Ferroelectric and optical properties of Ba6Ti2Nb8O30 single crystals

The dielectric, optical and non-linear optical properties of Ba₆Ti₂Nb₈O₃₀ single crystals were examined from room temperature up to the Curie temperature of 245°C. The spontaneous polarization at room temperature was estimated as 0·22±0·01 C/m². The linear electrooptic constants were measured as r₃₃^T=(1·17±0·02)×10^?10 and r₁₃^T=(0·42±0·01)×10^?10 m/V. The non-linear optical coefficients were d₃₃=(15·1±2·0)×10^?12 and d₃₁=(11·0±2·0)×10^?12 m/V, which are comparable to those of Ba₄Na₂Nb₁₀O₃₀. Temperature dependences of δ₃₃ and δ₃₁ (Miller's δ) were found to be proportional to that of P_s.     

Alpha-heavy-ion angular correlations from 28Si + 12C

Alpha particles have been measured in coincidence with heavy recoil nuclei from the ²⁸Si + ¹²C reaction. At E_lab = 87 MeV angular correlations for alphas between 15° and 55° and heavy ions at angles ?9°, ?12° and ?15° have been taken. An excitation function of coincidence events with θ_α = 30° and θ_HI = ?12° has been measured for 84 MeV < E_lab < 91.5 MeV. The results are well described by a statistical-model calculation for compound nucleus decay. No evidence is found for additional processes.     

Polymorphism in Bi2Sn2O7

Single crystals of Bi₂Sn₂O₇ were grown in a Bi₂O₃ flux. Phase transitions were identified at about 90 and 680° using X-ray, SHG, DSC, dielectric, and optical data. γ-Bi₂Sn₂O₇, which exists above 680°C is centric and cubic with a = 10.73 Å at 700°, and it probably has the ideal pyrochlore structure. β-Bi₂Sn₂O₇, which exists between 680° and about 90°C, is acentric but remains cubic with a = 21.40 Å. α-Bi₂Sn₂O₇, which exists from about 90°C to below room temperature, is acentric and noncubic, probably tetragonal with a = 21.328 and c = 21.545 Å. The α-β transition is first order, and the β-γ transition appears to be second order. Substitutions of Pb²⁺ or Cd²⁺ for Bi³⁺ and of Ga³⁺, Rh³⁺ Sc³⁺, In³⁺, Sb⁵⁺ Nb⁵⁺ or Ta⁵⁺ for Sn⁴⁺ lower the α-β transition temperature.     

The temperature dependence of the angular variation of,and the critical point exponent for the EPR linewidth in the two-dimensional canted antiferromagnetic (C2H5NH3)2MnBr4: Evidence for a structural phase transition

The angular variation of the EPR linewidths in single crystals of (C₂H₅NH₃)₂MnBr₄ has been measured as a function of temperature. The angular dependence is well characterized by δH(θ) = a + b(3 cos²θ ? 1) + c(3 cos²θ ? 1)². The temperature dependence of the expansion coefficients is reported, and the effect of critical point fluctuations near the Néel temperature as well as a linear temperature dependence at high temperature are observed. A sharp decrease in linewidths at 160°K is attributed to a structural phase transition. The Néel temperature is determined to be 46°K (± 1°) from linewidth measurements of a powder sample. The linewidths diverge exponentially near the Néel temperature with a critical point exponent of 1.5.     

Lithium aluminum nitride,Li3AlN2 as a lithium solid electrolyte

Single phase of Li₃AlN₂ was prepared from the mixture of Li₃N/AlN = 1.2 to 1.5 in molar ratio at 700°C and at 900°C. It crystalizes in the cubic system derived from antifluorite-type structure having the lattice parameter $\text{a = 9.470}\text{A}\text{?}$. It is a pure ionic conductor having conductivity of 5 × 10^?8ω^?1cm^?1 at room temperature and an activation energy of 52 kJ/ mol. Its decomposition voltage was 0.85 V at 104°C. The TiS₂/Li₃AlN₂/Li cell could be discharged at a constant current of 45 μA/cm² at 104°C.     

