Thermo-optic properties of B2O3 doped Li2O-Al2O3-SiO2 glass-ceramics

Reduction in the temperature coefficient of the optical path length, dS/dT of Li₂O-Al₂O₃-SiO₂ glass-ceramics with near-zero thermal expansion coefficient was attempted using control of the temperature coefficient of electronic polarizability, ?, and the thermal expansion coefficient, α. The dS/dT value of 2.6 mol% B₂O₃-doped glass-ceramic was 12.5  × 10⁻⁶/°C, which was 0.9 ×  10⁻⁶/°C smaller than that of B₂O₃-free glass-ceramic. On the other hand, reduction in dS/dT through B₂O₃ doping was not confirmed in precursor glasses. Results showed that reduction in dS/dT of the glass-ceramic through B₂O₃ doping is caused by the reduction in ?. The reduction in ? from B₂O₃ doping was probably attributable to numerical reduction in non-bridging oxide ions with larger ? value by the concentration of boron ions in the residual glass phase. In addition, application of hydrostatic pressure during crystallization was effective to inhibit precipitation of β-spodumene solid solution, which thereby decreases dS/dT. The dS/dT value of B₂O₃-doped glass-ceramic crystallized under 196 MPa was 11.7 ×  10⁻⁶/°C. That value was slightly larger than that of silica glass. The α value of this glass-ceramic was smaller than that of silica glass.     

Crystal Growth and Elastic Properties of Hopeite,Zn3(PO4) · 4 H2O

Single crystals of orthorhombic Zn₃(PO₄)₃ · 4 H₂O of optical quality with dimensions up to 12 × 10 × 8 mm were grown from aqueous solutions of ZnSO₄ and NaH₂PO₄ by controlled diffusion of NH₃ into the solution. The elastic constants c_ij and the thermoelastic constants T_ij = dc_ij/dT, T temperature, were determined from ultrasonic resonance frequencies of thick plates in the range between 5 and 40 MHz and between 250 and 320 K. In respect to the longitudinal elastic stiffness hopeite behaves quasi isotropically, however, the elastic shear stiffness shows a large anisotropy of about a factor 2.5. Above 260 K the shear stiffness c₆₆ possesses a quite anomalous temperature dependence (T₆₆ > 0). Further, the linear thermal expansion reveals a strong anisotropy (α₁₁ = −3.3, α₂₂ = 3.4, α₃₃ = 33 · 10⁻⁶/K).     

Dielectric characteristics of neodymium heptamolybdate crystals grown by gel encapsulation technique

Results obtained from the dielectric studies of neodymium heptamolybdate crystals grown in the system Nd(NO₃)₃ –MoO₃ –NH₄OH– HNO₃ —Na₂SiO₃ by gel encapsulation technique are presented. The variation of dielectric constant (ε′), dielectric loss (tanδ) and conductivity (σ) with frequency at different temperatures is studied. The dielectric constant of the material increases sharply, attains a peak value and then decreases rapidly, as material's temperature rises from room temperature to higher degrees. The temperature at which the peak value is attained is the transition temperature of the material. Dielectric loss (tan δ) follows almost a similar behaviour. The conductivity (σ) is also found to be temperature-and frequency-dependent. This sharp rise in ε′ is attributed to the contribution from space charge polarization. Theoretically obtained data using the expression ε′ = a₀ + a₁ T² and —In σ = a + b(T — T₀)² for T < T₀) fits very well with the experimentally obtained data indicating that space charge polarization increases as some power of temperature larger than one.     

Crossover temperature (TCO) and temperature gradient of refractive indices and length to breadth ratio of 4O.m mesomorphic compounds – an optical study

Refractive indices as a function of temperature are measured in a number of liquid crystals which belong to the N-(p-n-butoxy benzylidene)-p-n alkyl anilines, 4O.m compounds of the famous Schiff’s base nO.m liquid crystal compounds with m = 4 to 10 and 12. The temperature gradient of refractive indices, dn_e/dT and dn_o/dT, of these compounds are estimated. It is well known that in the case of dn_o/dT, there exists a crossover temperature, T_CO, which exhibits an odd–even effect with the alkyl chain length as expected. Further, using the birefringence data, the length to breadth ratio, k, for these compounds is estimated, which shows not exactly even–odd effect but irregular change with the chain number. The results are discussed with the body of the data.     

