Direct measurement of the magnetocaloric effect in La0.67Ca0.33MnO3

Polycrystalline perovskite La_0.67Ca_0.33MnO₃ was synthesized by a sol–gel method. Its adiabatic temperature change ΔT_ad induced by a magnetic field change was measured directly. At 268 K, near its Curie temperature T_C, ΔT_ad of La_0.67Ca_0.33MnO₃ induced by a magnetic field change of 2.02 T reaches 2.4 K. The latent heat Q and magnetic entropy change −ΔS_M induced by a magnetic field change were calculated from the temperature dependence of ΔT_ad and zero-field heat capacity C_p. The maximum values of Q and −ΔS_M in La_0.67Ca_0.33MnO₃ induced by a magnetic field change of 2.02 T are 1.85 J g⁻¹ and 6.9 J kg⁻¹ K⁻¹, respectively. The former is larger than the phase transition latent heat of heating or cooling, which is about 1.70 J g⁻¹.     

Interactions of some peptides with sodium acetate and magnesium acetate in aqueous solutions at 298.15 K: A volumetric approach

The apparent molar volumes, V of diglycine, triglycine and glycyl-l-leucine have been determined in water and in aqueous sodium acetate (0.5, 1.0, 2.0, and 4.0 m_B) and magnesium acetate (0.5, 1.0, 1.5, and 2.0 m_B) solutions at 298.15 K by the measurement of densities using vibrating-tube digital densimeter. The partial molar volumes, V_2,m⁰ obtained from V have been used to calculate the partial molar volumes of transfer, Δ_trV_2,m⁰ for these peptides from water to aqueous solutions of sodium acetate (SA) and magnesium acetate (MA) solutions. The hydration numbers, n_H and volumetric interaction coefficients have also been calculated. The Δ_trV_2,m⁰ data suggest that ion-charged/or peptide group interactions of peptides are stronger with MA in comparison to SA.     

Neutrino oscillations induced by two-loop radiative mechanism

Two-loop radiative mechanism, when combined with an U(1)_L′ symmetry generated by L_e − L_μ − L_τ (=L′), is shown to provide an estimate of Δm²/Δm²_atm εm_e/m_τ, where ε measures the U(1)_L′-breaking. Since Δm²_atm 3.5×10⁻³ eV², we find that Δm² ε10⁻⁶ eV², which will fall into the allowed region of the LOW solution to the solar neutrino problem for ε 0.1.     

Determination of the K(1800) spin parity

A spherical harmonic moment analysis of the reactions K⁻p → K⁻π⁺n and K⁺p → K⁺π⁻Δ⁺⁺ at 13 GeV/c demonstrates the existence of a broad K^* state with mass in the vicinity of 1800 MeV and spin parity 3⁻.     

Projective and affine connections on S and integrable systems

It is known that the Korteweg–de Vries (KdV) equation is a geodesic flow of an L² metric on the Bott–Virasoro group. This can also be interpreted as a flow on the space of projective connections on S¹. The space of differential operators Δ⁽ⁿ⁾=∂ⁿ+u₂∂ⁿ⁻²++u_n form the space of extended or generalized projective connections. If a projective connection is factorizable Δ⁽ⁿ⁾=(∂−((n+1)/2−1)p₁)(∂+(n−1)/2p_n) with respect to quasi primary fields p_i’s, then these fields satisfy ∑_i=1ⁿ((n+1)/2−i)p_i=0. In this paper we discuss the factorization of projective connection in terms of affine connections. It is shown that the Burgers equation and derivative non-linear Schrödinger (DNLS) equation or the Kaup–Newell equation is the Euler–Arnold flow on the space of affine connections.     

