Pressure effect on grain boundary wetting at various temperatures

Bicrystals of Fe-6 at.% Si alloy containing <001> 5 tilt grain boundaries with a deposited zinc layer have been annealed at various hydrostatic pressure at four temperatures between 700° and 905°C. After the anneals the dihedral angle of the grain boundary groove formed at the site of the grain boundary intersection with the solid-melt interphase boundary has been measured. The transition from complete to incomplete wetting of the grain boundary by the zinc-rich melt (dewetting phase transition) has been found to occur as the pressure increased at all temperatures studied. The temperature dependence of the dewetting transition pressure p _w has been determined. That dependence has a minimum at a temperature of 790°C, which is close to the peritectic temperature in the Fe–Zn system (782°C). A thermodynamic analysis of the wetting phenomena in the two-component system, based on Becker's regular solution model for the surface tension of the interphase boundary, explains the minimum in the p _w (T) dependence.     

Study of air heat treatment on Bi-2223/Ag superconducting tapes

Heat treatment has been carried out on commercially available Bi-2223/Ag superconducting tape under various temperature conditions in air. The critical currents (I_C) of tape after heat treatment at different annealing temperatures were tested at the liquid-nitrogen temperature. The microstructures and phase constituents of the tapes were investigated by SEM and XRD, respectively. The results indicate that annealing temperature has a very important influence on the superconducting properties of the tapes. When the temperature is above 840 °C, I_C value drops dramatically. Furthermore, when the temperature reaches up to 860 °C, the tape loses most of its superconducting property because of the decomposition of the superconducting phase Bi-2223.     

Chiral superconducting phase transition in 3-K phase of Sr2RuO4

We have investigated the transports of micro-fabricated sample of 3-K phase superconductivity (T_c  3 K) in Sr₂RuO₄–Ru eutectic system in order to clarify the pairing symmetry. Up to now, pure Sr₂RuO₄ (T_c = 1.5 K: 1.5-K phase) is widely recognized to be a spin-triplet odd-parity superconductor. However, the enhancement mechanism of T_c up to 3 K and the pairing symmetry of the 3-K phase have not been cleared yet. By using micro fabrication technique with focused ion beam, we have succeeded to extract individual superconducting channels for the 3-K phase in which only a few pieces of Ru inclusions are contained. Multiple kink structures observed in differential resistance–current (dV/dI − I) characteristics indicate serially connected superconducting filaments in the 3-K phase. We confirm that the 3-K phase is an odd-parity superconductor similar to pure Sr₂RuO₄ from the monotonous temperature dependence of the critical currents. In addition, we observed a quite unusual hysteresis in dV/dI − I below 2 K, which suggests the internal degrees of freedom in the superconducting state: the most probably the chiral p-wave state.     

Oxygen nonstoichiometry of Sr(Co,Fe)O3−δ-based perovskites: I. Coulometric titration of SrCo0.85Fe0.10Cr0.05O3−δ by the two-electrode technique

The p(O₂)–T–δ diagram of perovskite-type SrCo_0.85Fe_0.10Cr_0.05O_3−δ was determined by the coulometric titration technique in the temperature range 770–1250 K at oxygen partial pressures from 8 10⁻¹⁰ to 0.5 atm. Stability of the cubic perovskite phase of SrCo_0.85Fe_0.10Cr_0.05O_3−δ, existing down to the oxygen pressures of 10⁻³–10⁻⁵ atm, was found to be slightly higher than that of SrCo_0.80Fe_0.20O_3−δ, probably due to stabilization of oxygen octahedra neighboring Cr⁴⁺ cations. When the oxygen nonstoichiometry of the Cr-containing perovskite decreases from 0.47 to 0.38, the partial molar enthalpy and entropy for overall oxygen incorporation reaction vary in the ranges −165 to −60 kJ mol⁻¹ and 90 to 150 J mol⁻¹ K⁻¹, respectively. Within the stability limits of the single perovskite phase, the p(O₂)–T–δ diagram can be adequately described by equilibrium processes of oxygen incorporation, cobalt disproportionation and interaction of cobalt and iron cations, with the thermodynamic functions independent of defect concentrations. Increasing grain size in SrCo_0.85Fe_0.10Cr_0.05O_3−δ ceramics from submicron size to 100–200 μm has no effect on the oxygen thermodynamics. The two-electrode coulometric titration technique, based on the alternate use of electrodes for oxygen pumping and e.m.f. measurements, is described and verified by studying oxygen nonstoichiometry of La_0.3Sr_0.7CoO_3−δ and PrO_x.     

