Solute-diffusion-controlled dislocation creep in pure aluminium containing 0.026 at.% Fe

Pure aluminium containing about 200?at.ppm Fe in solution is shown to creep about 10⁶ times slower at 200°C than the same aluminium containing a negligible amount of iron in solution. The high creep resistance of the Al–200?at.ppm?Fe alloy is attributed to the presence of subgrain boundaries containing iron solute atoms. It is proposed that the opposing stress fields from subgrain boundaries and from the piled-up dislocations during creep are cyclically relaxed, by iron solute diffusion, to allow climb of the lead dislocation in the pile-up. The mechanism is a form of mechanical ratcheting. The model is applied to Al–Fe alloys and correctly predicts that the creep rate is controlled by the rate of iron solute diffusion and by a temperature dependence equal to the activation energy for iron diffusion, namely Q _c?=?221?kJ?mol^?1. Basic creep studies on solid-solution alloying with solute atoms that diffuse slowly in the lattice of aluminium (e.g. manganese, chromium, titanium and vanadium) appear worthy of study as a way of enhancing creep strength and of understanding creep mechanisms involving solute-atom-containing subgrain boundaries.     

Self-diffusion in α-Fe2O3 natural single crystals

Measurements of¹⁸O self-diffusion in hematite (Fe₂O₃) natural single crystals have been carried out as a function of temperature at constant partial pressure a_{O 2}=6.5·10^?2 in the temperature range 890 to 1227 °C. The a_{O 2} dependence of the oxygen self-diffusion coefficient at fixed temperature T=1150 °C has also been deduced in the a_{O 2} range 4.5·10^?4 - 6.5·10^?1. The concentration profiles were established by secondary-ion mass spectrometry; several profiles exhibit curvatures or long tails; volume diffusion coefficients were computed from the first part of the profiles using a solution taking into account the evaporation and the exchange at the surface. The results are well described by $$D_O \left( {{{cm^2 } \mathord{\left/ {\vphantom {{cm^2 } s}} \right. \kern-\nulldelimiterspace} s}} \right) = 2.7 \cdot 10^8 a_{O_2 }^{ - 0.26} \exp \left( { - \frac{{542\left( {{{kJ} \mathord{\left/ {\vphantom {{kJ} {mol}}} \right. \kern-\nulldelimiterspace} {mol}}} \right)}}{{RT}}} \right)$$ From fitting a grain boundary diffusion solution to the profile tails, the oxygen self-diffusion coefficient in sub-boundaries has been deduced. They are well described by $$D''_O \left( {{{cm^2 } \mathord{\left/ {\vphantom {{cm^2 } s}} \right. \kern-\nulldelimiterspace} s}} \right) = 3.2 \cdot 10^{25} a_{O_2 }^{ - 0.4} \exp \left( { - \frac{{911\left( {{{kJ} \mathord{\left/ {\vphantom {{kJ} {mol}}} \right. \kern-\nulldelimiterspace} {mol}}} \right)}}{{RT}}} \right)$$ Experiments performed introducing simultaneously¹⁸O and⁵⁷Fe provided comparative values of the self-diffusion coefficients in volume: iron is slower than oxygen in this system showing that the concentrations of atomic point defects in the iron sublattice are lower than the concentrations of atomic point defects in the oxygen sublattice. The iron self-diffusion values obtained at T>940 °C can be described by $$D_{Fe} \left( {{{cm^2 } \mathord{\left/ {\vphantom {{cm^2 } s}} \right. \kern-\nulldelimiterspace} s}} \right) = 9.2 \cdot 10^{10} a_{O_2 }^{ - 0.56} \exp \left( { - \frac{{578\left( {{{kJ} \mathord{\left/ {\vphantom {{kJ} {mol}}} \right. \kern-\nulldelimiterspace} {mol}}} \right)}}{{RT}}} \right)$$ The exponent - 1/4 observed for the oxygen activity dependence of the oxygen self-diffusion in the bulk has been interpreted considering that singly charged oxygen vacancies V _O ^? are involved in the oxygen diffusion mechanism. Oxygen activity dependence of iron self-diffusion is not known accurately but the best agreement with the point defect population model is obtained considering that iron self-diffusion occurs both via neutral interstitals Fe _x ⁱ and charged ones.     

