Effect of nanoparticles agglomeration on electrical properties of La1−xAxMnO3 (A = Sr,Ba) nanopowder and ceramic solid solutions

Peculiar features of the sol–gel synthesis of substituted manganites La_1−xA_xMnO₃ (A = Sr, Ba) have been investigated. Variation of the gel pH during synthesis was shown to affect the aggregation of particles and their crystal structure. Electrical properties of nanopowder and ceramic La_1−xA_xMnO₃ solid solutions were studied. Additional heat treatment was revealed to affect not only the resistivity, but also the character of its temperature dependence. It was shown that under the synthesis and heat treatment conditions used in the work, the La_1−xBa_xMnO₃ solid solutions with x = 0.15 have the lowest conductivity at 1200 K, which allows using them as thick-film cathodes.     

Hyperconjugation versus back bonding in AH3−nXn species (A = Si and Ge; X = F,Cl and Br; and n = 1, 2 and 3)

In this research two competing phenomena, back bonding and hyperconjugation, have been investigated based on Natural Bond Orbital (NBO) and Atoms in Molecules (AIM) analyses for radical AH_3?nX_n species, where A = Si and Ge, and n = 1, 2 and 3. It is demonstrated in this article that both above phenomena will be occurred significantly, while back bonding is the only event in analogous compounds with carbon and hyperconjugation is rather negligible. It was also found that only one back bonding with the help of keyword $CHOOSE in NBO analysis can be found in this type of compounds with reasonable structure, while it can be sometimes detected in AH_3?nX_n without using keyword $CHOOSE. It is also shown that there is always an increase in bond length in comparison with reference molecules in mentioned species due to existing hyperconjugation, while if the central atom is carbon, we have always a decrease of bond length due to only having back bonding. Additionally, from AIM point of view, the delocalization indices for α-spin (majority spin) is more than β-spin (minority spin) in radical species for molecules without back bonding, while the situation in our compounds is quite reverse, which can be attributed to the π back bonding in the β-spin electrons.     

Thermodynamic study of (alkyl esters + α,ω-alkyl dihalides) III. HmEandVmE for 20 binary mixtures {xCu − 1H2u − 1CO2C4H9 + (1 − x)α,ω-ClCH2(CH2)v − 2CH2Cl}, where u = 1 to 4, α = 1 and v = ω = 2 to 6

In this article, the experimental data of excess molar enthalpies $H_{\mathrm{m}}^{\mathrm{E}}$ and excess molar volumes $V_{\mathrm{m}}^{\mathrm{E}}$ are presented for a set of 20 binary mixtures comprised of the first four butyl alkanoates (methanoate to butanoate) and five α,ω-dichloroalkanes (1,2-dichloroethane to 1,6-dichlorohexane), obtained at atmospheric pressure and at a temperature of 298.15 K. The results indicate the existence of specific interactions between both kinds of compounds resulting in exothermic processes for most mixtures, except for those containing butyl methanoate which give rise to net endo/exothermic effects. The $V_{\mathrm{m}}^{\mathrm{E}}$ are positive for mixtures of (butyl esters + 1,2-dichloroethane or 1,3-dichloropropane) and negative for the remaining ones. The change in $H_{\mathrm{m}}^{\mathrm{E}}$ with the dichloroethane chain length for a same ester is regular although the $V_{\mathrm{m}}^{\mathrm{E}}$ presents an irregular variation. It can, therefore, be deuced from this that the mixing process involves both effects, exothermic/endothermic and expansion/contraction, simultaneously. The behaviour of the mixtures is interpreted on the basis of the results observed and attributed to different effects taking place among the molecules studied.To improve application of the UNIFAC model using the version of Dang and Tassios, average values were recalculated again for parameters of the ester/chloride interaction, distinguishing, during its application, the functional group of the acid part of the ester. In spite of this, the model does not adequately reproduce the systems’ behaviour.     

Magnetic properties of RE5Ir2X (RE = Y,Gd–Ho,X = Sn,Sb, Pb,Bi) and magnetocaloric characterization of Gd5Ir2X