Estimation of activation parameters for diffusion-controlled crystallization of barium tungstate from sodium tungstate melts by differential thermal analysis

The proximity (d₁₂) between a diffusing species and its host crystal necessary for a successful diffusion for diffusion-controlled crystallization of barium tungstate from sodium tungstate melts in platinum crucibles was estimated. These distances increased with increased cooling rates (R_T) and crystallization temperatures (T₀). Energy (E), enthalpy (ΔH_a), entropy (ΔS_a) and free-energy (ΔG_a) of activation and the pre-exponential factor (k₀) were evaluated using an ordinary Arrhenius equation k_D1 = k₀e^−E/RT, where k_D1 was the diffusion rate-constant. These parameters were virtually unaffected by the changes in T₀ and R_T.     

Molecular structure and spectra of bis (1,4-dimethylpyridinium)-tetrachlorocuprate(II)

Reaction of 1,4-dimethylpyridinium chlorosulphite with anhydrous copper(II) chloride in an atmosphere of dry nitrogen yields an ionic complex containing discrete [CuCl₄]^2– anions and 1,4-dimethylpyridinium cations. Electronic (solid and in solution), far infrared and¹H NMR spectral data predict a distortedT _d structure which has been confirmed by X-ray crystallography. The crystal structure was solved by the heavy-atom method and refined by full-matrix least squares toR=0.059 for 1685 observed reflections. The [CuCl₄]^2– anions exhibit twofold symmetry and there are no unusual interactions with the cations. Bond lengths and angles place it in the select class of complexes with the least flattenedT _d structure.     

Differential thermal analysis studies on the crystallization of strontium tungstate melts. Variation of rate constants with crystallization temperatures and cooling rates

Kinetics of strontium tungstate crystallization from sodium tungstate melts were studied in platinum crucibles (by DTA) by continuous cooling from initial crystallization temperatures T₀ = 800° to 1000° to below the eutectic temperature at cooling rates R_T = 0.67° to 3.3° min⁻¹. Heterogeneous nuclei first formed slowly onto metal platinate particles within the solution during induction periods (t ); the main crystal growth then started after the development of some exces solute concentration (ΔC ) at the induction temperature (T ). The actual growth after t was diffusion rate-controlled. The diffusion rate-constants (k_Dt) for growth after the induction periods along the major axis were estimated; the increased with T₀ and R_T. These values were higher than those for diffusion-controlled crystal growth of strontium tungstate from sodium tungstate melts in alumina crucibles but much smaller than the real diffusion rate-constants (k_Dl)_real.     

Growth,structure, and superconducting properties of Bi2Sr2Ca2Cu3O10 and (Bi,Pb)2Sr2Ca2Cu3O10‐y crystals

Large and high‐quality single crystals of both Pb‐free and Pb‐doped high temperature superconducting compounds (Bi_1‐xPb_x)₂Sr₂Ca₂Cu₃O_10‐y (x = 0 and 0.3) were grown by means of a newly developed “Vapour‐Assisted Travelling Floating Zone” technique (VA‐TSFZ). This modified zone‐melting technique was realised in an image furnace and allowed for the first time to grow Pb‐doped crystals by compensating for the Pb losses occurring at high temperature. Crystals up to 3×2×0.1 mm³ were successfully grown. Post‐annealing under high pressure of O₂ (up to 10 MPa at T = 500°C) was undertaken to enhance T_c and improve the homogeneity of the crystals. Structural characterisation was performed by single‐crystal X‐ray diffraction (XRD) and the structure of the 3‐layer Bi‐based superconducting compound was refined for the first time. Structure refinement showed an incommensurate superlattice in the Pb‐free crystals. The space group is orthorhombic, A2aa, with cell parameters a = 27.105(4) Å, b = 5.4133(6) Å and c = 37.009(7) Å. Superconducting studies were carried out by A.C. and D.C. magnetic measurements. Very sharp superconducting transitions were obtained in both kinds of crystals (ΔT_c ≤ 1 K). In optimally doped Pb‐free crystals, critical temperatures up to 111 K were measured. Magnetic critical current densities of 2�10⁵ A/cm² were measured at T = 30 K and μ₀H = 0 T. A weak second peak in the magnetisation loops was observed in the temperature range 40‐50 K above which the vortex lattice becomes entangled. We have measured a portion of the irreversibility line (0.1‐5 Tesla) and fitted the expression for the melting of a vortex glass in a 2D fluctuation regime to the experimental data. Measurements of the lower critical field allowed to obtain the dependence of the penetration depth on temperature: the linear dependence of λ(T) for T < 30 K is consistent with d‐wave superconductivity in Bi‐2223. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Emissionselektronenmikroskopische Untersuchungen am Zweistoffsystem Niob-Eisen