Surface reaction kinetics in oxygen nonstoichiometry re-equilibration of BaTiO3−δ

We report the (bare) surface redox-reaction rate constant that was determined, along with the chemical diffusivity , by a conductivity relaxation technique on Al-doped single crystal and undoped polycrystal BaTiO_3−δ as a function of oxygen activity in its range of −16≤log a_O2≤0 at elevated temperatures of 800–1100 °C. It takes a value in the range of −4<log( /cm s⁻¹)≤−1, which is even larger than that of the oxides that are considered best as oxygen membranes. It has been found that the surface reaction step grows more rate controlling as the electronic transference number gets smaller or the electronic stoichiometric composition (δ≈0) is approached. The oxygen potential drop due to the surface reaction was estimated by an oxygen concentration cell technique. The oxygen potential drop grows larger as the stoichiometric composition is approached, that is in accord with the variation of against oxygen activity.     

Gas-phase Crystallization of Titanium Dioxide Nanoparticles

We have investigated the development of crystal morphology and phase in ultrafine titanium dioxide particles. The particles were produced by a droplet-to-particle method starting from propanolic titanium tetraisopropoxide solution, and calcined in a vertical aerosol reactor in air. Mobility size classified 40-nm diameter particles were conveyed to the aerosol reactor to investigate particle size changes at 20–1200°C with 5–1-s residence time. In addition, polydisperse particles were used to study morphology and phase formation by electron microscopy. According to differential mobility analysis, the particle diameter was reduced to 21–23-nm at 600°C and above. Precursor decomposition occurred between 20°C and 500°C. The increased mobility particle size at 700°C and above was observed to coincide with irregular particles at 700°C and 800°C and faceted particles between 900°C and 1200°C, according to transmission electron microscopy. The faceted anatase particles were observed to approach a minimized surface energy by forming {101} and {001} crystallographic surfaces. Anatase phase was observed at 500–1200°C and above 600°C the particles were single crystals. Indications of minor rutile formation were observed at 1200°C. The relatively stable anatase phase vs. temperature is attributed to the defect free structure of the observed particles and a lack of crystal–crystal attachment points.     

Studies on sintering of solid state synthesized Ba1−xKxBiO3−δ superconducting phase

Superconducting Ba_1−xK_xBiO_3−δ pellets were synthesized by solid state reaction followed by sintering. Thermo-gravimetric and differential thermo-gravimetric analysis (TG-DTA) of the mixture of nitrates was carried out to study the reactions during the phase formation. The effect of different sintering temperatures on the phase formation was studied. The X-ray diffraction data confirms the formation of superconducting Ba_0.6K_0.4BiO_2.23 phase at 700 °C. The surface morphological studies as a function of sintering temperature were studied by SEM. It is observed that the pellets prepared by solid state reaction followed its sintering at 700°C shows the superconducting transition at 26.8 K.     

Possible highT c superconductivity in the Ba−La−Cu−O system

Metallic, oxygen-deficient compounds in the Ba–La–Cu–O system, with the composition Ba _x La_5–x Cu₅O_5(3–y) have been prepared in polycrystalline form. Samples withx=1 and 0.75,y>0, annealed below 900°C under reducing conditions, consist of three phases, one of them a perovskite-like mixed-valent copper compound. Upon cooling, the samples show a linear decrease in resistivity, then an approximately logarithmic increase, interpreted as a beginning of localization. Finally an abrupt decrease by up to three orders of magnitude occurs, reminiscent of the onset of percolative superconductivity. The highest onset temperature is observed in the 30 K range. It is markedly reduced by high current densities. Thus, it results partially from the percolative nature, bute possibly also from 2D superconducting fluctuations of double perovskite layers of one of the phases present.     

