Preparation and superconductivity of (B1−xCx)(Sr1−yBay)2Ca2Cu3Oz

Preparation of (B_1−xC_x)(Sr_1−yBa_y)₂Ca₂Cu₃O_z has been studied using high-pressure synthesis technique to improve sample quality. Samples were prepared from various starting compositions of 0.2≤x≤0.8 and 0≤y≤1. Nearly single-phased samples were obtained for (B_0.6C_0.4)(Sr_1−yBa_y)₂Ca₂Cu₃O_z (0≤y≤0.75) and (B_1−xC_x)-(Sr_0.25Ba_0.75)₂Ca₂Cu₃O_z (0.3≤x≤0.6). We have found that the partial substitution of Ba is effective to improve the sample quality as well as to enhance the T_c. The C substitution was also demonstrated to affect the sample preparation and the physical properties. Based on the substitution study, a maximum T_c of 120 K was observed for the sample with a starting composition of (B_0.65C_0.35)(Sr_0.3Ba_0.7)₂Ca₂Cu₃O_9+δ. Critical current density (J_c) and irreversibility field (H_irr) were estimated from magnetization measurements. The J_c at 77 K in a field of 1 T was about 1.1×10⁴ A/cm³ and the H_irr at 77 K was about 2.5 T. The H_irr was well-described by H_irr=a(1−T/T_c)ⁿ with a=39.1 and n=2.38.     

Synthesis,phase formation,and properties of nanomaterials based on the titanium dioxide−iron(III) oxide binary system

The properties of nanomaterials based on the titanium dioxide?iron(III) oxide binary system prepared by low-temperature coprecipitation from aqueous solutions are studied. The effect of thermal treatment conditions and other factors on the process of phase formation and the properties of the synthesized products is examined. It is demonstrated that these materials have a relatively low photocatalytic activity but a high sorption capacity.     

Geometric and electronic structure of epitaxial NbxTi1−xO2 on TiO2(110)

We have investigated the detailed geometric and electronic structure of MBE-grown Nb_xTi_1−xO₂ on TiO₂(110) by means of high-resolution transmission electron microscopy, X-ray photoelectron diffraction, ultraviolet and X-ray photoemission and electron energy loss spectroscopy. We find no measurable change in the NbO bond length relative to that for TiO bonds in TiO₂ in the dilute limit (x = 0.05), and that the epitaxial layers remain strained and coherent with the substrate for x ⩽ ≈ 0.3. However, significant dislocation generation occurs for x > ≈ 0.3. Nb substitution for Ti in the lattice introduces an additional valence electron per atom. The resulting density of states falls in the valence band region, but no new state density occurs in the either the band gap or conduction band. This result is in contrast to what occurs in the very dilute limit (parts per thousand), where Nb electrons occupy a shallow donor level near the conduction band minimum. Based on the electron counting rule, the extra Nb electrons form a non-bonding band which is degenerate with the valence band. The significance of these results for enhanced thermal and photochemistry on Nb_xTi_1−xO₂ surfaces vis a vis TiO₂ is discussed.     

Solid-state2H NMR studies of methyl group dynamics in aspirin and aspirin · β-cyclodextrin

The dynamics of the methyl group in aspirin, and in the inclusion complex aspirin · β-cyclodextrin, have been studied by deuterium nuclear magnetic resonance spectroscopy and relaxation time measurements. The methyl group in aspirin undergoes fast thermally activated rotation about its axis of symmetry within the temperature range studied, 120 ≤T ≤ 295 K, with an activation energy of 4.9±0.05 kJ/mol and a correlation time at 230 K of (2.47±0.3) · 10^?12 s. The motionally averaged electric field gradient tensor, however, remains axially asymmetric because of electronic effects of a neighbouring oxygen atom. In aspirin · β-cyclodextrin the methyl group rotation about its axis of symmetry is less hindered with an activation energy of 2.1 ± 0.7 kJ/mol and a correlation time at 230 K of (2.5 + 0.4) · 10^?12 s. The axis of symmetry undergoes a slow reorientation with a higher activation energy of 21 ±9 kJ/mol and a correlation time at 230 K of (1.7±1.5) · 10^?6 s.     