Results from emission electron microscope investigations of thermal and mechanical behaviour of the Laves-phase NbFe₂ and of two-phase areas in the binary system Nb Fe are presented. The melting process of NbFe₂ samples with included μ-phase NbFe was observed in the emission microscope and supported the existence of a eutectic between both intermetallic compounds. The Laves-phase NbFe₂ was deformed plastically by a microhardness tester and also homogenously by a compressive device during electron microscope observations. Both yield stress and microhardness of NbFe₂ were measured as a function of temperature up to 1550 K. The relation between a critical temperature T₀ of the hardness-temperature curve and the melting temperature T_m was T₀/T_m = 0,64, in good agreement with results from other Laves-phases. During the heating of NbFe₂ samples a niobium oxide decoration structure appeared at residual air pressures from 1 · 10⁻⁶ torr to some 10⁻⁴ torr. The observed density of decoration points amounted to (1…5) · 10⁸ cm⁻². A discussion shows the possibility of a connection between decoration points and dislocations emerging from the crystal.     

Synthesis and Nonlinear Optical Properties of Novel Polyester Containing Nitrophenylazonitroresorcinoxy Group

A new X-type polyester (4) containing nitrophenylazonitroresorcinoxy groups as NLO chromophores, which are components of the polymer backbone was prepared. Polyester 4 is soluble in common organic solvents such as N,N-dimethylformamide and dimethylsulfoxide. It shows a thermal stability up to 280°C from thermogravimetric analysis with glass-transition temperature (T_g) obtained from differential scanning calorimetry near 120°C. The second harmonic generation (SHG) coefficient (d₃₃) of poled polymer films at the 1064 nm fundamental wavelength is around 5.08 × 10^?9 esu. The dipole alignment exhibits a thermal stability even at 5°C higher than T_g, and no SHG decay was observed below 125°C due to the partial main-chain character of polymer structure, which is acceptable for NLO device applications.     

Nematic-Isotropic Transition in MBBA and its Mixtures with 4-Methoxybenzaldehyde: Applications to the Purity Control of Liquid Crystals

The nematic-isotropic transition temperatures of MBBA(1) + 4-methoxybenzaldehyde(2) mixtures (where MBBA=N(4-methoxybenylidene)-4-n-butylaniline) for 0  x₂  0.06 and additionally the transition enthalpy of pure MBBA were measured by a calorimetric method. Straight lines were found for the T¹(x₂) and Tⁿ(x₂) curves respectively where T¹ and Tⁿ are the upper and the lower limiting temperatures of the transition range for a given x₂. The results are compared with literature data on similar systems and confirm the wellknown rule that the decrease of the nematic-isotropic transition temperature with increasing x₂ depends more strongly on the size and the shape than on the polarity of component 2. From a plot of δT [tbnd] T¹ - Tⁿ against x₂ the mole fraction of impurity in the original sample can be extrapolated.     

Thermodynamic properties of strontium tungstate crystal growth from sodium tungstate melts

Energy (E), enthalpy (ΔH_a), entropy (ΔS_a) and free-energy (ΔG_a) of activation and the pre-exponential factor (k₀) of the ordinary Arrhenius equation k_Dl = k₀e–E/RT were estimated for diffusion-controlled crystal growth of SrWO₄ from Na₂WO₄ melts. E increased slightly with increased cooling rates (R_T). k₀ was parallel to k_Dl and increased with increasing R_T. ΔH_a, ΔS_a, and ΔG_a did not change with the changes in R_T and crystallization temperature (T₀). The distance (d₁₂), between a diffusing particle and its host necessary for a successful diffusion, was estimated. Such distances slightly increased with T₀ and R_T.     