Tandem diazonium salt electroreduction and click chemistry as a novel, efficient route for grafting macromolecules to gold surface

Bis-alkynylated oligoethyleneglycol (OEG) and a monopropargyl-functionalized perfluorinated ethylene glycol (FEG) were clicked to azide-functionalized gold surface (Au–N₃) at room temperature via the well known 1,3 cycloaddition click chemical reaction. The Au–N₃ substrate was obtained by nucleophilic attack of NaN₃ on gold substrates modified by the electrochemical reduction of the , ⁺N₂–C₆H₄–CH₂Br diazonium salt. This electrochemical process yields aryl layer-modified gold of the type Au–C₆H₄–CH₂Br (hereafter Au–Br). The untreated and modified gold plates were examined by XPS, PMIRRAS and contact angle measurements. XPS brought evidence for electrografting aryl layers by the detection of Br3d; azide functionalization by the increase of the N/Br atomic ratio; and click reaction of OEG with Au–N₃ by the increase of O/N ratio. In addition, the perfluorinated plate (Au-FEG) exhibited F1s and characteristic C1s peaks from -(CF₂)₇- chain and terminal CF₃. Infra red spectroscopy (PMIRRAS) evidenced (i) grafting N₃ to Au–Br; (ii) characteristic stretching bands, from ethylene glycol units, C–O–C (1100–1300 cm⁻¹); CF₂ (1000–1100 cm⁻¹) and CF₃ (1100–1350 cm⁻¹) from FEG grafts; and (iii) suppression of alkynyl bands from OEG and FEG after surface click chemistry. More importantly, PMIRRAS results support an important bridging of the bispropargyl oligoethylene glycol at the gold surface. Water drop contact angles were found to be 48.7° and 83.0° for Au-OEG and Au-FEG, respectively, therefore highlighting the control over the hydrophilic/hydrophobic character of the clicked substrate.This work shows that clicking macromolecules to grafted, diazonium salt-derived aryl layers is a novel, simple and valuable approach for designing robust, functional surface organic coatings.     

The temperatures of protons andπ − mesons in central nucleus-nucleus interactions at a momentum of 4.5 GeV/c per incident nucleon

An estimate of the temperature of protons and ^– mesons in central He–Li, He–C, C–C, C–Ne, C–Cu, C–Pb, O–Pb, Mg–Mg interactions is presented. The results indicate an increase of the proton temperature with increasing mass numbers of projectile and target nuclei (A _p ,A _T ) fromT _p =(118±3) MeV for He–Li toT _p =(141±2) MeV for C–Pb. The temperature of ^– mesons does not depend onA _P ,A _T andT 95 MeV. A satisfactory fit for ^– mesons in C–Cu, C–Pb, O–Pb, Mg–Mg collisions can be achieved by using a form involving two temperatures,T ₁ andT ₂. The relative yield of the high temperature component (T ₂) is 24% for C–Cu, C–Pb, and Mg–Mg interactions. The observed results forT _P in C–Ne, C–Cu and C–Pb collisions are consistent with the prediction of the thermodynamic hagedorn model.     

2H NMR of Deuterofullerites C60D x

Deuterofullerites C₆₀D _x have been studied by means of ²H NMR spectroscopy. It has been established that there are two types of carbon–deuterium bindings in the samples under study: tip C–D with quadrupole constant coupling (QCC) 171 kHz and bridge –C...D...C– with QCC 56 kHz. It is possible that the latter bond is a result of the rigidity of the lattice, which is unusual for fullerene compounds.     

