Softening and hardening of yield stress by hydrogen–solute interactions

Abstract

Hydrogen atoms have a wide variety of effects on the mechanical performance of metals, and the underlying mechanisms associated with effects on plastic flow and embrittlement remain to be discovered or validated. Here, the reduction in the plastic flow stress (softening) due to hydrogen atoms in solute-strengthened metals, previously proposed by Sofronis et al. is demonstrated at the atomistic level. Glide of an edge dislocation through a field of solutes in a nickel matrix, both in the absence of hydrogen and in the presence of H bound to the solutes, is modelled. The ‘solutes’ here are represented by vacancies, enabling use of accurate binary Ni–H interatomic potentials. Since vacancies have a misfit strain tensor in the Ni matrix and also bind hydrogen atoms, they are excellent surrogates for study of the general phenomenon. The binding of H to the solute (vacancy) reduces the misfit volume to nearly zero but also creates a non-zero tetragonal distortion. Solute strengthening theory is used to establish the connection between strength and solute/hydrogen concentration and misfit strain tensor. Simulations show that when a dislocation moves through a field of random vacancy ‘solutes’, the glide stress is reduced (softening) when H is bound to the solutes. Trends in the simulations are consistent with theory predictions. Trends of softening or hardening by H in metal alloys can thus be made by computing the misfit strain tensor for a desired solute in the chosen matrix with and without bound hydrogen atoms. Pursuing this, density functional theory calculations of the interaction of H with carbon and sulphur solutes in a Ni matrix are presented. These solutes/impurities do not bind with H and the complexes have larger misfit strains, indicative of H-induced strengthening rather than softening for these cases. Nonetheless, H/solute interactions are the only mechanism, to date, that shows nanoscale evidence of plastic softening due to hydrogen associated with the hydrogen-enhanced localised plasticity concept in fcc metals.     

A TD-DFT study on the hydrogen bonding of three esculetin complexes in electronically excited states: strengthening and weakening

Time-dependent density functional theory (TD-DFT) method was used to study the excited-state hydrogen bonding of three esculetin complexes formed with aprotic solvents. The geometric structures, molecular orbitals (MOs), electronic spectra and the infrared (IR) spectra of the three doubly hydrogen-bonded complexes formed by esculetin and aprotic solvents dimethylsulfoxide (DMSO), tetrahyrofuran (THF) and acetonitrile (ACN) in both ground state S(0) and the first singlet excited state S(1) were calculated by the combined DFT and TD-DFT methods with the COSMO solvation model. Two intermolecular hydrogen bonds can be formed between esculetin and the aprotic solvent in each hydrogen-bonded complex. Based on the calculated bond lengths of the hydrogen bonds and the groups involved in the formation of the intermolecular hydrogen bonds in different electronic states, it is demonstrated that one of the two hydrogen bonds formed in each hydrogen-bonded complex is strengthened while the other one is weakened upon photoexcitation. Furthermore, it is found that the strength of the intermolecular hydrogen bonds formed in the three complexes becomes weaker as the solvents change from DMSO, via THF, to ACN, which is suggested to be due to the decrease of the hydrogen bond accepting (HBA) ability of the solvents. The spectral shifts of the calculated IR spectra further confirm the strengthening and weakening of the intermolecular hydrogen bonds upon the electronic excitation. The variations of the intermolecular hydrogen bond strengths in both S(0) and S(1) states are proposed to be the main reasons for the gradual spectral shifts in the absorption and fluorescence spectra both theoretically and experimentally.     

Theoretical and experimental investigations on migration behavior of weak monoprotic acids in continuous two‐dimensional ion exchange/reversed phase CEC

A continuous 2D ion exchange/RP CEC system was constructed in this report and retention characteristics of weak monoprotic acids in the column were investigated theoretically. The transport equations were deduced for predicting migration behavior of weak monoportic acids based on mixing model combining ion exchange, RP, and electrophoretic separation mechanism. The influences of separation voltage, length of capillary, pH value, and ionic strength of buffer and concentration of organic modifier in mobile phase on the separation were well described by the equations. It was verified that the migration rate of solute was linearly related to voltage in the case of lower voltage, decreased with the increase of the first‐dimensional length, and . The retention time of solute increased with enhancing ionic strength and concentration of organic modifier. These theoretical results were all demonstrated by the relevant experiments. The relevant application was performed for the aqueous extract of Rhizoma gastrodiae, showing the obvious potential in method development for the analysis of complex samples.     