Magnetic annealing and crystallization kinetics of the metallic glass Fe5Co70Si15B10

Magnetic annealing and crystallization kinetics of amorphous ribbons of Fe₅Co₇₀Si₁₅B₁₀ were studied. For a toroid stress-relieved at 365°C for 2 h, the anistropy energy K_u obtained by cooling in a magnetic field from 300°C was ≈1.1 × 10³erg/cm³ at room temperature. The reorientation of induced anisotropy of this toroid followed the equation for first-order kinetics closely, yielding an activation energy ΔE = 1.9 eV and a pre-exponential frequency factor v₀ = 3.2 × 10¹³s^-1. Anisotropy reorientation in a toroid partially stress-relieved at 220°C, although was clearly reversible during 8 cycles of isothermal annealing in tranverse and in longitudinal field, exhibited significant deviations from the equation for first order kinetics. Treating the data in terms of the equation for first order kinetics, a narrow spectrum of activation energy from 1.2 to 1.8 eV, with corresponding frequency factors from 1.8 × 10⁸ s^-1 to 5.6 × 10¹² s^-1, was obtained. The difference in behavior between the two samples is discussed in the light of concepts in structural relaxation recently proposed by T. Egami. Crystallization kinetics was studied on a DSC apparatus, using Kissinger's method. At 10 K/min heating rate, the temperature of incipient crystallization was found to be 770 K. The activation energies found were in the range 4.8–4.2 eV.     

Investigation of the reaction 2H(n,np) at θn = 0°

The differential cross section of the ²H(n, np) reaction was measured at θ_n = 0°. Because of the applied special geometry the experimental data extend over a large fraction of the phase space, including several final state interaction regions as well as regions far from the dominance of quasi-two-body processes. The experiment was analysed with an exact three-body calculation using s-wave separable potentials (CEE). The analysis of the n-n and n-p final state interaction peaks gave a_nn = ?16.3 ± 1.6 fm for the n-n ¹S₀ scattering length and r_nn = 3.15 ± 0.7 fm for the effective range. Remarkable deviations from the calculated cross sections-were found in regions where no strong final state interaction was present.     

The heat capacity of the layer compounds (CH3CH2CH2NH3)2MnCl4 and (CH3CH2CH2NH3)2CdCl4 from 10 K TO 300 K

The heat capacity of the layer compounds tetrachlorobis (n-propylammonium) manganese II and tetrachlorobis (n-propylammonium) cadmium II, (CH₃CH₂CH₂NH₃)₂MnCl₄ and (CH₃CH₂CH₂NH₃)₂CdCl₄ respectively, has been measured over the temperature range 10 K ?T ? 300 K.Two known structural phase transitions were observed for the Mn compound in this temperature region: at T = 112.8 ± 0.1 K (ΔH_t= 586 ± 2 J mol^?1; ΔS_t = 5.47 ± 0.02 J K^?1mol^?1) and at T =164.3 ± (ΔH_t = 496 ± 7 J mol^?1; ΔS_t =3.29 ± 0.05 J K^?1mol^?1). The lower transition is known to be from a monoclinic structure to a tetragonal structure, while the upper is from the tetragonal phase to an orthorhombic one. From comparison with the results for the corresponding methyl Mn compound it is deduced that the lower transition primarily involves changes in H-bonding while the upper transition involves motion in the propyl chain.A new structural phase transition was observed in the Cd compound at T= 105.5 ± 0.1 K (ΔH_t= 1472.3 ± 0.1 J mol^?1; ΔS_t = 13.956 ± 0.001 J K^?1mol^?1), in addition to two transitions that have been observed previously by other techniques. The higher of these transitions(T = 178.7 ± 0.3 K; ΔH_t = 982 ± 4 J mol^?1 ΔS_t = 6.16 ± 0.02 J K^? mol^?1) is known to be between two orthorhombic structures, while the structural changes at the lower transition (T= 156.8 ± 0.2 K; ΔH_t = 598 ± 5 J mol^?1, ΔS_t = 3.85 ± 0.03 J K^?1 mol^?1) and at the new transition are not known. It is proposed that these two transitions correspond respectively to the tetragonal to orthorhombic and monoclinic to tetragonal transitions in the propyl Mn compounds.In addition to the structural phase transitions (CH₃CH₂CH₂NH₃)₂MnCl₄ magnetically orders at t? 130 K. The magnetic contribution to the heat capacity is deduced from the heat capacity of the corresponding diamagnetic Cd compound and is of the form expected for a quasi 2-dimensional Heisenberg antiferromagnet.     