Rapid nickel diffusion in cold-worked carbon steel at 320–450 °C

The diffusion coefficient of nickel in cold-worked carbon steel was determined with the diffusion couple method in the temperature range between 320 and 450 °C. Diffusion couple was prepared by electro-less nickel plating on the surface of a 20% cold-worked carbon steel. The growth in width of the interdiffusion zone was proportional to the square root of diffusion time to 12,000 h. The diffusion coefficient (D_Ni) of nickel in cold-worked carbon steel was determined by extrapolating the concentration-dependent interdiffusion coefficient to 0% of nickel. The temperature dependence of D_Ni is expressed by D_Ni = (4.5 + 5.7/?2.5) × 10^?11 exp (?146 ± 4 kJ mol^?1/RT) m²s^?1. The value of D_Ni at 320 °C is four orders of magnitude higher than the lattice diffusion coefficient of nickel in iron. The activation energy 146 kJ mol^?1 is 54% of the activation energy 270.4 kJ mol^?1 for lattice diffusion of nickel in the ferromagnetic state iron.     

Diffusion of chromium and manganese in γ-TiAl

The γ-TiAl intermetallic compound with suitable alloying additions has shown considerable promise as a material for high-temperature applications. Diffusion studies in this alloy system are useful in assessment of their creep behaviour and structural stability in service conditions. Tracer diffusion coefficients of ⁵¹Cr and ⁵⁴Mn in a γ-TiAl intermetallic compound containing 54.1 at. % aluminium were determined in the temperature range from 1095 to 1470?K. The temperature dependence of both the diffusing species follows a linear Arrhenius behaviour and can be expressed as D _Cr?=?4.4?×?10^?3exp(?350?kJ?mol^?1/RT)?m^2?s^?1 and D _Mn?=?1.2?×?10^?3?×exp(?326?kJ?mol^?1/RT)?m^2?s^?1. The data are analysed on the basis of empirical correlations between the diffusion and melting parameters applicable for conventional mono-vacancy diffusion mechanism in metals. It is concluded that impurity diffusion in γ-TiAl occurs through the migration of thermal vacancies via nearest-neighbour or next-nearest neighbour jumps.     

Enthalpies of formation and isomerization of cis‐ and trans‐decalin,and their oxa‐analogs by G3(MP2)//B3LYP calculations

G3(MP2)//B3LYP calculations have been carried out on trans‐ and cis‐decalin, and their mono‐, di‐, tri‐, and tetraoxa‐analogs. The main purpose of the work was to obtain enthalpies of formation for these compounds, and to study the relative stabilities of the cis–trans and positional isomers of the various (poly)oxadecalins. Comparison of the computational enthalpies of formation with the respective experimental ones, known only for the decalins and 1,3,5,7‐tetraoxadecalins, shows that in both cases the computational values are more negative than the experimental ones, the deviations being ?5 to ?7 kJ mol^?1 for the decalins and ?12 to ?17 kJ mol^?1 for the 1,3,5,7‐tetraoxadecalins. The respective computational enthalpies of cis–trans isomerization, however, are in excellent to satisfactory agreement with the experimental data. The cis–trans enthalpy differences vary from +11.0 kJ mol^?1 for decalin to ?15.4 kJ mol^?1 for 1,4,5,8‐tetraoxadecalin. Low relative enthalpy values were also calculated for the cis isomers of 1,8‐dioxadecalin (?3.7 kJ mol^?1), 1,3,6‐trioxadecalin (?4.6 kJ mol^?1), 1,3,8‐trioxadecalin (?9.7 kJ mol^?1), 1,4,5‐ trioxadecalin (?5.6 kJ mol^?1), 1,3,5,8‐tetraoxadecalin (?7.3 kJ mol^?1), and 1,3,6,8‐tetraoxadecalin (?14.5 kJ mol^?1). Copyright © 2009 John Wiley & Sons, Ltd.     

