Proton-induced grain boundary segregation in stainless steel

Abstract

A technique is developed which addresses the problem of irradiation assisted stress corrosion cracking of stainless steels in light water reactors using high energy protons to induce grain boundary segregation. These results represent the first grain boundary segregation measurements in bulk produced by proton irradiation of stainless steel. The technique allows the study of grain boundary composition with negligible sample activation, short irradiation time, rapid sample turnaround and at minimal cost. Scanning Auger electron microscopy is used to obtain grain boundary composition measurements of irradiated and unirradiated samples of ultra high purity (UHP) type 304L stainless steel and UHP type 304L steels with the additions of phosphorus (UHP + P) and sulphur (UHP + S). Results show that irradiation of all three alloys causes significant Ni segregation to the grain boundary and Cr and Fe away from it. Irradiation of the UHP + P alloy also results in segregation of P at the grain boundary from 5.3 to 8.7 at %, over 80 times the bulk value. No radiation-induced grain boundary segregation of S was measured in the UHP + S alloy. Results also indicate that the presence of P or S may enhance radiation-induced segregation of major alloying elements at the boundary. Comparison of irradiated and unirradiated regions of the UHP + P alloy indicate that while a prior thermal treatment segregates P to the grain boundary to 5.3 at %, the major element concentrations at the grain boundary are completely different from those under irradiation.     

Quantum Monte Carlo study of the CO interaction with a dimer model surface for Cr(110)

The chemisorption of CO on a Cr (110) surface is investigated using the quantum Monte Carlo method in the diffusion Monte Carlo (DMC) variant and a model Cr₂CO cluster. The present results are consistent with the earlier ab initio HF study with this model that showed the tilted/near-parallel orientation as energetically favoured over the perpendicular arrangement. The DMC energy difference between the two orientations is larger (1.9 eV) than that computed in the previous study. The distribution and reorganization of electrons during CO adsorption on the model surface are analysed using the topological electron localization function method that yields electron populations, charge transfer and clear insight on the chemical bonding that occurs with CO adsorption and dissociation on the model surface.     

Characterization of aromatic-thiol π-type hydrogen bonding and phenylalanine-cysteine side chain interactions through ab initio calculations and protein database analyses

In this study, the aromatic-thiol π hydrogen bonding and phenylalanine-cysteine side chain interactions are characterized through both molecular orbital calculations on a C₆H₆-HSCH₃ model complex and database analyses of 609 X-ray protein structures. The aromatic-thiol π hydrogen bonding interaction can achieve a stabilization energy of 2.60 kcal mol^?1, and is stronger than the already documented aromatic-hydroxyl and aromatic-amino hydrogen bonds. However, the occurrence of the aromatic-thiol hydrogen bond is rather rare in proteins. This is because most of the thiol groups participate in the formation of either disulphide bonds or stronger S—H…O (or N) ‘normal’ hydrogen bonds in a protein environment. Interactions between the side chains of phenylalanine and cysteine residues are characterized as the phenyl(Phe)(HSCH₂-)(Cys) interaction. The bonding energy for such interactions is approximately 3.71 kcal mol-¹ and is achieved in a geometric arrangement with an optimal phenyl(Phe)-(HS-)(Cys) π-type hydrogen bonding interaction. The interaction is very sensitive to the orientation of the two lone electron pairs on the sulphur atom relative to the π electron cloud of the phenyl ring. Accordingly, the interaction configurations that can accomplish a significant bonding energy exist only within a narrow configurational space. The database analysis of 609 experimental X-ray protein structures demonstrates that only 268 of the 1620 cysteine residues involve such phenylalanine-cysteine side chain interactions. Most of these interactions occur in the form of π (aromatic)-lone pair(sulphur) attractions, and correspond to a bonding energy less than 1.5 kcal mol^?1. A few were identified as the aromatic-thiol hydrogen bond with a bonding energy of 2.0–3.6 kcal mol^?1.     