Experimental study of the time-dependent rate of K → πππ

The time-dependence of the decay rate of initially pure K⁰ into the final state (π⁺π⁻π⁰) has been studied in search for the decay k_S⁰→π⁺π⁻π⁰. No evidence is found in a sample of 384 observed events. The ratio of the CP -violating K_S⁰ amplitude and the K_L⁰ amplitude is η₊₋₀ = (0.13_−0.20^+0.17) + i(0.17_−0.26^+0.27); the ratio of the CP-conserving K_S⁰ amplitude and the K_L⁰ amplitude is < 0.4. The energy dependence of the K⁰→π⁺π⁻π⁰ matrix element is found to be a₊₋₀ = −0.31 ± 0.03.     

Studies on the iodine complexes of pyridine picolines and aminopyridine by constant activity method

The iodine complexes of pyridine, -, β-, γ- picolines, 2-aminopyridine and 2,2′-bipyridine in cyclohexane were studied by the constant activity method, their spectral characteristics and thermodynamic parameters were determined. The equilibrium constants, molar extinction coefficients of the charge-transfer band maxima, _CT, at 25°C and heats of complexation, ΔH°, are respectively as follows:

1. (a) pyridine-iodine, 107 dm³mol⁻¹ 24200 dm³mol⁻¹m⁻¹ and 31 KJ/mol;

2. (b) -picoline-iodine, 172 dm³mol⁻¹m⁻¹, 49700 dm³mol⁻¹m⁻¹ and 33 KJ/mol;

3. (c) β-picoline-iodine, 243 dm³mol⁻¹, 50300 dm³mol⁻¹m⁻¹ and 35 KJ/mol;

4. (d) γ-picoline-iodine, 342 dm³mol⁻¹, 55900 dm³mol⁻¹m⁻¹ and 41 KJ/m;

5. (e) 2-aminopyridine-iodine, 427 dm³mol⁻¹, 60800 dm³mol⁻¹m⁻¹ and 47 KJ/mol;

6. (f) 2,2′-bipyridine-iodine, 6.0 dm³mol⁻¹,−, 21 KJ/mol.

The values of the blue shifted iodine band maxima of the above mentioned donors and their molar extinction coefficients are, 420 nm (1450 dm³mol⁻¹m⁻¹), 419 nm (1470 dm³mol⁻¹m⁻¹), 418 nm (1640 dm³mol⁻¹m⁻¹), 417 nm (1570 dm³mol⁻¹m⁻¹), 410 nm (1574 dm³mol⁻¹m⁻¹) and 452 nm (1370 dm³mol⁻¹m⁻¹) respectively. The oscillator strengths and transition dipole moments of the blue-shifted iodine bands are characterised.     

Electromagnetic final-state interactions in the leptonic decays of the neutral kaon (I) Kℓ3 mode

We present a calculation of the Coulomb final-state interaction effects in the decays K_L → π ℓ^±V_ℓ. Specifically we investigate the charge asymmetry and the transverse polarization of the charged lepton. We consider the effects of possible ΔQ = −ΔS amplitudes and the q² dependence of the form factors. The variation of the effects over the Dalitz plot is discussed and many numerical results are given.     

Comments on CP, T and CPT violation in neutral kaon decays

We comment on CP, T and CPT violation in the light of interesting new data from the CPLEAR and KTeV Collaborations on neutral kaon decay asymmetries. Other recent data from the CPLEAR experiment, constraining possible violations of CPT and the ΔS=ΔQ rule, exclude the possibility that the semileptonic-decay asymmetry A_T measured by CPLEAR could be solely due to CPT violation, confirming that their data constitute direct evidence for T violation. The CP-violating asymmetry in K_L→e⁻e⁺π⁻π⁺ recently measured by the KTeV Collaboration does not by itself provide direct evidence for T violation, but we use it to place new bounds on CPT violation.     

