Diffusion of 55Fe in Fe2O3 single crystals

The diffusion of ⁵⁵Fe has been measured parallel to the c axis of Fe₂O₃ single crystals at temperatures in the range 708–1303°C and at an oxygen activity of unity. The tracer penetration profiles were determined using sectioning techniques. For temperatures above 900°C the tracer diffusion coefficient is given byD¹(Fe) = 1.6 × 10⁹ exp[?6.0 (eV)/kT] cm² s^?1 and below 900°C by 2.8 × 10^?9 exp[?1.8 (eV)kT]. The high-temperature behaviour is probably characteristic of pure Fe₂O₃, whereas diffusion at lower temperatures may be influenced by impurities. The most likely defects responsible for diffusion of Fe are iron interstitials and, for oxygen, oxygen vacancies, and the observed activation energies are discussed in terms of the properties of these defects. The diffusion data and defect models have been used to predict the rate of growth of Fe₂O₃ and indicate that outward Fe diffusion is the dominant transport process. Previously published data for Fe₂O₃ growth in a variety of experimental situations have been corrected to a single rate constant using a model for multilayer growth. The corrected data are all in good agreement but are approximately two orders of magnitude greater than predicted from diffusion data, which suggests that grain boundary diffusion controls the growth of Fe₂O₃ in practice.     

Diffusion and correlation effects in iron-doped CoO

The diffusion of ⁵⁹Fe and ⁶⁰Co has been measured in pure CoO and dilute iron-doped CoO, (Co_1?cFe_cO, as a function of temperature (1000–1400°C) and oxygen partial pressure P_{o2), (10^?7 ≦ Po2 ≦ 0 21 atm) The enhancement factors for the diffusivities of iron and cobalt are nearly identical, which suggests that the primary cause of the enhancement is the increased concentration of charge-compensating cation vacancies with the addition of iron. The Fe ions dissolved in CoO appear to exist as a mixture of Fe²⁺ and Fe³⁺ ions, the fraction of iron ions in the three-plus state decreases with decreasing Po2 The simultaneous diffusion of ⁵²Fe and ⁵⁹Fe has been measured as a function of (itpo; at 1200°C The correlation factor for Fe impurity diffusion determined from the isotope-effect measurements is about the same as that for self-diffusion in CoO at high (itPo2} (2 × 10^?3 ≦ p_o2 ≦ 0 21 atm), but increases slightly with decreasing p_O2 Both the enhancement-effect and isotope-effect experiments suggest that the nearestneighbor interactions between Fe ions and vacancies is small, and that the dissolved Fe ions do not have strongly bound electron holes.     

Chromium tracer diffusion in NiO crystals

Diffusion of ⁵¹Cr in NiO single crystals in air has been studied by the tracer-sectioning technique. In the temperature range 1192–1642°C, the diffusion coefficient can be expressed by the Arrhenius expression D=D_oexp(-Q/RT), with D_o=(8·6±1·2)×10^?3 cm²/sec and Q=67·4±1·1 kcal/mole. The use of a high specific-activity tracer and a special configuration for the diffusion anneal prevented the self-dopling effect found by Seltzer and the evaporation of chromium from the sample surface. The present results, in conjunction with published results on nickel self-diffusion in NiO and interdiffusion in the NiO?Cr₂O₃ system, are used to determine a chromium ion-vacancy binding energy of about 5 kcal/mole in pure NiO.     

Correlation and isotope effects for cation diffusion in magnetite

The simultaneous diffusion of ⁵²Fe and ⁵⁹Fe has been measured in Fe₃O₄ as a function of equilibrium oxygen partial pressure (10^?9 <p_o2 < 10^?4 atm) at 1200°C. The p_o2 dependence of D goes through a minimum near 10^?6 atm in agreement with earlier data of Dieckmann and Schmalzried. Comparison of the isotope effect results with correlation-factor calculations suggests that at p_o2 γ 10^?6, diffusion occurs predominantly by vacancy jumps between the normally occupied octahedral sites on the spinel lattice; jumps between tetrahedral sites probably play a lesser role. At p_o2< 10^?6 atm, diffusion occurs by an interstitialtype mechanism involving the simultaneous migration of two atoms. Five of the seven interstitialcy jumps considered in our correlation-factor calculations are consistent with the experimental results.     