Electrical conductivity of Ag/Na ion-exchanged titanosilicate glasses

The Ag₂O–TiO₂–SiO₂ glasses were prepared by Ag⁺/Na⁺ ion-exchange method from Na₂O–TiO₂–SiO₂ glasses at 380–450 °C below their glass transition temperatures (T_g), and their electrical conductivities were investigated as functions of TiO₂ content and the ion-exchange ratio (Ag/(Ag+Na)). In a series of glasses 20R₂O·xTiO₂·(80−x)SiO₂ with x=10, 20, 30 and 40 in mol%, the electrical conductivities at 200 °C of the fully ion-exchanged glasses of R=Ag were in the order of 10⁻⁵ or 10⁻⁴ S cm⁻¹ and were 1 or 2 orders of magnitude higher than those of the initial glasses of R=Na. The glass of x=30 exhibited the highest increase of conductivity from 3.8×10⁻⁷ to 1.3×10⁻⁴ S cm⁻¹ at 200 °C by Ag⁺/Na⁺ ion exchange among them. When the ion-exchange ratio was changed in 20R₂O·30TiO₂·50SiO₂ system, the electrical conductivity at 200 °C exhibited a minimum value of 7.6×10⁻⁸ S cm⁻¹ around Ag/(Ag+Na)=0.3 and increased steeply in the region of Ag/(Ag+Na)=0.5–1.0. When the ion-exchange temperature was changed from 450 to 400 °C, the conductivity of the ion-exchanged glass of x=30 decreased. The infrared spectroscopy measurement revealed that the ion-exchange temperature of 450 °C induced a structural change in the glass of x=30. The T_g of the fully ion-exchanged glass of x=30 was 498 °C. It was suggested that the incorporated silver ions changed the average coordination number of titanium ions to form higher ion-conducting pathway and resulted in high conductivity in the titanosilicate glasses.     

Apparent conflicting indications on the conformation of dimethylether–argon from the rotational spectra of the d6 and C species

The rotational spectra of dimethylether–d₆–Ar and dimethylether–¹³C–Ar have been investigated by molecular beam Fourier transform microwave spectroscopy. The obtained rotational constants, when compared to those of the normal species, give contrasting indications on the conformation of the complex. We believe the indications given by the dimethylether–Ar/dimethylether–¹³C–Ar pair to be the correct ones. They suggest the Ar atom to lie in the σ_ν symmetry plane of dimethylether perpendicular to the C–O–C plane, shifted towards the oxygen atom. This conformation is in agreement with several kinds of theoretical calculations. Probably isotopic substitution effects make the data from dimethylether–d₆–Ar not directly compatible with those of the other species.     

Stability of soliton lattice phase in the bilayer quantum Hall state under tilted magnetic fields

The bilayer quantum Hall (QH) state at the filling factor ν=1 shows various fascinating quantum phenomena due to the layer degree of freedom called ‘pseudospin’. We report an experimental evidence of the soliton lattice (SL) phase, which is a domain structure of pseudospin, by the appearance of a local maximum of magnetoresistance near the ν=1 QH state. We investigate the stability of the SL phase by changing B and the total electron density n_T. Detailed magnetotransport measurements under tilted magnetic fields were carried out to obtain a B–n_T plane phase diagram containing the C, IC and SL phases. We found the SL phase is only stable at low n_T region. Namely, the C–SL–IC phase transition occurs only at low n_T region as B increases. On the contrary, the C–IC phase transition directly occurs without passing through the SL phase at high n_T region.     

High-T c superconducting Bi−Sr−Ca−Cu−O thin films prepared by laser-induced plasma deposition

High-T _c superconducting thin films of Bi–Sr–Ca–Cu oxides were prepared by laser-induced plasma deposition of high-T _c superconducting Bi₂Sr₂Ca₁Cu₂O_x and Bi₂Sr₂Ca₂Cu₃O_x targets in vacuum and a short post-annealing in air at 875°C. Thin films (thickness <500 nm) with a critical temperatureT _c -onset of 95 K can be prepared on silicon substrate material with a SrTiO₃ interface layer. The thin films were completely superconducting between 80 and 90 K. The stoichiometry transfer of superconducting target material by laser-induced plasma deposition was investigated.     

IR absorption spectrum (4200–3100 cm) of H2O and (H2O)2 in CCl4. Estimates of the equilibrium constant and evidence that the atmospheric water absorption continuum is due to the water dimer