1H NMR Studies of 1-Ethylimidazole Binding to Cytochrome C

Abstract

Kinetic and equilibrium data for 1-EtIm binding to cyt c at temperature range of 303–319K have been determined at pH 7.0 by using ¹HNMR method. Thermodynamic values (ΔH°=39.5 kJ mol^?1, ΔS° = 154 J mol^?1K^?1 and Ea = 142 kJ mol^?1) are obtained from Van't Hoff and Arrhenius's relations. Some hyperfine shifted resonances of l-EtIm cyt c have been assigned for the first time using 1D saturation transfer experiments. The origin of the asymmetric spin density distribution in heme groups of 1-EtIm cyt c and the reason of low affinity of cytochrome c for 1-EtIm are also discussed move toward upfield from original position. However, Te-2, 4 substituents in cyt c are more electron withdrawing than the propionic acid side chains, which lead to the 5-methyl group going toward downfield.     

Diffusional transport in manganous sulphide

Using a novel diffusion-evaporation method, the self-diffusion coefficient of manganese in manganous sulphide has been determined as a function of temperature (1073–1373 K) in equilibrium with the metallic phase. It has been shown that the activation energy of this process at constant sulphur activity amounts to 269 kJ/mol and the self-diffusion coefficient is the following function of temperature and sulphur vapour pressure: . Diffusion of Mn²⁺ cations in Mn_1+yS proceeds via the interstitialcy mechanism and the activation enthalpy of successive jumps of these defects, δH_m is equal to 118 kJ/mol. It has been demonstrated that the mobility of interstitial cations in the Mn_1+yS lattice does not depend on their concentration and the diffusion coefficient of these defects has the following function of temperature: D_i=0.759 exp(-118 kJ/mol/RT).     

Ferrimagnetic transition in Fe0.9S: Magnetic,thermodynamic and kinetic aspects

Antiferromagnetic Fe_0.9S forms a ferrimagnetic superlattice in a narrow temperature range centred at 475 K (γ-transition). We have made a study in single crystals by specific heat, Mössbauer spectroscopy and magnetic susceptibility of the magnetic structure and kinetics and thermodynamics of formation of the ferrimagnetic component.The antiferromagnetic alignment and the spontaneous moment lie in the c-plane. The magnetic anisotropy energy is of the order of 0.4 K per Fe ion. Above 475 K and below T_N ≈ 598 K there is a change in ordering of the vacancies and a new antiferromagnetic structure is formed. At lower temperatures our value (100 kJ mol^?1) of the activation energy of diffusion of iron vacancies, determined from magnetic susceptibility, is in quite good agreement with the value (88 kJ mol^?1) obtained from radiotracer measurements by Condit et al.     

Infrared Study of the Hydrogen Bond Complexes Between N-Methylsuccinimide and Phenols

Abstract

The hydrogen bonded complexes between N-methylsuccinimide and phenols (pKa = 10.2 → 6) are investigated by infrared spectrometry. The thermodynamic parameters for the 1–1 complexes are determined in carbon tetrachloride-. The formation constants at 298 K range from 15 to 150 dm³ mol^?1, the enthalpies of complex formation from - 20 to - 30 kJ mol^?1, the changes of entropy from - 22 to - 40 J K^?1 mol^?1 and the frequency shifts of the v(OH) stretching vibration from 170 to 340 cm^?1. The complexes are weaker than those involving the monocarbonyl bases. The decrease of the force constant of the bonded carbonyl group ranges from 0.48 to 0.65 N cm^?1. The force constant of the free C=O group slightly increases upon complex formation, in agreement with the cooperatively theory.     