TiO2–carbon nanotube composites for visible photocatalysts – Influence of TiO2 crystal structure

We investigated the influence of the crystal structure of TiO₂ and the use of different TiO₂ precursors on the properties and photocatalytic activity of carbon nanotube (CNTs)–titania composites. We found that the crystal structure and properties of starting TiO₂ nanomaterial significantly affected the effect of CNTs incorporation on the photocatalytic activity under simulated solar and visible light illumination (simulated solar illumination with UV-blocking filter). In case of significant photocatalytic activity under visible light illumination (anatase TiO₂), likely due to the presence of native defects, composites exhibited lower activity under visible illumination only, but higher activity under simulated solar illumination. The opposite trends were observed for P25 (anatase + rutile) and rutile TiO₂, where incorporation of CNTs resulted in a significant increase of photocatalytic activity under visible illumination. Thus, control over crystal structure and native defects is essential for the development of efficient visible light activated photocatalysts.     

Concentration dependence of EPR spectra in mixed (BaF2)1 − x (CeF3) x crystals

Physics of the Solid State - In the EPR spectra of the (BaF2)1 − x (CeF3) x system, additional lines appear as the concentration x in the mixture increases from 10−3 to 10−2, some...     

Lattice dynamics and electronic structure of cobalt–titanium spinel Co2TiO4

Physics of the Solid State - The results are presented on phonon excitations and the electronic structure of Co2TiO4 inverse spinel in which magnetically ordered cobalt ions Co2+ (3d 7) are in...     

Synthesis and excess conductivity analysis of TlBa2(Ca3−y Be y )Cu4O12−δ superconductors

TlBa₂(Ca_3?y Be _y )Cu₄O_12?δ (y = 0, 0.5, 1.0, 1.5, 2) samples are synthesized at normal pressure and the influence of doped Be-atoms on the superconductivity parameters at the microscopic level is investigated by carrying out excess conductivity analyses of conductivity data. The samples have shown tetragonal structure and the unit cell volume decreases with increased Be-doping. The onset temperature of superconductivity [T _c(onset)] and zero resistivity critical temperature [T _c(R = 0)] decrease with increased Be, however, the magnitude of diamagnetism is enhanced with Be (except for Be-doping of y = 1.0). The apical oxygen mode of the type Tl–O_A–Cu(2) and CuO₂ planar oxygen mode are softened as observed in FTIR absorption measurements. The FIC analyses of conductivity data have shown an increase in the coherence length along the c-axis and inter-plane coupling. The values of B _c0(T), B _c1(T), J _c(0), τ _φ are improved with the doping of Be. These observations suggested that due to the proximity effect there is less suppression in the value of the order parameter of the Cooper pairs from |ψ|² = 1 value in the CuO₂ planes in Be-doped samples that maintains the density of carriers in the conducting CuO₂ planes [since the |ψ|² = n/2] which promotes enhancement in the magnitude of superconductivity.     

Diffusion and point defects in TiO2−x

The self-diffusion of ⁴⁴Ti has been measured both parallel to and perpendicular to the c axis in rutile single crystals by a serial-sectioning technique as a function of temperature (1000–1500°C) and oxygen partial pressure (10^?14 ? 1 atm). The oxygen-partial-pressure dependence of. D¹_Ti indicates that cation selfdiffusion occurs by an interstitial-type mechanism and that both trivalent and tetravalent interstitial titanium ions may contribute to cation self-diffusion. At p_o2 = 1.50 × 10^?7 atm where impurity-induced defects are unimportant,

$\text{D}{}^1{}_{\mathrm{<mtext>Ti</mtext>}}\text{(∥c)=}\text{6.50}\text{+1.33}\text{?1.11}\text{exp}\text{?}\text{(66.11±0.56}\text{kcal}\text{mole}\text{RT}\text{cm}{}^2\text{S}$

and

$\text{D}{}^1{}_{\mathrm{<mtext>Ti</mtext>}}\text{(⊥c)=}\text{4.55}\text{+1.78}\text{?1.28}\text{exp}\text{?}\text{(64.08±0.99)}\text{kcal}\text{mole}\text{RT}\text{cm}{}^2\text{S}\text{.}$