Line width measurements of Cr in a zinc borate glass

The temperature dependence of the homogeneous line width (Γ_h) of the R-line of Cr³⁺ in 4ZnO·3B₂O₃ glass in the region between 15 K and room temperature has been measured. We found that Γ_h has a T ² dependence down to approximately 30 K. Below 30 K the data do not follow the power law, T ². The results are compared with those of Cr³⁺ in mullite and ED2 silicate glasses where the crossover was observed at about 80 K and with the data for Eu³⁺ in zinc borate and other glasses. The comparison indicates that the local environment affects Γ_h. In fact, the Cr³⁺ ions appear to form more defined complexes with the oxygen ligands than do the Eu³⁺ ions, which have a larger distribution of sites in the glass.     

Effect of the magnetic flux trapping upon the temperature dependence of the flow stress change at the superconducting transition

The effect of the superconducting transition on the flow stress in single and polycrystals of Pb-In and Pb-Sn alloys has been studied in the temperature range 1.8 K to T_e. Unlike earlier efforts, these experiments involved investigation of the magnetic flux trapping. Two types of temperature dependences of the magnetic flux trapping, B₀(T), were revealed. In Pb-1.9 at.% In and Pb-6 at.% Sn alloys (subjected to various thermal treatment), B₀ monotonically rises with lowering temperature. In Pb-1.8, 3 at.% Sn single crystals the flux trapping arises at high strains (> 50%) and low temperatures (<2.5 K). In this case B₀ magnitude depends on the strain rate. The difference in the B₀(T) behaviour is associated with dissimilar flux pinnig by pinning centres. The date on B₀(T) obtained give an insight into the two types of the Δσ(T) dependences; taking into account of the flux trapping allowed the Δσ values to be corrected, so that as a result, a single Δσ_SN(T) curve was obtained for all the alloys and structures studied.     

Optimization of parameters for deposition of ZnO films by sol gel using Taguchi method

ABSTRACT

ZnO transparent conductive films were deposited on glass substrates by sol-gel spin coating method. Taguchi method was used to find the optimal deposition parameters, three influential parameters were selected in this experiment, Concentration of zinc (II) ions. Zn²⁺, annealing temperature T_r and pre-annealing temperature T_P. By employing the analysis of variance, we found that the annealing temperature T_r and the precursor Zn²⁺ are the most influencing parameters on the properties of ZnO films. Under the optimized deposition conditions, the ZnO films showed high crystal quality, and high transmittance of 90% in the visible region.     

Wide band-gap organic molecules containing benzodithiophene and difluoroquinoxaline derivatives for solar cell applications

Abstract

Two new semiconducting organic small molecules, namely BDTQ-BDT(EH) and BDTQ-BDT(OC), were prepared by attaching electron accepting 2,3-didodecyl-6,7-difluoro-5,8-di(thiophen-2-yl)quinoxaline (DTQ) unit on 2,6-position of electron donating 4,8-bis(2-ethylhexyloxy)benzo[1,2-b:4,5-b']dithiophene (BDT(EH)) and 4,8-bis(octyloxy)benzo[1,2-b:4,5-b']dithiophene (BDT(OC)) units. Molecule BDTQ-BDT(EH) showed higher thermal stability (5% weight loss temperature, T_d “349 ^оC), slightly lower band-gap (E_g “2.10?eV) and deeper highest occupied molecular orbital energy level (HOMO “–5.36?eV) level compared to those (T_d “336 ^оC, E_g “2.11?eV, and HOMO “–5.30?eV, respectively.) of the molecule BDTQ-BDT(OC). The organic solar cells (OSCs) made with the synthesized molecules as an electron donor and [6,6]-phenyl C₇₁ butyric acid methyl ester (PC₇₀BM) as an electron acceptor gave a maximum power conversion efficiency (PCE) of 1.20% and 0.83%, respectively, for BDTQ-BDT(EH) and BDTQ-BDT(OC). This study confirmed that the substituents attached on the 4,8-position of BDT unit greatly alter the properties of the resulting molecules.     