IR absorption spectra, 4200–3100 cm⁻¹, of water in CCl₄ solutions are presented. It is shown that for saturated solutions significant amounts of water are present as dimer (ca. 2%). The IR spectra of the monomer and dimer are retrieved. The integrated absorption coefficients of the monomer absorption are significantly enhanced relative to the gas phase values. The dimer spectrum consists of 5 bands, of which 4 were expected from data from cold beams and cold matrices. The origin of the “extra” band is discussed. In addition it is argued that the dimer absorption bands intensities must be enhanced relative to the gas phase values. Based on recent calculations of band strengths, and observed frequency shifts relative to the gas phase, the intensity enhancement factors are estimated as well as the monomer/dimer equilibrium constant in CCl₄ solution at T=296 K (K_c=1.29 mol⁻¹ L). It is noted that the observed dimer spectrum has a striking resemblance with the water vapour continuum determined by Burch in 1985 which was recently remeasured by Paynter et al. and it is concluded that the atmospheric water absorption continuum in the investigated spectral region must be due to water dimer. Based on the newly published spectral data a revised value of the gas phase equilibrium constant is suggested (K_p=0.035 atm⁻¹ at T=296 K) as well as a value for the standard enthalpy of formation, ΔH⁰=15.4 kJ mol⁻¹.     

Investigation of the Fiban K-1 Sulfocationite by the IR Spectroscopy Method

Using the IR spectroscopy method, we have studied the state of water, sulfogroups, and adsorbed methanol in a Fiban K-1 fibrous cationite under different conditions of preparation of a sample. It is shown that on an air-dried cationite protonation of methanol is performed by the ionic pair [(H_2n+1O _n )⁺·SO₃ ^–] after vacuum treatment at 20°C and by the ionic pair [H⁺·SO₃ ^–] after vacuum treatment at 90°C.     

Magnetic and magnetotransport properties of Co-doped manganites with perovskite structure

A systematic study of the doping of the Mn-sites by cobalt in three series of manganites — La_0.76Ba_0.24(Mn_1−xCo_x)O₃ single crystals, La_2/3Ba_1/3(Mn_1−xCo_x)O₃ and La(Mn_1−xCo_x)O₃ ceramics has been performed. It was found that La(Mn_1−xCo_x)O₃ annealed at 800°C in the range 0.4x0.9 is a mixture of ferromagnetic domains with ordered Mn and Co ions and ionically disordered spin-glass domains. In the quenched samples the fraction of spin-glass-type component increases strongly. The La_2/3Ba_1/3(Mn_1−xCo_x)O₃ solid solutions exhibit also an evidence for phase separation in the range 0.5x0.8. All the La(Mn_1−xCo_x)O₃ samples show an insulating behavior, however, magnetoresistance reduces strongly when the cobalt content rises to x=0.5. The La_0.76Ba_0.24(Mn_1−xCo_x)O₃ single crystals show first-order phase transition below their Curie points associated with a change of ground state of the Co²⁺ ions. The magnetic phase diagrams are depicted. The results are discussed in terms of positive Mn³⁺–O–Mn⁴⁺, Mn³⁺–O–Mn³⁺, Mn⁴⁺–O–Co²⁺ and negative Mn⁴⁺–O–Mn⁴⁺, Co²⁺–O–Co²⁺, Co²⁺–O–Mn³⁺ superexchange interactions as well as Co²⁺ and Mn⁴⁺ ionic ordering.     

Preparation and properties of the single 110 K phase Bi(Pb)-Sr-Ca-Cu-O superconductor

The single 110 K phase Bi(Pb)–Sr–Ca–Cu–O superconductor was made by sintering in air. Its zero-resistance temperature is 106 K, and it is an orthorhombic cell witha=5.403 Å,b=5.412 Å andc=37.062 Å. It formed around the low-T _c phase. The forming period of the 110 K phase can be shortened by multiple sintering and grinding. If PbO is mixed into the samples after the 85 K phase has formed, the forming rate of the 110 K phase can be increased significantly. EDAX analysis of grain composition confirms that the Pb atoms enter the unit cell, and probably Pb cations replace some Ca cations.     

Vortex glass phase and flux creep in YBa2Cu3O y epitaxial film

Nonlinear I–V characteristics of YBa₂Cu₃O _y epitaxial film at different temperatures in a magnetic field of up to 5T and angles between the direction of the field and the a–b plane of 0°, 30°, 45°, 60°, and 90° were measured. We find that there are the vortex glass phase and vortex liquid phase in the mixed state. The flux creep exists in the vortex glass phase, and it obviously appears in the area around the boundary between the vortex glass phase and the vortex liquid phase.