system contains BO₃ and BO₄ units in the disordered manner.     

Effect of zirconium addition on the recrystallization behaviour of a commercial Al-Cu-Mg alloy

It is well known that the second phase particles have an effect on recrystallization and grain growth behaviour of an alloy. Particularly the bimodal distribution of second phase particles has an effect which is opposite in sense where coarse second phase particles (> 1 μm) stimulate nucleation while fine particles exhibit Zener drag. In the literature, the effect of zirconium addition to aluminium alloys has been well documented in order to produce superplasticity by giving ultra fine grain size to the alloy. Addition of zirconium produces Al ₃ Zr particles which pin the grain boundaries during recrystallization and grain growth. In the present work, zirconium was added to a commercial Al-Cu-Mg alloy and by heat treatment Al ₃ Zr particles were precipitated and after forging, the grain size was an order of magnitude lower than the alloy without zirconium. Transmission electron microscopy was employed to characterize the second phase particles, i.e. Al ₃ Zr particles and found to be rod shaped and identified to be cubic ordered L 1 ₂ phase with a lattice parameter of 0.408 nm. Further, it was observed that fine (100 nm) Al ₃ Zr particles promote only continuous recrystallization which is polygonization of subgrains and subgrain growth. It was found that the fine dispersion of Al ₃ Zr particles inhibits both recrystallization and grain growth in the commercial Al-Cu-Mg alloy.     

Local analysis of Eu2+ emission in CaAlSiN3

Abstract

We have investigated the local luminescence properties of Eu-doped CaAlSiN₃ by using low-energy electron beam (e-beam) techniques. The particles yield broad emission centered at 655 nm with a shoulder at higher wavelength under light excitation, and a broad band around 643 nm with a tail at 540 nm under e-beam excitation. Using cathodoluminescence (CL) in a scanning electron microscope (SEM), we have observed small and large particles, which, although with different compositions, exhibit Eu²⁺-related emissions at 645 and 635 nm, respectively. Local CL measurements reveal that the Eu²⁺ emission may actually consist of several bands. In addition to the red broad band, regularly spaced sharp peaks have been occasionally observed. These luminescence variations may originate from a variation in the composition inside CaAlSiN₃.     

SERS property of Co complex on boron nitride nanosheets/silver nanoparticles aggregates and photophysical characterisation of interactions among Co complex ion-exchanged within zirconium phosphate

ABSTRACT

The Co(II) complex of [Co(bpy)₂(NO₃)]Cl·3H₂O, bpy = 2,2'-bipyridine, has been synthesised by the solution crystallisation method. The boron nitride nanosheets/silver nanoparticles/[Co(bpy)₂(NO₃)]Cl·3H₂O nanoaggregate was prepared in order to better analyse the adsorption orientation of the cobalt complex on the surface of silver nanoparticles. The result of the surface-enhanced Raman scattering measurement indicates that the molecular plane of the cobalt complex presents a tilted orientation with respect to the surface of silver nanoparticles. The luminescence property of [Co(bpy)₂(NO₃)]⁺ two-dimensional arrangements within the layers of zirconium phosphate (ZrP) was also investigated. Steady-state luminescence spectra of the [Co(bpy)₂(NO₃)]⁺-exchanged ZrP materials show an increase in the luminescence intensity.     

Influence of Structural Effects on the Superconductivity of Ammonia‐Doped NaK2C60

Abstract

The role of structural effects on the anomalous superconducting properties of (NH₃) _x NaK₂C₆₀ fullerides was investigated using ²³Na and ²H NMR. In the metallic (NH₃) _x NaK₂C₆₀ (0.5 < x < 1) compounds, the ²³Na quadrupolar splitting is observed to be independent from ammonia concentration x which, on the other hand, substantially affects the superconducting transition temperature. The marginal influence of sodium cation displacement in the superconducting properties is confirmed also by the absence of any electric field gradients in the recently synthesized nonmagnetic insulator (NH₃)₂NaK₂C₆₀. ²H NMR measurements on deuterated samples enabled us to study the ND₃ reorientational dynamics, indicating a hampered ammonia rotation in the insulating (x = 2) case, where the Na⁺ ions become centered.     

Precipitation of cetyl (hexadecyl) pyridineum chloride using mono and divalent oxyanions

Experimental investigations have been carried out to observe the performance of precipitation behavior of potassium permanganate (KMnO₄) and potassium dichromate (K₂Cr₂O₇) in cetyl (hexadecyl) pyridineum chloride (CPC) solution. As in the case of Al³⁺-dodecylbenzenesulfonate systems [P. Somasundaran, K.P. Anathapadmanabhan, M.S. Celik, Langmuir 4 (1988) 1061–1063], the precipitation is found to be caused by interaction of CPC micelles with oxyanions. The counter oxyanions have a strong tendency to bind themselves to the surface of cationic CPC micelles. This lowered the free oxyanion concentration in solution. Therefore, to start precipitation, higher oxyanion concentration is required for higher CPC concentration. The effects of temperature, concentrations of both counter ions and CPC on the precipitation have been studied in detail. It has been observed that at CPC to KMnO₄ concentration ratio of 1.0 (concentration of CPC and KMnO₄ is 400 ppm), the percentage precipitation of CPC is around 99.3 at 30 °C. The percent precipitation of CPC decreases to about 94% when temperature increases to 70 °C at the same condition. The extent of CPC precipitation increases at the same experimental condition when K₂Cr₂O₇ is used instead of KMnO₄.     

Y2O3:Eu3+ phosphor: a novel solution for an increase in color rendering index of multi-chip white LED packages

Abstract

In this study, a novel compound is synthesized by adding the red-emitting Y₂O₃:Eu³⁺ dopant to conformal phosphor package (CPP) or in-cup phosphor package (IPP), to be employed as a component in multi-chip white LEDs lamps (W-LEDs). It was found that this solution can enhance the color rendering index (CRI) of W-LEDs that have correlated color temperatures of 5600 K through 8500 K to more than 86. Besides, the impacts of the Y₂O₃:Eu³⁺ phosphor on the attenuation of light through the phosphor layers, CPP and IPP, are also demonstrated based on the Beer–Lambert law and Mie theory. These results provide important information for producing W-LEDs with higher CRI.