Nonlinear optical properties of strontium tartrato‐antimonate(III) dihydrate,Sr[Sb2{(+)‐C4H2O6}2]·2H2O

The tensor of nonlinear optical susceptibility for second harmonic generation [d^SHG _ijk ] of hexagonal (point group 6) strontium tartrato‐antimonate(III) dihydrate, Sr[Sb₂{(+)‐C₄H₂O₆}₂]·2H₂O, was determined using the Maker fringes method and a Nd:YAG laser with a wavelength of 1064 nm. The largest component of the tensor d^SHG ₃₃₃ amounts two times d^SHG ₁₁₁ of α‐quartz. Effective nonlinear optical susceptibility d^SHG _eff is given for phase matching type I for several wavelengths (for type II d^SHG _eff is nearly zero). The thermal stability of crystals of Sr[Sb₂{(+)‐C₄H₂O₆}₂]·2H₂O was determined in the temperature range from 153 K to 573 K by means of thermal expansion measurements and thermogravimetry. The temperature dependence of thermal expansion coefficients is given in the range from 153 K to 293 K. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

The annealing of alkaline-earth metal polymetaphosphate powders (I). Crystallisation and sintering processes

Amorphous barium, strontium, calcium and magnesium polymetaphosphate powders (MP₂O₆)_n, n = 20 were prepared by dehydration of the corresponding polymetaphosphate hydrate precipitates. These powders were annealed by different continuous and isothermal heat treatments over the temperature range 450° to 700 °C, the glass transition temperatures T_g to above (T_g + 120) °C. The morphologies at different degrees of crystallisation were studied by scanning electron microscopy. For the main crystallisation process (ten to sixty-seventy percent crystallisation), the powder particles retained their original pea-pod form; then after seventy percent crystallisation, these crystallised particles sintered laterally to lozenge-shaped twin-hexagonal crystals of lengths 0.5 to 3 μm. Differential thermal analysis confirmed that a markedly exothermic crystallisation process (overall enthalpy changes from about 30 to 45 kJ mol⁻¹) was occurring within the powder particles. Crystallisation rates varied from < 0.005 min⁻¹ at temperatures near T_g to > 0.5 min⁻¹ at higher temperatures; the activation energies for this process varied from 360 to 560 kJ mol⁻¹. The completely annealed crystals were studied by scanning electron microscopy, X-ray diffraction and further differential thermal analysis to 1000 °C. The X-ray diffraction d value patterns, the fusion temperatures and the enthalpies of fusion were all in close agreement with the literature values for the corresponding beta alkaline-earth metal polymetaphosphates prepared by melt crystallisation.     

Nuclear Spin-Lattice Relaxation in the Linear Chain Metal,NbSe3

Abstract

The nuclear spin-lattice relaxation time T ₁ of ⁹³Nb in NbSe₃ has been observed as a function of frequency v _N in the range 6-40 MHz at 4.2 K and of temperature T in the range 1.3-77 K at 10 MHz. [T ₁ T]^?1 is found to be proportional to 1/√ν corresponding to characteristic divergence of spin correlation function in 1-D system. Below ~10 MHz, a break down of the divergence is observed. The important features of the T dependence observed are a sharp minimum at ~45 K and an asymptotical approach to the metallic relation, T ₁ T= const, with decreasing T down to helium temperature. This [T ₁ T]^?1 minimum is explained by the destruction of the Fermi surface due to the CDW gap formation. The re-increase of [T ₁ T]^?1 below the CDW transition may suggest a partial recovery of the destructed Fermi surface.     

Dielectric properties of fluorinated silicon dioxide films

Amorphous fluorinated Si dioxide (a-SiO₂:F) films were deposited at 300°C by plasma-enhanced chemical vapor deposition (PECVD) using SiH₄–O₂–CF₄ mixtures with different RF power and deposition temperatures T_d. Their bonding and dielectric properties were investigated. The F content, deposition rate and dielectric constant, _s, decreased and water resistance improved as either RF power or T_d increased. However, for obtaining a film with both small _s and high water resistance, the value of _s was limited to _s ≈ 3. It is proposed that increased water absorption could be caused by occurrence of high tensile stress in the films, and that high-decomposition rates of CF₄, high-energy ion bombardment and/or easier surface migration of adsorbates during film growth, caused by increasing RF power or T_d, act to remove weak Si–O and Si–F bonds, resulting in films with low _s and high water resistivity.