土壤水流与溶质耦合运移问题的混合元-迎风广义差分法研究

本文研究了一维非饱和土壤水流与溶质耦合运移问题的数学模型, 建立了求其数值解的守恒混合元-迎风广义差分格式. 对非线性土壤水分入渗方程, 采用守恒混合元法进行离散模拟, 同时得到了土壤含水量和水分通量; 而对对流-扩散形式的溶质运移方程, 利用迎风的广义差分法离散求解. 且分析了解的存在唯一性, 并讨论了误差估计. 最后给出数值算例, 模拟结果表明利用本文格式来求解非饱和土壤水流与溶质耦合运移问题是可靠的, 且该格式具有稳定性和可实用性.     

玻璃质光学元件表面微裂纹的研究

研究了影响玻璃质光学元件表面质量的主要因素,认为表面微裂纹是表面强度改变的主要原因。用机械磨削初成形工艺方法分析研究了表面微裂纹产生的原因;通过裂纹尖端应力集中及Griffith能量平衡理论,分析了裂纹扩展方式;结合表面结构缺陷理论及研磨处理表面微缺陷工艺,阐述了HF腐蚀法对微裂纹的去除机理及效果;最后,综述了通过生产工艺提高玻璃强度的方法,重点讨论了离子交换法,镀膜法和HF腐蚀法等表面处理技术,指出使用HF腐蚀法去除表面微裂纹更适用于玻璃质光学元件的表面加工。     

Optimization Models for Forest Road Upgrade Planning

Road blocking due to thawing or heavy rains annually contribute to a considerable loss in Swedish forestry. Companies are forced to build up large stocks of raw material (saw and pulp logs) in order to secure a continuous supply when access to the road network is uncertain. Storage outdoors leads to quality deterioration and monetary losses. Other related costs due to road blocking are road damage and longer haulage distances. One approach to reduce the losses due to road blocks is to upgrade the road network to a standard that guarantees accessibility. We consider the road upgrade problem from the perspective of Swedish forest companies with a planning horizon of about one decade. The objective is to minimize the combined upgrade and transportation costs. We present two mixed integer programming models, which are uncapacitated fixed charge network flow problems including multiple assortments, several time periods and a set of road classes. One model is based on arc flows and one on route flows. For a typical planning instance, the models become large and we propose how to improve solution performance through model strengthening. The models are tested in a case study for a major Swedish forest company.      

Comparative study of some commercial chemically bonded phases in classical reversed-phase chromatography and in ion-pair reversed-phase liquid chromatography

Summary The behaviour of various octadecyl commercial bonded phases are compared in classical reversed-phase chromatography and in ion-pair reversed-phase chromatography. Great differences are exhibited by the packings studied according to the polarity of the solutes. Whereas hydrocarbonaceous bonded phases show very similar selectivity versus apolar or weakly polar solutes, great differences are observed when analyzing more polar solutes even when ion-pair reversed-phase chromatography is performed.Presented at the 14th International Symposium on Chromatography London, September, 1982     

界面不稳定现象与相间迁移

包含有流动界面的多相体系中的溶质相间迁移在一定条件下可导致表现为界面变形、界面流和多种形式界面运动的不稳定现象．该现象的直接驱动力是界面局部区域出现的张力梯度，表面活性物质在该现象中起重要作用[1，2]．溶质相间迁移通常可考虑为三步：（1）溶质在原所在相内部向     

Threshold temperatures for solute mobility. Their determination and effect on programmed temperature gas chromatographic separations

The threshold temperature for solute mobility is defined as that temperature at which a solute band, which was initially cold trapped at the head of the column, begins moving through the column. It is shown that the separation of compounds by programmed temperature gas Chromatography (PTGC) occurs primarily at the head of the column as a result of differences in threshold temperatures. Additional column length beyoud that needed to trap the compounds improves resolution, primarily by delaying emergence (while maintaining the temperature and time spacing) thus allowing the column temperature to rise, the solute terminal velocities to increase, and narrower peak widths to be recorded. For maximum resolution in minimum analysis time, the initial temperature must be at or below the threshold temperature of the most volatile compound in the mixture to be separated. Three methods for determining threshold temperatures are presented.