Cation self-diffusion and the isotope effect in Mn1−δO

Diffusion of ⁵⁴Mn in Mn_1?δO single crystals has been measured by a serial sectioning technique as a function of temperature (1000–1500°C) and deviation from stoichiometry (0.00003 < δ < 0.12). The value of m in the expression varies from about 6 at low Po₂ at all temperatures to a value approacing 2 at high Po₂ and high temperatures, thus suggesting that diffusion occurs by doubly charged vacancies at low Po₂ with increasing contributions from singly charged and neutral vacancies as Po₂ (and vacancy concentration) increases. For δ near 0.1, the values of D fall below the values extrapolated from smaller defect concentrations. The isotope effect for cation self-diffusion was measured by simultaneous diffusion of ⁵²Mn and ⁵⁴Mn in Mn_1?δO (0.0004 < δ < 0.116) at 1300 and 1500°C. The measured values of fΔK are independent of temperature within experimental error, and decrease from a value of 0.70 at low defect concentrations to 0.37 for large values of δ. The isotope-effect results suggest that diffusion occurs by single non-interacting vacancies at low defect concentrations; defect-defect interactions become important for δ ? 0.01. The defect-defect interactions may involve essentially individual defects or may result in defect clusters; the similarity between the present isotope-effect results and those for Fe_1?δ0 suggests that defect clustering plays a significant role in mass transport in Mn_1?δO at large values of δ.     

The effect of duration of diffusion on Ag diffusion coefficients in YBa2Cu3O7

The Ag diffusion in superconducting YBa₂Cu₃O₇ (YBaCuO) ceramic has been studied over the duration of the diffusion range 5-24 h in the temperature range 700-850 °C by the energy-dispersive X-ray fluorescence (EDXRF) technique. For the excitation of silver atoms, an annular Am-241 radioisotope source (50 mCi) emitting 59.543 keV photons was used. The temperature dependences of silver diffusion coefficients in grains (D₁) and over the grain boundaries in the range 700-850 °C (D₂) are described by the relations D₁=1.4×10⁻² exp[−(1.18±0.10)/kT] and D₂=3.1×10⁻⁴ exp[−(0.87±0.10)/kT].     

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.     

Cation self-diffusion and the isotope effect in Fe2O3

Self-diffusion of ⁵⁹Fe parallel to the c axis in single crystals of Fe₂O₃ has been measured as a function of temperature (1150–1340°C) and oxygen partial pressure (2 × 10^?3 ? p_O2 ? 1 atm) The temperature dependence of the cation diffusivity in air is given by the expression

$\text{D}{}_{\mathrm{<mtext>Fe</mtext>}}{}^1\text{= (1.9}{}_{\mathrm{?1.4}}{}^{\mathrm{+5.2}}\text{× 10}{}^9\text{exp}\text{(?}\text{141.4 ± 4.0 kcal/mole}\text{RT}\text{)}\text{cm}{}^2\text{/}\text{s}$

.The unusually large value of D₀ is interpreted in terms of the values of the preexponential terms in the reaction constants for the creation of defects in Fe₂O₃. The oxygen-partial-pressure dependence of the diffusivity indicates that cation self-diffusion occurs by an interstitial-type mechanism The simultaneous diffusion of ⁵²Fe and ⁵⁹Fe has been measured in Fe₂O₃. The small value of the isotope effect suggests that iron ions diffuse by an noncollinear interstitialcy mechanism, which is consistent with the crystal structure of Fe₂O₃.     

Cd0.9Zn0.1Te晶体的Cd气氛扩散热处理研究

将生长得到的Cd_0.9Zn_0.1Te晶体在Cd气氛下及不同的温度条件下进行了退火处理. 借助已建立的退火处理过程中Cd_1-xZn_xTe晶体材料电阻率及导电类型变化和扩散杂质的扩散系数之间关系的模型，结合实验数据，获得了1073K，973K和873K下Cd在Cd_0.9Zn_0.1Te晶体中的扩散系数，并估算了其激活能. 通过使用获得的扩散系数，研究了在不同温度及饱和Cd气氛下，退火时间对Cd_0.9Zn_0.1Te晶体电阻率分布及导电类型等的变化的影响.     