Effect of Fe2O3 nanoparticles on combustion of coal surrogate (Anisole): Enhanced ignition and formation of persistent free radicals

This contribution explores the effect of nanoparticles of iron (III) oxide (Fe₂O₃) on the combustion of coal surrogate, i.e., anisole, identifying the changes in ignition features as well as the occurrence of persistent organic pollutants in the initiation channels. The method applies packed-bed reactor coupled with Fourier transform infrared (FTIR) spectroscopy to quantitate the ignition temperature under typical fuel-rich conditions, in-situ electron paramagnetic resonance (EPR) to elucidate the formation of environmentally-persistent free radicals (EPFR), diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) to monitor the chemisorption of organic substrates on the nanoparticles, as well as X-ray diffraction for particles characterisation (PXRD). We employ cluster-based quantum mechanical calculation to map the reaction pathway within the scope of the density functional theory. The results of Fe₂O₃-mediated combustion of anisole depict an excessive reduction in ignition temperature from 500?°C around 220?°C at λ?=?0.8. As confirmed both from EPR and DRIFTS measurements, the chemisorption of anisole on α-Fe₂O₃ surfaces follows the direct dissociation of the O–CH₃ (and OCH₂–H), leading to the formation of surface-bound phenoxy radicals at temperatures as low as 25?°C and incurring an estimated energy barrier of E_a?=?18?kJ mol^?1 and a preexponential factor of A?=?2.7?×?10¹² M^?1 s^?1. This insight applies to free-radical chain reactions that induce spontaneous fires of coal, as coal comprises ferric oxide nanoparticles, and equally to coexistence of aromatic fuels with thermodynamically reactive Fe₂O₃ surface, e.g., in fly ash, at the cooled-down tail of combustion stacks.     

Na+ ion conductivity and crystallographic cell characterization in the Hf-nasicon system Na1+xHf2SixP3−xO12

We have measured the effect of varying the mobile ion concentration on the sodium ion conductivity in the Hf-Nasicon system, Na_1+xHf₂Si_xP_3-xO₁₂, for 1.4 ? x ? 2.8. The conductivity is greatest for Na_3.2Hf₂Si_2.2 P_0.8O₁₂: σ_25°C = 2.3 × 10^?3 (ω cm)^?1, and σ_250°C = 1.7 × 10^?1 (ω cm)^?1. These values are approximately 50% greater and worse, respectively, than the values reported for the best Zr-Nasicon. We have characterized the variation of lattice parameters with composition and found the behavior to be similar to that of Zr-Nasicon. A small distortion from rhombohedral to monoclinic symmetry occurs for compositions 1.8 ? x ? 2.2.     

Alignment and resonances in 12C+12C inelastic scattering

Using the out-of-plane γ-ray particle coincidence method we have measured the spin alignment P_zz of excited ¹²C(2⁺) nuclei from ¹²C+¹²C inelastic scattering in the energy range 16 MeV ? E_cm ? 33 MeV.P_zz varies strongly as a function of energy and angle. The correlation of resonant structures in the cross section with maxima of the alignment is particularly clear in mutual inelastic scattering and in θ_cm = 90° single inelastic scattering.     