Systematic phase analytical studies of the systems RE-Ir-X (X = Sn, Pb, Sb, Bi) led to 15 new stannides, plumbides, antimonides and bismuthides with the composition RE₅Ir₂X. The compounds have been synthesized and characterized by X-ray powder diffraction. The structures of Gd₅Ir₂Sb and Dy₅Ir₂Bi have been refined from single crystal X-ray diffractometer data: Mo₅SiB₂ type, I4/mcm, a = 775.2(2), c = 1361.3(5) pm, wR2 = 0.0933, 404 F² values, 16 variables for Gd₅Ir₂Sb and a = 767.5(1), c = 1368.9(3) pm, wR2 = 0.0694, 571 F² values, 16 variables for Dy₅Ir₂Bi. Magnetic measurements of Gd₅Ir₂X (X = Sn, Pb, Sb, Bi), Tb₅Ir₂X (X = Sn, Pb, Sb, Bi), Dy₅Ir₂Pb, Dy₅Ir₂Bi and Ho₅Ir₂Pb indicate ferromagnetic transitions at T_C = 154.3, 159.3, 124.4, 119.3, 99.2, 98.2, 65.5, 68.6, 45.1, 35.6 and 23.5 K, respectively. Gd₅Ir₂Bi and Gd₅Ir₂Sb show an additional antiferromagnetic transition at T_N = 118.5 and 91.0 K. The magnetocaloric effect of Gd₅Ir₂X (X = Sn, Pb, Sb, Bi) in terms of the isothermal entropy change ΔS_m is −7.3(3), –6.5(3), –8.7(3) and −9.0(3) J kg⁻¹ K⁻¹ at temperatures of 153, 157, 120 and 126 K for a 5 T field change. ¹¹⁹Sn Mössbauer spectra of Gd₅Ir₂Sn at 78 K show a huge transferred hyperfine field of 21.9(1) T and an isomer shift of 1.94(1) mm s⁻¹, typical for stannides. ¹²¹Sb Mössbauer spectra of Gd₅Ir₂Sb at 78 K show a transferred hyperfine field of 14.2(3) T and an isomer shift of −7.45(8) mm s⁻¹ reflecting the antimonide character.     

Synthesis,characterization and thermochemistry of Cs(ASP) · nH2O (n = 0, 1)

New compounds of aspartic acid Cs(ASP) · nH₂O (n = 0, 1) have been synthesized and characterized by XRD, IR and Raman spectroscopy as well as TG. The structural formula of this new compound was Cs(ASP) · nH₂O (n = 0, 1). The enthalpy of solution of Cs(ASP) · nH₂O (n = 0, 1) in water were determined. With the incorporation of the standard molar enthalpies of formation of CsOH(aq) and ASP(s), the standard molar enthalpy of formation of −(1202.9 ± 0.2) kJ · mol⁻¹ of Cs(ASP) and −(1490.7 ± 0.2) kJ · mol⁻¹ of Cs(ASP) · H₂O were obtained.     

Sr induced modification of structural,optical and magnetic properties in Bi1−xSrxFeO3 (x = 0, 0.01, 0.03, 0.05 and 0.07) multiferroic nanoparticles

Multiferroic nanoparticles of Bi_1?xSr_xFeO₃ (x = 0, 0.01, 0.03, 0.05 and 0.07) were prepared by a facile sol–gel route and the variation of their structural, optical, dielectric and magnetic properties on strontium concentration has been studied. XRD and TEM results confirm the phase purity of the samples having high degree of crystallinity and monodispersity. The average particle size shows an exponential decline with increase in Sr concentration. A shape transformation from a multifaceted polygon to a spherical one has been observed as Sr concentration in the sample increases to 5%. In the second derivative FTIR spectra, the intensity of vibration peak at ～593 cm^?1 that is characteristic of rhombohedral BiFeO₃ is seen to decrease after Sr doping. All the samples showed typical M–H behavior of a ferromagnet with saturation magnetization achieved within an applied magnetic field of 10 kOe. The sample with 3% Sr substitution displayed saturation and remanent magnetization values 1.37 emu/g and 0.32 emu/g respectively that are highest among all the samples studied. Presence of exchange coupling produced due to interaction between the antiferromagnetic core and ferromagnetic shell is also observed in all Bi_1?xSr_xFeO₃ nanoparticles.     

Synthesis,characterization and reactions of the transition metal halogenoalkyl carbocation complexes [Cp(CO)2M{η2-CH2CH(CH2)nX}]PF6 (n = 1–8, 10, M = Fe; n = 3, 4 M = Ru; X = Br,I)

The halogenoalkyl complexes [Cp(CO)₂M{(CH₂)_nX}] (n = 3–10, 12, M = Fe; n = 5, 6, M = Ru, X = Br, I) react with Ph₃CPF₆ in dry CH₂Cl₂ to give the corresponding carbocation complexes [Cp(CO)₂M{η²-(CH₂CH(CH₂)_n?2X}]PF₆ in high yields. NMR evidence indicates that the metals form metallacyclopropane type structures with the carbocation ligand. The reactions of some of the cationic complexes with NaI, PPh₃, Na[Cp(CO)₂Fe] and Et₃N are discussed. NaI and Na[Cp(CO)₂Fe] displace the halogeno-olefin, while PPh₃ adds at the β-CH^δ+ giving the unstable phosphonium adducts [Cp(CO)₂Fe{CH₂CH(PPh₃)(CH₂)_n?2X}]PF₆ which decompose to the halogeno-olefins and the cationic PPh₃ complex [Cp(CO)₂Fe(PPh₃)]⁺. Et₃N causes allylic deprotonation forming internal olefin complexes of the type [Cp(CO)₂Fe{CH₂CHCH(CH₂)_n?3X}]PF₆.     

Gas-tight proton-conducting Nd2 − xCaxZr2O7 − δ (x = 0, 0.05) ceramics

Journal of Solid State Electrochemistry - Gas-tight Nd2 − xCaxZr2O7 − δ (x = 0, 0.05) pyrochlore materials have been prepared via...     