Search for narrow NNπ resonances in exclusive pp→ppππ measurements

Narrow structures in the range of a few MeV have been searched for in ppπ⁺ and ppπ⁻ invariant mass spectra (M_ppπ⁺ and M_ppπ⁻) obtained from exclusive measurements of the pp→ppπ⁺π⁻ reaction at T_p=725,750 and 775 MeV using the PROMICE/WASA detector at CELSIUS. The selected reaction is particularly well suited for the search for dibaryon resonances decoupled from NN and/or NΔ. In the mass range 2020 MeV/c²<m_dibaryon<2085 MeV/c² no narrow structures could be identified on the 3σ level of statistical significance neither in M_ppπ⁻ nor in M_ppπ⁺ giving an upper limit (95% C.L.) for dibaryon production in this reaction of σ<20 nb.     

Ion-pair and triple-ion studies of some tetraalkylammonium halides in pure 1,3-dioxolane at 298.15 K

Conductivities of some tetraalkylammonium halides, viz. tetramethylammonium iodide (Me₄NI), tetraethylammonium bromide (Et₄NBr), tetraethylammonium iodide (Et₄NI), tetra-n-propylammonium bromide (Pr₄NBr), tetra-n-butylammonium bromide (Bu₄NBr), tetra-n-butylammonium iodide (Bu₄NI) and tetra-n-heptylammonium bromide (Hp₄NBr) were measured at 298.15 K in 1,3-dioxolane which has a low permittivity (ε = 7.13). A minima in the conductometric curves (molar conductance, Λ vs. square root of concentration, √c) was observed for concentrations which were dependant upon both the salt and the solvent. The observed molar conductivities were explained by the formation of ion-pairs (M⁺ + X⁻ ↔ MX, K_P) and triple-ions (2M⁺ + X⁻ ↔ M₂X⁺; M⁺ + 2X⁻ ↔ MX₂⁻, K_T). A linear relationship between the triple-ion formation constants [log (K_T/K_P)] and the salt concentrations at the minimum conductivity (log C_min) was given for all the salts in 1,3-dioxolane. The formation of triple-ions might be attributed to the ion sizes in solutions in which Coulombic interactions and non-Coulombic interactions act as the main forces between the ions (R₄N⁺…..X⁻).     

On the luminescence of LiBaF3:Eu

From the temperature dependence of the line—band luminescence intensity ratio of LiBaF₃:Eu²⁺ a 4f−5d activation energy (Δ) of 800 cm⁻¹ is derived, being much higher than the value reported in the literature (100 cm⁻¹). The temperature dependence of the luminescence decay can be well described with Δ = 800 cm⁻¹ and with 4f−4f and 5d−4f radiative probabilities of 4×10²s⁻¹ and 6×10⁵s⁻¹, respectively.     

Multilayer relaxation of Rh(311)

The multilayer relaxation of the Rh(311) surface was investigated by means of LEED structure determination both for vertical and surface parallel (registry) relaxations. Excellent agreement between experimental and calculated spectra could be achieved mirrored by a minimum Pendry R-factor R = 0.174. The first three layer spacings are oscillatorily relaxed by Δd₁₂/d₀ = −14.5 ± 1.8%, Δd₂₃/d₀ = +4.9 ±2.0% and Δd₃₄/d₀ = −1.0 ±2.0%. There seems to be a coherent registry shift of the fir Δs = 0.03 ± 0.07 Å which, however, is within the error limits of the structure determination. Moreover, an energy dependent inner potential is detected. The results are discussed in comparison to equivalent surfaces of other materials as well as for the less open surfaces of rhodium.     