Ab initio calculations for propyne and the hydrogen bonded complex NH H C C CH 3 3

The hydrogen-bonded cluster NH₃ …H—C≡C—CH₃ has been investigated by means of the coupled electron pair approximation, making use of a basis set of 198 contracted Gaussian-type orbitals. The calculated equilibrium structure is r _1^e (N—H) = 1?0127 Å, α_e(∠HN…H) = 112?32°, R _1^e (N…H) = 2?3593 Å, r _2^e (acetylenic C—H) = 1?0690 Å, R _2^e (C≡C) = 1?2078 Å, R _3^e (C—C) = 1?4711 Å, r _3^e (C—H) = 1?0894 Å and β_e(∠CCH) = 110?50°. The recommended equilibrium dissociation energy is D _e = 12?4±0?5 kJ mol^-1 and the calculated equilibrium dipole moment is μ_e = – 1?468 D, with the positive end of the dipole at the ammonia protons. Harmonic wavenumbers and absolute infrared intensities for the totally symmetric modes are calculated. Compared with free propyne the acetylenic CH stretching vibration experiences a bathochromic shift of 93 cm^-1 and an intensity enhancement by a factor of 5?5.     

The (γ, n) reaction on 16O between giant resonance and pion threshold

A new TOF facility has been built for measurements of differential (γ, n) cross sections to discrete final states of light nuclei in the photon energy range between giant resonance and pion threshold. The observed neutron angle θ_n can continuously be varied between 0° and 150°, and additionally measurements at 175° and 180° are possible. Differential cross sections for the reaction ¹⁶O(γ, n₀)¹⁵O are presented for E_γ = 60 MeV (40° ? θ_n ? 149°) and for θ_n = 90° (60 MeV ? E_γ ? 160 MeV). The results, combined with the corresponding (γ, p₀) cross sections, indicate an absorption mechanism of high energy photons by neutron-proton pairs.     

Non-statistical effects in the 12C(12C, α)20Ne reaction near Ec.m. = 15 MeV

The ¹²C(¹²C, α)²⁰Ne reaction is studied near E_c.m. = 15 MeV. Angular distributions for three energies and excitation functions at θ_{lab = 30°} over an energy range E_c.m. = 14.5?15.4 MeV for about 20 levels in ²⁰Ne (E_ex = 0–13 MeV) are examined. The statistical analysis yields the results that a correlated resonance is present at E_c.m. = 14.75 MeV. A nonstatistical contribution to the reaction is also apparent when energy-averaged cross sections are compared with the Hauser-Feshbach model predictions. Strong population of the 0⁺₃ band in ²⁰Ne is observed.     

Covalent distribution of spin in V2O3:O17 nuclear resonance

O¹⁷ nuclear magnetic resonance has been observed in metallic V₂O₃ with frequency shifts from (?0.10 ± 0.02)-(?0.05 ± 0.02) per cent between 170 and 460°K respectively, a linewidth of 37 ± 5 oe and spin-lattice relaxation rate 1/T₁ ≈ 60 sec^?1 at 296°K. From these quantities, covalency parameters f_s/2S = ? 0.35 × 10^?3 and ?_π/2S ≈ ? 0.07 are calculated. One of the two vanadium 3d electrons in the antiferromagnetic state below the 170°K metal-insulator transition is inferred to lie in a non-magnetic state, while covalent charge transfer augments the spin moment of the other 3d electron to the observed 1.2 μ_B.     

Projectile fragments from 86 MeV/nucleon 12C induced reactions

An 86 MeV/nucleon ¹²C beam has been used to bombard targets of C, Ag and Au. Energy spectra of reaction products with Z = 3?6 and A = 6?12 have been measured at angles between 3° and 20°. A simple fragmentation model, while predicting approximately the gross features of the data, fails to describe the results in detail.     