In the intrinsic region, the ratio D¹_Ti (⊥c)/D¹_Ti(∥c) was found to increase from 1.2 to 1.6 as the temperature decreased from 1500 to 1000°C. Computations based upon the defect model of Kofstad (involving the atomic defects Ti^..._iTi^...._iand V^.._o), of Marucco etal. (Ti^...._i and V^.._o), and of Blumenthal etal. (Ti^..._i and Ti^...._i) are compared with the experimental data on deviation from stoichiometry, electrical conductivity, cation self-diffusion and chemical diffusion in TiO_2?x. These comparisons provide values of the defect concentrations, cation-defect diffusivities, electron mobility and reasonable values of the correlation factor for cation diffusion by the interstitialcy mechanism. Only the model of Kofstad is inconsistent with the data.     

Dielectric and piezoelectric properties of (1−x)Ba0.7Sr0.3TiO3−xBa0.7Ca0.3TiO3 perovskites

Dielectric and piezoelectric properties of (1?x)Ba_0.7Sr_0.3TiO₃?xBa_0.7Ca_0.3TiO₃ (BST?xBCT) (x=0.2–0.9) perovskite ceramics have been investigated. BCT has fully incorporated into BST lattice, forming a complete perovskite solid solution, whose lattice constant χ decreases almost linearly with increase in x from 0.2 to 0.4, while showing an anomalous expansion at 0.4<x≤0.6. This, together with the deviation of tetragonal–orthorhombic phase transition temperature (T_O–T) from the linear relation T_O–T (K)=?103.7x+239.3 at x=0.5, suggests that a small amount of Ca²⁺ has substituted for Ti⁴⁺. Curie temperature T_C increases linearly with increase in x from 0.2 to 0.9, which is mainly contributed to the increase of the Ba/Sr ratio. The calculated degree of relaxation (γ) is in the range of 1.41–1.53, indicating that the BST–xBCT ceramics are ferroelectric materials with diffuse phase transition. Strain and piezoelectric constant (d₃₃) decrease with increasing x, whereas planar electromechanical coefficient (k_p) reaches a maximum (17.0%) at x=0.6.     

Physical and electrical properties of band-engineered SiO2/(TiO2) x (SiO2)1−x stacks for nonvolatile memory applications

In our study, the physical properties of (TiO₂) _x (SiO₂)_1?x , including band-gap, band-offset, and thermal stability and the electrical properties of band-engineered SiO₂/(TiO₂) _x (SiO₂)_1?x tunnel barrier stacks, including the tunneling current and charge-trapping characteristics for applications to nonvolatile memory devices were investigated. It was observed that the band-gap and band-offset of (TiO₂) _x (SiO₂)_1?x can be controlled by adjustment in the composition of the (TiO₂) _x (SiO₂)_1?x films. Ti-silicate film with TiO₂:SiO₂ cycle ratio of 1:5 was maintained in an amorphous phase, even after annealing at 950 °C. The tunneling current of the band-engineered SiO₂/(TiO₂) _x (SiO₂)_1?x stacked tunnel barrier was larger than that of a single SiO₂ barrier under a higher external bias, while the tunneling current of a SiO₂/(TiO₂) _x (SiO₂)_1?x stacked tunnel barrier under a lower external bias was smaller. Charge-trapping tests showed that the voltage shift for SiO₂/(TiO₂) _x (SiO₂)_1?x is slightly larger than that for single SiO₂.     

Synthesis and native defectivity of Zn1−x V x O (0 ≤ x ≤ 0.03) photocatalysts

Nanodisperse solid solutions Zn_1?x V _x O (0 ≤ x ≤ 0.03) with high numbers of defects in an oxygen sublattice are synthesized via the precursor technique. ESR analysis reveals that V _O ⁺ oxygen vacancies are the main defects of the oxygen sublattice in the Zn_1?x V _x O structure. The Zn_1?x V _x O (0 < x ≤ 0.15) solid solutions exhibit high photocatalytic activity during hydroquinone oxidation in water upon irradiation with UV and visible light.     