Desorption of H2 from W(110) and Fe covered W(110) surfaces

The kinetics of H₂ desorption from H/W(110) and H/Fe₁/W(110) were studied by measuring work function changes Δø vs time at a number of temperatures. Combination with previously determined Δø vs coverage data and differentiation at various fixed coverages gave rate vs T data from which activation energies of desorption could be obtained. E vs coverage results agree well with previously determine ΔH_des results. In the case of H/Fe₁/W(110) this includes a rise from 20 to 30 kcal mol⁻¹ of H₂ at H/Fe = H/W > 0.3. Plots of rate −dθ/dt vs θ (θ being coverage in units of H/W) vary much more steeply than θ² at most coverages for both systems. The θ dependence can be explained almost quantitatively in terms of the variations of ΔH_des and surface entropy S_s with coverage, by assuming that rates of desorption are equal to the equilibrium rates of adsorption. The latter can be formulated thermodynamically, except for a sticking coefficient, s. Values for s(θ, T) can also be obtained and show relatively little temperature dependence.     

Kinetic aspects of aluminium titanate layer formation on titanium alloys by plasma electrolytic oxidation

The paper reports on a systematic investigation into the effects of process parameters on the growth kinetics and associated changes in the structure, phase composition and mechanical properties of surface layers formed on Ti–6Al–4V alloy by plasma electrolytic oxidation (PEO) treatment in 0.05–0.2 mol l⁻¹ solutions of sodium aluminate. Methods of gravimetric, SEM and XRD analysis, as well as microhardness and scratch testing, are employed to investigate mass transfer and phase-structure transformations in the surface layer. The probable mechanisms of layer formation are discussed, which comprise electrochemical oxidation of the Ti-electrode by OH⁻ anions, complimented by chemical precipitation of Al(OH)₃ and plasma-induced transformations in the surface discharges. Running with a total yield efficiency of 20–30%, these processes lead to the formation of predominantly the Al₂TiO₅ phase with heterogeneous precipitation of Al₂TiO₅·TiO₂ and 3Al₂TiO₅·Al₂O₃ eutectics. Al- and Ti-enriched constituents of this structure show hardnesses of 1050–1480 and 300–845 H_K, 0.02, respectively. The layer growth rate increases with increasing electrolyte concentration, providing a maximum thickness of over 60 μm and a surface roughness (R_a) of 3–4 μm. Increasing the electrolyte pH from 12.0 to 12.8 results in smoothing and thickening of the surface layer but a lower sample weight gain, associated with an enhancement of the Ti electro-oxidation process. Morphological changes during PEO formation of the surface layer include gradual transformation of the original fine grained but porous structure into a dense, fused morphology which is adversely affected by discharge-induced thermal stresses, causing a degradation of the layer adhesion strength.     

Conductivity anisotropy in directionally solidified CaZrO3---CaSZ and MgO-MgSZ eutectics

The results of the impedance spectroscopy measurements on eutectic samples based on zirconium oxide are presented here. Samples of CaZrO₃---ZrO₂(cubic) and MgO---ZrO₂(cubic) have been grown by a directional solidification procedure such that the different phases appear nearly oriented along the growth direction (lamellae in the system of CaZrO₃-ZrO₂(cubic) and fibers of MgO in a ZrO₂ matrix in the other system). The DC electrical conductivity has been measured by impedance spectroscopy along and across the growth axis. For CaZrO₃---ZrO₂ the coductivity is clearly anisotropic. The following values for σT have been obtained: the conductivity at 600 °C equals 2.0 × 10⁻⁶ Ω⁻¹ cm⁻¹ perpendicular to the fiber axis and 1.4 × 10⁻⁵ Ω⁻¹ cm⁻¹ parallel to it and with an activation energy of 1.3 eV for σT. For MgO---ZrO₂(cubic) the isotropic value of the conductivity at 600 °C is 10⁻⁴ Ω⁻¹ cm⁻¹ with activation energy for σT of 1.5 eV. The anisotropic conductivity in the CaZrO₃---ZrO₂ (cubic) system has been explained by a model of an ordered stacking of oxygen conducting (cubic ZrO₂) and non-conducting (CaZrO₃ or MgO) phases.     