High efficiency second-harmonic generation in KNbO3 crystals

Second-harmonic generation in KNbO₃ crystals has been studied with CW and pulsed Al_xGa_1?xAs and dye lasers. High conversion efficiencies were obtained by noncritical Type I phase-matching at room temperature for the wavelength λ_PM = (860±2) nm using the nonlinear optical coefficient d₃₂ = 21 pm/V. The measured peak power was P_2ω=13.6 μW for a fundamental power P_ω=21 mW with a crystal of l = 8.97 mm in length. The phase-matching wavelength in the orthorhombic phase of KNbO₃ can be temperature tuned between 838 nm (for T = -36°C) and 950 nm (for T = +180°C).     

The thermoelectric power in AgxTiS2 and AgxNiPS3. Part II. The ionic component of the thermoelectric power

The EMF of the isothermal cells: Ag/AgI/Ag_xTiS₂: 0<x<1, T=150–200°C/Ag_xNiPS₃: 0<x<3, T=150–350°C has been measured. From the EMF-x curves the existence ranges of the 2-phase (stage I and II) regions ?0.16<x<0.32 for the Ag/Ag_xTiS₂ system at 190°C; 0.20 < x < 0.50 and 1 < x < 2 for the Ag/Ag_xNiPS₃ system at 400°C - have been determined. The results are sustained by X-ray diffraction and electrical conductivity measurements. From the EMF-T curves the partial enthalpy (ΔH?_Ag) and entropy (ΔS?_Ag) of dissolution of silver in the Ag_xSSE (solid solution electrode) materials were obtained. In the case of Ag_xTiS₂, ΔH?_Ag has a low absolute value, while ΔS?_Ag is distinctly positive. The EMF of the Ag/Ag_xNiPS₃ system also has a positive temperature coefficient. Furthermore, the ionic component of the thermoelectric power, ΔE/ΔT, of the thermogalvanic cells: Ag/AgI/Ag_xSSE/AgI/Ag Ag_xTiS₂: 0 < x < 1, T = 150–200°C( T ) (T+ΔT) Ag_xNiPS₃: 0 < x < 1, T= 150–350°C has been measured. The kinetically important heat of transport of silver ions in the Ag_xSSE materials has been determined in two ways: first from the dependence of the ionic Seebeck coefficient (?_Ag+) on reciprocal temperature; and second from direct calculation, using the data for ?_Ag+ and ΔS?_Ag. The heat of transport is much smaller than the activation enthalpy for Ag⁺-conduction, indicating a high ionic polaron binding energy in these materials.     

Thermoelectric power of (Me4N)2Ag13I15 and (Et4N)2Ag13I15

Thermoelectric power using reversible silver electrodes and electrical conductivity on the compressed pellets of (Me₄N)₂Ag₁₃I₁₅, and (Et₄N)₂Ag₁₃I₁₅ have been measured between room temperature and below 160°C. The results of θ can be expressed by the equations:?θ = 0.115 (10³/T)+0.2905VK^?1 and ?θ = 0.150 (10³/T) + 0.305mV K^?1; and those of conductivity by the equations; σ = 28.7 exp (?0.17eV/kT) ohm^?1cm^?1 and $\text{σ = 216.6 exp (?0.24e}\text{V}\text{kT}\text{)}$ ohm^?1cm^?1; respectively for Me- and Et-electrolytes. The results are discussed and compared with those of previous authors.     

Energies of the n2S12 and n2D32,52 states of Cs

Using the technique of Doppler-free two-photon spectroscopy the energies of the n²S_{$\text{1}\text{2}$} (12 ? n ? 35) and n²D_{$\text{3}\text{2}$,$\text{5}\text{2}$} (11 ? n ? 48) states of CsI have been measured with a thermionic detector. The absorption spectrum of molecular iodine was used as a reference giving us a total estimated accuracy of about 2 × 10^-7. Taking also into account the energies of the 7–11 ²S_{$\text{1}\text{2}$} and 5 and 6 ²D_{$\text{3}\text{2}$,$\text{5}\text{2}$} states measured by other authors and using an extended Ritz-formula we found the ionization limit to be E_i = 31406.468 ± 0.006 cm^-1.