The energetics of naphthalene derivatives. II. The isomeric 1— and 2—naphthyl acetates

The isomeric 1- and 2-naphthyl acetates (acetoxynaphthalenes) are at the confluence of diverse concepts, techniques and classes of organic compounds. Summing the results of literature measurements of the enthalpy of formation of their solids and of our new sublimation enthalpies reported herein, we derive gas phase enthalpies of formation of ?209.9 ± 1.4 and ?213.3 ± 1.3 kJ mol^?1 respectively. This corresponds to 2-naphthyl acetate being more stable than its 1-isomer by 3.4 ± 1.9 kJ mol^?1. We also performed MP2(full)/6-31G(d) calculations on these species, resulting in enthalpies of formation of ?212.9 ± 3.9 and ?212.2 ± 3.9 kJ mol^?1 for 1- and 2-naphthyl acetate and a difference of ?0.7 kJ mol^?1 respectively in satisfactory agreement with the above experimental results.     

Phonon coupled cooperative low-spin 1A1high-spin 5T2 transition in [Fe(phen)2(NCS)2] and [Fe(phen)2(NCSe)2] crystals

Heat capacities of [Fe(phen)₂(NCS)₂] and [Fe(phen)₂(NCSe)₂] were measured between 13⁵ and 375 K. A heat capacity anomaly due to the spin-transition from low-spin ¹A₁ to high-spin π₂ electronic ground state was found at 176·29 K for the SCN-compound and at 231·26 K for the SeCN-compound, respectively. Enthalpy and entropy of transition were determined to be ΔH = 8·60 ± 0·14 kJ mol^?1 and ΔS = 48·78 ± 0·71 J K^?1 mol^?1 for the SCN-compound and ΔH = 11·60 ± 0·44 kJ mol^?1 and ΔS = 51·22 ± 2·33 J K^?1 mol^?1 for the SeCN-compound. To account for much larger value of ΔS compared with the magnetic contribution, we suggest that there is significant coupling between electronic state and phonon system. We also present a phenomenological theory based on heterophase fluctuation. Gross aspects of magnetic, spectroscopic, and thermal behaviors were satisfactorily accounted for by this model. To examine closely the transition process, infrared spectra were recorded as a function of temperature in the range 4000 ? 30 cm^?1. The spectra revealed clearly the coexistence of the ¹A₁, and the ⁵T₂ ground states around T_c.     

Mass spectrometric and ab initio study of the interaction between 9-methylguanine and amino acid amide group

The temperature dependent field ionization mass spectrometry method combined with ab initio calculations was used to determine the interaction energies and the structures of 9-methylguanine-acrylamide dimers. Acrylamide mimics the side chain amide group of the natural amino acids asparagine and glutamine. The experimental enthalpy of the dimer formation derived from the van't Hoff plot is ?59.5 ± 3.8 kJ mol^?1. The value is higher than interaction energies between acrylamide and other nucleic acid bases which were determined to be ?57.0 for 1-methylcytosine, ?52.0 for 9-methyladenine, and ?40.6 kJ mol^?1 for 1-methyl-uracil. In total, eight hydrogen bonded dimers formed by the three lowest energy 9-methylguanine tautomers and acrylamide were found in the quantum chemical calculations performed at the DFT/B3LYP/6-31++G?? and MP2/6-31++G?? levels of theory. The relative stability and the interaction energies of the dimers were calculated accounting for the basis set superposition error and the zero-point vibrational energy correction. The lowest energy dimer found in the calculations is formed by acrylamide (Ac) with the keto tautomer of 9-methylguanine (Gk). It is stabilized by two intermolecular H bonds, C6=O(Gk) · · · H—N(Ac) and Nl—H(Gk) · · ·O(Ac), and it is more stable than the second lowest energy dimer by ≈ 25 kJ mol^?1. The calculated interaction energies of the lowest energy 9-methylguanine-acrylamide dimer are ?65.0 kJ mol^?1 and ?67.7 kJ mol^?1 at the MP2 and DFT levels of theory, respectively. The experimental enthalpy of the dimer formation is in good agreement with both the calculated interaction energies of the GkAc dimer and much higher than the interaction energies calculated for all other 9-methylguanine-acrylamide dimers. This proved that only one dimer was present in the experimental samples. To verify whether acrylamide is a good model of the amino acid-amide group, we performed direct calculations of the 9-methylguanine-glutamine dimers at the same levels of theory as used for the complexes involving acrylamide. The interaction energies found for the lowest energy 9-methylguanine-glutamine dimer are ?65.1 kJ mon^?1 (MP2/6-31++G??) and ?66.2 kJ mol^?1 (DFT/B3LYP/6-31++G??) and these values are very close (within 0.5 kJ mol^?1) to the interaction energies obtained for the 9-methylguanine-acrylamide dimers.     