A study on the nonstoichiometry of tin oxides by coulometric titration

In this investigation, nonstoichiometries and defect structures of tin oxides were studied between 694 and 990 K by coulometric titration using solid state electrolyte (YSZ) cells. The relationship between nonstoichiometry of the oxide (x) and equilibrium oxygen partial pressure (P_o2) was expressed by the proportionality: xP_O2^−1/6. An intermediate oxide phase, Sn₃O₄ between Sn and SnO₂ was observed in the temperature range of 696–732 K. The standard Gibbs energy of formation of Sn₃O₄ via the reaction; was found to be ΔG^o_Sn3O4 = −1163960+417.36 T (J/mol). The standard Gibbs energy change for the defect formation reaction in SnO_2−x was calculated to be ΔG^o_SnO2−x = 3.05×10⁵−38.97 T (J/mol)).     

Interactions between a tetraanionic porphyrin and the methylviologen dication in methanol studied by fluorescence quenching reaction

Fluorescence decay curves for 5,10,15,20-tetrakis(4-sulfonatophenyl)-21H,23H-porphine tetraanion (TPPS⁴⁻) have been measured in the absence and presence of the methylviologen dication (MV²⁺) with various ionic strengths in methanol. In the presence of MV²⁺ the fluorescence decays can be expressed by a double exponential function, I(t = I₁exp(−t/τ₁) + I₂exp(−t/τ₂). The contribution by the faster decay component to the total fluorescence signal increases with increasing MV²⁺ concentration. The faster decay process is attributed to fluorescence from the excited state of a solvent-separated ion pair (SSIP) formed between TPPS⁴⁻ and MV²⁺, and the slower process is attributed to fluorescence from free TPPS⁴⁻ ions in the solution. Rate constants for the quenching of fluorescence from free TPPS⁴⁻ by MV²⁺ (k_q) and formation constants for the SSIP (K_SSIP) were calculated and both are found to decrease with increasing ionic strength. The decrease in k_q and K_SSIP values can be interpreted in terms of the shielding of electrostatic attraction between the ions.     

Theoretical studies of spin-Hamiltonian parameters for Ni ions in CsMgX3 (X=Cl, Br, I) crystals from the two-mechanism model

In this paper, the high-order perturbation formulas of spin-Hamiltonian (SH) parameters (g factors g, g and zero-field splitting D), including both the crystal-field (CF) and for the first time charge-transfer (CT) mechanisms, are established for 3d⁸ ions in trigonal octahedral clusters. By using these formulas, the SH parameters of Ni²⁺ ions in CsMgX₃ (X=Cl, Br, I) crystals are calculated. The results are consistent with the experimental values. The calculations suggest that the sign of Q^CT (Q=Δg, Δg or D, where the g-shift Δg_i=g_i−g_e, g_e≈2.0023 is the value of free-electron) due to CT mechanism is the same as that of the corresponding Q^CF due to CF mechanism, and the relative importance of CT mechanism (characterized by Q^CT/Q^CF) increases with the increasing atomic number of ligand X. So, for the 3dⁿ ML_m clusters with ligand having large atomic number, the reasonable theoretical explanations of all SH parameters should take both CF and CT mechanisms into account. The defect structure of (NiX₆)⁴⁻ impurity centers in CsMgX₃:Ni²⁺ crystals is also considered in our model.     

Ionic conductivity of crystalline and glassy Mg4.5Na7(P2O7)4

In our work single crystals of Mg_4.5Na₇(P₂O₇)₄ were prepared, pulverized, pressed into pellets and sintered in order to measure the electrical conductivity of polycrystalline specimens. The conductivity was also measured on glassy specimens obtained by the melting of previously prepared crystals. The electrical conductivities at 25°C with values of the order of 10⁻¹⁶ Ω⁻¹ cm⁻¹ for polycrystalline samples and a value of the order of 10⁻¹⁴ Ω⁻¹ cm⁻¹ for glass, show that the glassy phase of Mg_4.5Na₇(P₂ because of its greater molar volume and loosely packed structure, is a better matrix for ionic motion.