Viscosity of {xCO2 + (1 − x)CH4} with x = 0.5174 for temperatures between (229 and 348) K and pressures between (1 and 32) MPa

A vibrating wire instrument, in which the wire was clamped at both ends, was used to measure the viscosity of {xCO₂ + (1 − x)CH₄} with x = 0.5174 with a combined uncertainty of 0.24 μPa · s (a relative uncertainty of about 0.8 %) at temperatures T between (229 and 348) K and pressures p from (1 to 32) MPa. The corresponding mass density ρ, estimated with the GERG-2008 equation of state, varied from (20 to 600) kg · m⁻³. The measured viscosities were consistent within combined uncertainties with data obtained previously for this system using entirely different experimental techniques. The new data were compared with three corresponding states-type models frequently used for predicting mixture viscosities: the Extended Corresponding States (ECS) model implemented in REFPROP 9.1; the SUPERTRAPP model implemented in MultiFlash 4.4; and a corresponding states model derived from molecular dynamics simulations of Lennard Jones fluids. The measured viscosities deviated systematically from the predictions of both the ECS and SUPERTRAPP models with a maximum relative deviations of 11 % at (229 K, 600 kg · m⁻³) and −16 % at (258 K, 470 kg · m⁻³), respectively. In contrast, the molecular dynamics based corresponding states model, which is predictive for mixtures in that it does not contain any binary interaction parameters, reproduced the density and temperature dependence of the measured viscosities well, with relative deviations of less than 4.2 %.     

The structural and thermal stability,electrochemical hydrogenation and corrosion behavior of LaT5−xMx(T = Co,Ni and M = Al,Ge, Li) phases

The structural and thermal stability, electrochemical hydrogenation and corrosion behavior of LaT_5−x(M/Li)_x (T = Co, Ni and M = Al, Ge) alloys have been investigated using x-ray diffraction, SEM with WDS/EDX, DSC and electrochemical techniques. The prepared ternary and quaternary samples are solid solutions on the base of binary LaCo₅ and LaNi₅ compounds with hexagonal CaCu₅ structure type. By partial substitution of transition metals (Ni and Co) by Al, Ge and Li in the LaT_5−x(M/Li)_x alloys the discharge capacity increased by 25%. Doping of LaCo₅ and LaNi₅ binary phases by Al, Ge and Li improves corrosion resistance, thermal stability and absorption capacity during the electrochemical hydrogenation. These alloys passivate effectively in strong alkaline solution.     

Relative permittivity increments for {xCH3OH + (1 − x)CH3OCH2(CH2OCH2)3CH2OCH3} fromT = 283.15 K toT = 323.15 K

Relative permittivities of { CH₃OH  +  CH₃OCH₂(CH₂OCH₂)₃CH₂OCH₃(2,5,8,11,14-pentaoxapentadecane, tegdme)} at temperatures from 283.15 K to 323.15 K and atmospheric pressure, were measured over the whole composition range. Experimental relative permittivities were fitted by a polynomial function in mole fraction. Values of relative permittivity were measured using a HP4284A precision LCR Meter together with the measuring cell HP16452A at 1 MHz. Relative permittivity increments were determined from experimental data and fitted to a variable-degree polynomial function. Different theoretical models were used to predict the permittivity of this mixture. The predictions are better when the volume change on mixing is considered.     

(Solid + liquid) equilibria for the ternary system (CsBr + LnBr3 + H2O) (Ln = Pr,Nd, Sm) at T = 298.2 K and atmospheric pressure,thermal and fluorescent properties of Cs2LnBr5·10H2O

The (solid + liquid) phase equilibria of the ternary systems (CsBr + LnBr₃ + H₂O) (Ln = Pr, Nd, Sm) at T = 298.2 K were studied by the isothermal solubility method. The solid phases formed in the systems were determined by the Schreinemakers wet residues technique, and the corresponding phase diagrams were constructed based on the measured data. Each of the phase diagrams, with two invariant points, three univariant curves, and three crystallization regions corresponding to CsBr, Cs₂LnBr₅·10H₂O and LnBr₃·nH₂O (n = 6, 7), respectively, belongs to the same category. The new solid phase compounds Cs₂LnBr₅·10H₂O are incongruently soluble in water, and they were characterized by chemical analysis, XRD and TG-DTG techniques. The standard molar enthalpies of solution of Cs₂PrBr₅·10H₂O, Cs₂NdBr₅·10H₂O and Cs₂SmBr₅·10H₂O in water were measured to be (52.49 ± 0.48) kJ · mol⁻¹, (49.64 ± 0.49) kJ · mol⁻¹ and (50.17 ± 0.48) kJ · mol⁻¹ by microcalorimetry under the condition of infinite dilution, respectively, and their standard molar enthalpies of formation were determined as being −(4739.7 ± 1.4) kJ · mol⁻¹, −(4728.4 ± 1.4) kJ · mol⁻¹ and −(4724.4 ± 1.4) kJ · mol⁻¹, respectively. The fluorescence excitation and emission spectra of Cs₂PrBr₅·10H₂O, Cs₂NdBr₅·10H₂O and Cs₂SmBr₅·10H₂O were measured. The results show that the upconversion spectra of the three new solid phase compounds all exhibit a peak at 524 nm when excited at 785 nm.