Anomalous acid proton self-diffusion in N(CH3)4HSO4 — A candidate for proton superionic conductivity

The appearance of a “liquid-like” proton T₂ component above 100°C and the relatively high value of the proton self-diffusion coefficient D = (5–8) × 10^-7cm²sec^-1 between 175°C and 200°C demonstrate the onset of a super-ionic state in N(CH₃)₄HSO₄. The ratio between the “liquid” and “solid” like components shows that acid protons are responsible for the high ionic conductivity.     

ESR study of Fe3+ and Mn2+ ions on trigonal sites in ilmenite structure MgTiO3

Electron spin resonance has been observed for Fe³⁺ and Mn²⁺ ions occupying sites with trigonal symmetry in undoped and doped Verneuil-grown crystals of the ilmenite type compound MgTiO₃. At 300 K, the fine structure parameters in the spin Hamiltonian are (in 10^?4cm^?1) D = +844 (± 1), (a? F) = +118 (± 1), a = 69 (± 7) for Fe³⁺ and D = +164 (± 1), (a ? F) = +10.2 (± l), a = 7.0 (± 1) for Mn²⁺. These values are compared with literature data for Fe³⁺ and Mn²⁺ in other oxides, especially Al₂o₃, with particular reference to the recent “superposition” theory of the effect of a trigonal distortion. From the orientation of the axes of cubic pseudosymmetry of the spin Hamiltonian, and with the assumption that a has the same sign for both ions, it is proposed that Fe³⁺ and Mn²⁺ occupy the same octahedral site, namely the Mg²⁺ site. Anomalous line splittings observed for one sample were attributed to twinning on (0001) or {1120} planes.     

Spectre de photoélectrons et calcul des facteurs de franck-condon pour H2O,D2O,HDO

The first band of the photoelectron spectrum of HDO has been recorded. In agreement with the selection rules of the group theory, the fundamental terms of the three symmetric vibrations of HDO (C_s symmetry) have been observed. Taking the geometry of the ion as parameters, the Franck-Condon factors for the ionization of H₂O, D₂O and HDO have been calculated. The geometry of the H₂O⁺, D₂O⁺, HDO⁺ ions (ground state) have been determined accurately by comparison of the calculated results with the corresponding photoelectron spectra. This geometry is approximately the same for the three ions: r_OH  1,00 Å and < HOH  110°.     

Mössbauer study of Fe2+ ions in trigonal sites of spinels: GeFe2O4, GeCo2O4, GeNi2O4

We discuss here the results and the interpretation in the crystalline-field approach of some Mössbauer experiments on Fe²⁺ ions in the spinels GeFe₂O₄, GeCo₂O₄ and GeNi₂O₄. Once the sign of the quadrupolar interaction e²qQ has been deduced from a magnetic spectrum, the thermal variation of e²qQ may be used for determining the electronic level scheme of the Fe²⁺ ion (including the energies and wavefunctions of the levels). Then we may predict the form and magnitude of the spin hamiltonian, of the magnetic anisotropy and of the hypefine field tensor. Below T_N the experimental results are expressed in terms of a molecular-field, the eventual variations of which have been studied in magnitude and in orientation; by using the same calculation for the three compounds, we obtained a reasonable agreement between the experimental and calculated values of the hyperfine field at 0°K.     

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.     

Study of the I=2 ππ scattering from the reaction π−d → π−π−psp at 9.0 GeV/c

We have studied the I=2, ππ scattering using the classical Chew-Low extrapolation method. Results are given on the cross sections and the phase shifts δ₀², δ₂² and δ₄² up to 2.2. GeV. δ₀² values are -7.8 ? 3.0° at the K^o mass, -15. ? 1.5° at the ? mass and -29. ? 2.2° of the f^o mass. Above the f^o mass |δ₀²| decreases.     