X-ray photoelectron spectroscopy analysis of (Ln1−xSrx)CoO3−δ (Ln: Pr,Nd and Sm)

The chemical states of the surface of (Ln_0.5Sr_0.5)CoO_3?δ (Ln (lanthanides) = Pr, Nd and Sm) used for cathode materials of intermediate temperature operating solid oxide fuel cells (IT-SOFCs) were investigated by X-ray photoelectron spectroscopy (XPS). Oxygen peaks comprised of lower binding energy (LBE) and higher binding energy (HBE) peaks from (Ln_0.5Sr_0.5)CoO_3?δ and Pr_0.3Sr_0.7CoO_3?δ (PSC37) showed that some merged oxygen peak behavior is a function of the Sr and lanthanide concentrations. By investigating the oxygen peaks, it was determined that more oxygen vacancies were generated on the surface of the cathodes when the lanthanides and Sr were substituted into perovskite oxides. When comparing the binding energies (BEs) of PSC37 with Pr_0.5Sr_0.5CoO_3?δ (PSC55), the LBE and HBE of the Sr peaks both increased when Sr was substituted at the A-site of a perovskite. Surface analysis of the Co peak on the surface of the cathode materials showed that the Co exists mainly as Co³⁺ and partially oxidized to Co⁴⁺ on the cathode materials. The partial existence of Co⁴⁺ can provide some polaron hopping providing electronic conduction for the solid oxide fuel cell.     

Unusual oxygen re-equilibration kinetics of TiO2−δ

Oxygen re-equilibration kinetics, along with the equilibrium conductivity, have been measured on undoped, single-crystal TiO_2−δ, by a four-probe d.c. conductivity relaxation technique, against oxygen partial pressure in the range of − 16 < log(P_O2/atm) ≤ 0 at different temperatures in the range of 1173 ≤ T/K ≤ 1373. The isothermal conductivity varies as σ ∝ P_O2^m with m ≈ − 1/4, − 1/5 and − 1/6 in turn with increasing P_O2 up to 1 atm, suggesting a sequential variation of the majority ionic disorder types from Ti_i to Ti_i to V_O, respectively. Contrary to the conventional knowledge that due to the local (defect) equilibrium postulate there should be one and only one chemical diffusivity or single relaxation time for a binary oxide, the oxygen re-equilibration kinetics has turned out to be twofold with two different relaxation times depending on oxygen activities. This is interpreted as being due to the independent relaxation of each sublattice of TiO₂ in an oxygen activity gradient applied, indicating a failure of local equilibrium during oxygen re-equilibration. From the two different relaxation times the chemical diffusion coefficients of component Ti and O are separately evaluated and subsequently, their self-diffusion coefficients. The latter are found to be in a good agreement with the literature data.     

模拟脉冲及2D NMR波谱程序──SIMPLTN(SIMulation of PuLse and Two-dimensional NMR)

—SIMPLTN（SIMulationofPuLseandTwo－dimensionalNMR）随着脉冲序列多样性的发展，选择所需最佳实验序列或参数，即使是专业人员也有一定困难．加上机时的宝贵，更不允许在仪器上筛选条件，反复试验．另一方面；计算机技术的飞速发展，又使普通的微机或工作站已能逐步替代过去的高档机，使一般用户已能完成过去为专业人员才能完成的任务，后一条件的成熟使前一困境得到了解决的途径．十多年前Baiu和Allman[1]就编写过SIMPLTN程序．当时限于商业利益，原程序没有公开，仅能在Bruker仪器的Asnect3000上应用，推广受到限制．近十…     

模拟脉冲及2D NMR波谱程序-SIM PLTN(SIMulation of PuLse and Two-dimensional NMR)

随着脉冲序列多样性的发展,选择所需最佳实验序列或参数,即使是专业人员也有一定困难.加上机时的宝贵,更不允许在仪器上筛选条件,反复试验.