Examples of the influence of the geometry on the propagation of progressive waves

In this paper, we give examples of the influence of the domain of propagation on progressive waves. More precisely, we numerically investigate the propagation of reaction diffusion waves in cylinders with variable radius. We show that, when the radius rapidly expands from a very small radius to a larger one, depending on the viscosity and the nonlinearity, the travelling wave may be blocked. The aim of this paper is to give numerical illustrations and quantifications of this effect, and to propose some conjectures which could be interesting subjects for further mathematical investigations.This work is linked to the study of spreading depression (SD), a propagative mechanism in brain and various tissues which has been observed in vivo and in vitro in many species since their discovery in 1944 by Leao. As a matter of fact, their direct observation in Man is still controversial. The complex structure of gray and white matter in humans may block the propagation of SD over large distances in brain and thus explain the difficulty of observing it. Medical consequences of the current numerical studies are detailed in [M.A. Dronne, et al., Influence of brain geometry on spreading depressions: A computationnal study, Progress in Biophysics and Molecular Biology 97 (1) (2008) 54–59] and a first mathematical approach given in [M.A. Dronne, E. Grenier, H. Gilquin, Modelization of spreading depressions following Nedergaard, preprint, 2003].     

Depth magnetization profile of a perpendicular exchange coupled system by soft-x-ray resonant magnetic reflectivity

The magnetic profile across the interface of a perpendicular exchange coupled [NiO/CoO]3/Pt-Co/Pt(111) system is investigated. The magneto-optic Kerr effect reveals a strong coupling between the antiferromagnetic (AFM) oxide and the ferromagnetic (FM) Pt-Co layer, by an increasing coercivity and a rotation of the easy magnetization axis of the FM layer along the AFM spins. Soft x-ray resonant magnetic reflectivity is used to probe the spatial distribution of the out-of-plane magnetization inside the oxide above its ordering temperature. It extends over 1 nm and exhibits a change of sign.     

Use of in situ Mössbauer spectroscopy for electrochemical reactions involving57Fe

An electrochemical cell and relevant electrodes have been carried out in order to study in situ various electrochemical reactions involving iron using⁵⁷Fe Mössbauer resonance. The electrochemical behaviour of iron in strongly alkaline solution (KOH 5N) in the potential range (?1200<E相似文献   

Boundary layers for parabolic regularizations of totally characteristic quasilinear parabolic equations

In this paper we study boundary layers of nonlinear characteristic parabolic equations as the viscosity goes to zero. We obtain and justify in small time a complete expansion of the solution with respect to the viscosity.     

A Non-linear Singular Perturbation Problem Arising in the Study of Chemical Flow Reactors

This paper presents a method of obtaining the complete asymptoticsolution of boundary value problems of the form for x [0,1] where b(x) is strictly positive andfor small and positive. Physically, the problem arises in determiningthe steady-state concentration of a substance in a chemicalflow reactor. A "two-variable" expansion procedure is used.     

DISTRIBUTIONS OF FREE RADICALS AMONG AMINO ACIDS FROM LYOPHILIZED ULTRAVIOLET-IRRADIATED PROTEINS

Abstract— The effects of u.v.-irradiation at 254 nm upon lyophilized ribonuclease, lysozyme, insulin, and chymotrypsinogen have been investigated by electron spin resonance (ESR). enzymatic assay, and labeling of free radical sites with tritiated hydrogen sulfide (HST). The ESR signal of the irradiated protein diminishes on exposure to HST, and tritium becomes covalently bound to carbon. The distribution of tritium among the amino acids of each protein. studied as an indicator of the carbon free radical distribution, differs markedly from those observed previously to result from exposure to gamma radiation, electrical discharge. or hydrogen atoms. However, the earlier observation that the tritium distribution is influenced by protein conformation holds true as well for u.v.-irradiation. Moreover, the distributions of tritium among the amino acids of u.v.-irradiated proteins indicate a broad scattering of free radicals. Tyrosine and phenylalanine, residues that absorb light energy in the region of the wavelength employed, are not particularly important as radical carriers. Thus, for ribonuclease, these residues incorporated 3.8 and 1.5 per cent of the total tritium, but they absorb 51 and 12 per cent of the light, respectively. These results, together with the observed low recoveries of methionine, an amino acid that does not absorb at 254 nm, add weight to the concept that a migration of energy ensues after the initial absorption of light energy and that photolytic damage may thus be due to destruction of amino acids other than those initially absorbing the u.v.-radiation.