Quasi-elastic neutron scattering of benzene in Na-mordenite

The rotational and translational dynamics of benzene adsorbed in Na-mordenite have been studied by incoherent quasi-elastic neutron scattering. The measurements were performed at two benzene coverages at 300, 400 and 450 K. The observed quasi-elastic broadenings are described by a uniaxial rotational model about the six-fold axis of benzene. The mean time between successive jumps, at 300 K, is τ=1.45 × 10^?12 s at low coverage and 2.05×10^?12 s at high coverage. The correlation times follow an Arrhenius law with E_A=4.51 kJ mol^?1, at both coverages. The translational diffusion coefficient has been measured at 300 K and was found to be 0.67 × 10^?6 cm²s^?1.     

Experimental determination of U diffusion in α-Ti

α-spectrometry was used in order to measure the diffusion of U in bulk α-Ti in the temperature range 863–1123?K (540–850?°C). A straight Arrhenius plot was found, giving diffusion parameters Q?=?297?kJ/mol and D ₀?=?5?×?10^?3?m²/s, which are similar to the α-Ti self-diffusion ones, when measured in Ti samples with a similar impurity content than presently. This behaviour is compatible with the hypothesis of U diffusing via a vacancy-assisted mechanism in the α-Ti lattice and contrasts with older results in which the activation energy is almost a third the self-diffusion one, even lower than the vacancy formation energy.     

Hardening and thermal stability of nanocrystalline AlMg4.8 powder

Ball milled nanocrystalline AlMg4.8 powder was investigated in terms of hardening and thermal stability. The validity of the Hall–Petch relation was confirmed down to the minimum grain size of ～44 nm. Prolonged milling in the range of the minimum grain size still increased the hardness. This development is discussed in terms of contamination effects and the influence of full and partial dislocations. Concerning thermal stability, recovery processes occur in the range of 100–230°C, whereas substantial grain growth starts at a temperature of ～250°C. The enthalpy release for recovery was detected to be ～39 J mol^?1 and ～208 J mol^?1 for grain growth. Dynamic strain ageing was indicated by an activation energy for recovery of Q?～?120 kJ mol^?1. The activation energy of grain growth was calculated by means of the Kissinger theory (Q?=?200–210 kJ mol^?1) and using the results of static grain growth (Q?=?204 kJ mol^?1).     

High pressure 17O NMR study of solvent exchange on square planar complexes: Water exchange on [Pd(dien)H2O]2+

Abstract

The water exchange reaction of [Pd(dien)H₂O]²⁺ (dien = diethylenetriamine) was studied as function of temperature (268-308 K) and pressure 0.1-197 MPa) using ₁₇O NMR techniques. The rate and activation parameters are: k_cx = 5100 s^?1 at 298 K; ΔH^# =38 kJ mol^?1; ΔS^# = -47 JK^?1 mol^?1; ΔV^# = -2.8 cm³ mol^?1 at 296 K. The results are discussed in reference to solvent exchange data for other Pt(II) and Pd(II) complexes, and are interpreted in terms of an associatively activated substitution process.     

Kinetic performance of Li4Ti5O12 anode material synthesized by the solid-state method

Li₄Ti₅O₁₂ anode was successfully synthesized by solid-state method. X-ray diffraction and scanning electron micrographs show that Li₄Ti₅O₁₂ prepared by solid-state method has a purity phase with a uniform particle size in the range of 0.5?C1???m. Cyclic voltammogram reveals that there is a big irreversible capacity for the first cycle. Li₄Ti₅O₁₂ shows a stable cycling stability at 1?C rate. After 152 cycles, the discharge capacity is 213?mAh?g^?1, which keeps 93% of it at the second cycle. Electrochemical impedance spectroscopy shows that the resistance of charge-transfer of Li₄Ti₅O₁₂ electrode decreased with increasing the storage temperatures, and the lithium diffusion coefficient is increased with increasing the storage temperatures, revealing that the kinetics of Li⁺ and electron transfer into the electrodes were much faster at high temperature than that at low temperature. The apparent activation energy of the charge transfer and lithium diffusion can be calculated to be 33.1 and 27.3?kJ?mol^?1, respectively.     