Pulsed magnetic field study of Fe2+ in some fluosilicates

Pulsed field experiments up to 450 kOe have been performed on FeSiF_6.6H₂O. We interpret the data: (i) in terms of spin hamiltonian constants: D = 12.3± 0.2 cm^-1 (E = 0.54cm^-1 being known from EPR data); (ii) in terms of axial-crystal-field parameters: $\text{δ}\text{λ}\text{=}\text{orbital trigonal splitting/spin-orbit coupling}\text{= 15 ± 2; λ = -100 ± 7cm}{}^{\mathrm{?1}}$. The magnetic axis is found to deviate from the cristallographie c axis by an angle 1° < θ < 2°. The adiabatic cooling obtained during the pulse is discussed.Similar experiments on Fe_0.15Zn_0.85SiF_6.6H₂O and Fe_0.30Zn_0.70SiF_6.6H₂O single crystals are reported; in both cases we measure $\text{D}\text{g}{}_{\mathrm{\parallel }}\text{= 6.0 ± 0.1cm}{}^{-1}$. Using EPR data, we obtain D = 14.3cm^-1, λ ～ ?75cm^-1, δ ～ 195cm^-1; using Mössbauer data, we obtain D = 15.3cm^-1, λ ～ ?88cm^-1, δ ～ 185cm^-1.     

Defect structure and migration in Fe3O4

We present the results of a computer simulation study of the defect formation and migration energies in Fe₃O₄. Calculated Frenkel and Schottky energies are found to be similar in magnitude and both are considerably reduced by screening due to electron redistribution around the charged-defect species. The calculations also suggest that cation diffusion is mainly effected by a colinear interstitialcy mechanism at low P_o2 and by a simple octahedral vacancy mechanism at higher P_o2.     

Cation self-diffusion in LaFeO3 measured by the solid state reaction method

Cation diffusion in LaFeO₃ has been studied using the solid state reaction between sintered bodies of La₂O₃ and Fe₂O₃ at 950–1350 °C in air or O₂–N₂ mixtures. LaFeO₃ was the only product formed. The growth was parabolic and demonstrated to take place predominantly by diffusion of Fe³⁺ through the LaFeO₃ layer. The self-diffusion coefficient of Fe³⁺ was accordingly calculated from the parabolic rate constant, and at constant activity of La₂O₃, a_La2O3 = 1, it shows Arrhenius-type behaviour with activation energy 320 ± 20 kJ/mol. It appeared to be independent of the surrounding pO₂, but this was ascribed to lack of equilibrium with the atmosphere during growth of the LaFeO₃ layer. Correspondingly, the product LaFeO₃ is probably stoichiometric, and differences between our diffusivity and activation energy and those in the literature are discussed in view of this.     

Structural and magnetic properties of Co1−xZnxFe2O4 nanoparticles by co-precipitation method

Co_1−xZn_xFe₂O₄ nanoparticles were prepared by co-precipitation method with x varying from 0 to 1.0. The powder samples were characterized by X-ray diffraction (XRD), vibrating sample magnetometer (VSM) and Fourier transform infrared spectroscopy (FTIR). The average crystallite sizes of the particles were determined from XRD. X-ray analysis showed that the samples were cubic spinel. The average crystallite size (D_aveXR) of the particles precipitated was found to vary from 6.92 to 12.02 nm decreasing with the increase in zinc substitution. The lattice constant (a_o) increased with the increase in zinc substitution. The specific saturation magnetization (M_S) of the particles was measured at room temperature. The magnetic parameters such as M_S, H_c, and M_r were found to decrease with the increase in zinc substitution. FTIR spectra of the Co_1−xZn_xFe₂O₄ with x varying from 0 to 1.0 in the range 400–4000 cm⁻¹ were reported. The spinel structure and the crystalline water adsorption of Co_1−xZn_xFe₂O₄ nanoparticles were studied by using FTIR.     

Absolute photoabsorption cross sections for H2O and D2O from λ 180–790 Å

Absolute photoabsorption cross sections for H₂O and D₂O have been measured photoelectrically from λλ 180 to 790 Å using synchrotron radiation. The cross sections increase smoothly with wavelength to ～λ610 Å, with both H₂O and D₂O displaying a broad absorption band extending above a nearly linear background from λλ 400 to 490 Å. The continuum has a maximum of ～ 22.5 Mb at λ 640 Å. Above λ 615 Å, superimposed on the continuum, a diffuse structure appears which is similar to the vibrational structure of the ²B₂ states of H₂O⁺ and D₂O⁺ as observed in photoelectron spectra. The structure is believed to arise from excitation of a 1b₂ electron to the vibrational levels of a Rydberg orbital with n¹ ≈ 2.64.