Effect of surface roughness on the development of protective Al2O3 on Fe-10Al (at.%) alloys containing 0-10 at.% Cr

The effect of alloy surface roughness, achieved by different degrees of surface polishing, on the development of protective alumina layer on Fe-10 at.% Al alloys containing 0, 5, and 10 at.% Cr was investigated during oxidation at 1000 °C in 0.1 MPa oxygen. For alloys that are not strong Al₂O₃ formers (Fe-10Al and Fe-5Cr-10Al), the rougher surfaces increased Fe incorporation into the overall surface layer. On the Fe-10Al, more iron oxides were formed in a uniform layer of mixed aluminum- and iron-oxides since the layer was thicker. On the Fe-5Cr-10Al, more iron-rich nodules developed on an otherwise thin Al₂O₃ surface layer. These nodules nucleated preferentially along surface scratch marks but not on alloy grain boundaries. For the strong Al₂O₃-forming Fe-10Cr-10Al alloy, protective alumina surface layers were observed regardless of the surface roughness. These results indicate that the formation of a protective Al₂O₃ layer on Fe-Cr-Al surfaces is not dictated by Al diffusion to the surface. More cold-worked surfaces caused an enhanced Fe diffusion, hence produced more Fe-rich oxides during the early stage of oxidation.     

Self-diffusion in a series of plastic organic solids studied by NMR

Proton nuclear magnetic resonance relaxation times and linewidth measurements have been made on five polycrystalline organic compounds, triethylenediamine, 3-azabicyclononane, norbornane, norbornylene and norbornadiene. Measurements for each sample were made throughout the plastic crystal phase. The results are analysed in terms of molecular motion. Correlation times τ and activation enthalpies for translational self-diffusion of molecules are evaluated: triethylenediamine τ=7·6×10^?19 exp (96·4/RT)s, 3-azabicyclononane τ=1·7×10^?16 exp (83·6/RT)s, norbornane for 131K<T<306 K, τ=4·6×10^?15 exp (54·5/RT)s for 306K<T<360K, τ=1·1×10^?16 exp (64·8/RT)s, norbornylene, τ=4·×10^?15 exp (48·6/RT)s and norbornadiene τ=6·8×10^?15 exp (39·9/RT)s, where R is the gas constant in units of kJ K^?1mol^?1. The results and mechanism of diffusion are discussed in relation to the thermodynamic properties of the materials.     

Hydrogen and deuterium diffusion in non-stoichiometric spinel

High pressure/temperature annealing experiments are used to determine diffusivities of H⁺ and D⁺ in non-stoichiometric spinel, a low-pressure analogue for nominally anhydrous minerals in Earth’s mantle. Data are fitted to the following Arrhenius law: Diffusivity (m²/s)?=?4?±?1?×?10^?12 exp(?54?±?2 kJ?mol^?1/RT). At low temperatures, H⁺ and D⁺ diffusion in non-stoichiometric spinel is charge balanced by flux of O vacancies, with infrared data consistent with protonation of both octahedral and tetrahedral O–O edges in non-stoichiometric spinel, and additional fine structure due to Mg–Al mixing and/or coupling of structurally incorporated H⁺ with cation vacancies. Absence of changes in the fine structure of O–H absorption bands indicates that H⁺ can become locally coupled and uncoupled to other defects during bulk diffusion. As such, proton conductivity in spinel group minerals, arising from faster flux of uncoupled H⁺, can only be calculated from H⁺ mobility data if the extent of defect coupling is constrained.