XPS study of Cr segregation in a martensitic stainless steel

Cr martensitic steels are promising materials for structural applications in future nuclear fusion reactors. Because the embrittlement after tempering treatments can be a serious problem, the fracture mode of a steel with 10.5 wt% of Cr treated at 700°C for 18 h has been investigated through Charpy tests in the temperature range from −100°C to +150°C. X-ray photoelectron spectroscopy (XPS) analyses carried out on the fracture surfaces evidenced the segregation of Cr in both ductile and brittle (quasicleavage) fields. The unexpected result indicates that Cr segregation weakens the atomic bonds; thus, the fracture path in both the cases corresponds to the zones with higher Cr content.     

基于FeWOx/SiO2载氧体的甲烷化学链部分氧化反应

甲烷具有价格低廉且储量丰富的优点,因此将甲烷转化为合成气(一种H2:CO为2的混合物),从而进一步合成有价值的化学品和液体燃料引起了人们的极大关注.化学链甲烷部分氧化(CLPOM)技术能避免甲烷与空气直接接触而引起爆炸的危险,可以降低后续对合成气与氮气分离操作所带来的费用,因此日益受到关注.CLOPM过程主要分为两步:第一步,CH4被载氧体所携带的氧部分氧化,载氧体被还原;第二步,利用氧化剂(例如空气)将被还原的载氧体再氧化恢复.因此,载氧体在CLOPM过程中起到至关重要的作用.载氧体的选择主要存在两个问题:(1)甲烷被活化所产生含碳产物的能力与晶格氧的给氧能力不匹配所带来的严重碳沉积;(2)金属离子间扩散速率不匹配而造成载氧体在氧化还原过程中结构的不可逆变化.基于上述两个问题,本文设计了FeWOx/SiO2载氧体用于CLPOM.与未改性的WO3/SiO2载氧体相比,甲烷的转化率和合成气的收率都有显著提高.FeWOx/SiO2在900℃、1 atm反应条件下表现出62%的甲烷转化率、93%的CO气相选择性、94%的H2选择性和2.4的H2/CO比值,同时在50个循环中表现出优异的催化活性和稳定性.本工作利用CH4脉冲反应研究了FeWOx/SiO2的甲烷表面反应过程;采用CH4-TPR和H2-TPR相结合探究了甲烷活化速率与晶格氧扩散速率之间的关系;通过XPS和XRD对FeWOx/SiO2在氧化还原过程中的结构稳定性进行了探讨.综合上述实验结果,对FeWOx/SiO2应用于CLPOM的反应机理进行了阐述.H2-TPR结果表明,在FeWOx/SiO2中,相较于Fe2O3/SiO2,Fe-O的活性受到抑制,使其更倾向于与甲烷发生部分氧化反应;相较于WO3/SiO2,W-O的活性得到明显提升,因此更多的晶格氧可以参与到部分氧化反应中来氧化积碳,从而使合成气收率大幅度提升.从CH4-TPR结果可以看出,对于FeWOx/SiO2,CO与H2的生成温度最接近,意味着晶格氧的传输速率较快并且能够与甲烷活化产生含碳中间物种的速率相匹配,将其及时氧化生成CO,避免由于积碳造成的催化剂失活.结合XPS和XRD结果可以得出,在甲烷还原过程中,FeWOx经历一步还原形成Fe-W合金,由于其间存在强相互作用,因而抑制了还原过程中催化剂相分离现象的发生.同时,根据铁钨离子在空气条件下扩散速率的公式计算可以得出,其相近的离子氧化速率也保证了在氧化过程中催化剂结构的稳定性.本工作为进一步构建用于甲烷化学链部分氧化制合成气的复合金属氧化物载氧体提供了研究思路.     

回转窑多粒径颗粒流动与偏析的DEM模拟与实验研究

为明晰回转窑内颗粒的运动行为及偏析机理,以绿豆、黄豆和黑豆为颗粒介质,依次对3种装填顺序下的颗粒流动过程进行离散元模拟与实验研究,以颗粒质量分数和平均粒度为判据,对颗粒偏析进行评价。结果表明,回转窑内颗粒流动区可分为自由滚落区、渗流呆滞区以及窑壁携带区,自由滚落区颗粒流速最大,而渗流呆滞区流速最小。窑内颗粒沿轴向输运过程发生径向偏析,形成夹层结构,小颗粒受渗流作用在渗流呆滞区中心形成内核,大粒径和中等粒径颗粒集中在自由滚落区和窑壁携带区。窑内颗粒力链分布不均匀,强力链分布于近窑壁区,弱力链分布于自由滚落区和渗流呆滞区,且渗流呆滞区力链细而密集。当窑头附近不同粒径颗粒存在轴向速度差时,颗粒在轴向发生掺混,并产生径向偏析。     

Incorporation of smooth spherical bodies in the Lattice Boltzmann method

A method to simulate bodies suspended in a Lattice Boltzmann solvent is proposed. It is based on a generalized reaction force that enforces no-slip boundary conditions at the fluid–body interface as the limiting case of an iterative procedure. A smooth version of the Heaviside function allows to treat spherical particles of arbitrary size and produces smooth hydrodynamic forces as particles move in the continuum. Numerical tests demonstrate the accuracy of the method in reproducing the hydrodynamic field around a single particle and the fluid-mediated forces between pairs of particles. The drag force experienced by a particle moving in a straight channel and at various Reynolds numbers is studied as a non-trivial testcase.     

Linear stability analysis of a boundary crisis in a minimal chaotic flow

We present a mechanism that explains the boundary crisis presented by the first Malasoma class P minimal chaotic flow, which is equivalent to the simplest Sprott flow. The treatment followed resorts to the existence of two invariant sets of points of the flow, in addition to the chaotic attractor, to which linear stability theory is applied.     

The Kalman condition for the boundary controllability of coupled parabolic systems. Bounds on biorthogonal families to complex matrix exponentials

This paper is devoted to prove the controllability to trajectories of a system of n one-dimensional parabolic equations when the control is exerted on a part of the boundary by means of m controls. We give a general Kalman condition (necessary and sufficient) and also present a construction and sharp estimates of a biorthogonal family in L²(0,T;C) to {tje−Λkt}.     

Prediction of binary interaction coefficients in grain boundary segregation

A simple semiempirical method is proposed for prediction of the values of the binary interaction coefficients in grain boundary segregation (Fowler interaction). The method is based on the volume solid solubility, the maximum possible concentration of the solute at the grain boundary, and an additional parameter that represents an activity exponent of both the solute and the host metal. Values of the interaction coefficients for numerous solutes in α‐iron are predicted. The comparison with available literature data shows reasonable agreement.     

Piecewise shooting reproducing kernel method for linear singularly perturbed boundary value problems

In this letter, a new numerical method is proposed for solving second order linear singularly perturbed boundary value problems with left layers. Firstly a piecewise reproducing kernel method is proposed for second order linear singularly perturbed initial value problems. By combining the method and the shooting method, an effective numerical method is then proposed for solving second order linear singularly perturbed boundary value problems. Two numerical examples are used to show the effectiveness of the present method.     

Position calculation of the frequency band gap in the finite photonic crystal with multiple alternations using boundary element method

In this paper, the wave transmission from finite photonic crystals with multiple alternations is investigated using boundary element method (BEM). Since that, in these structures the alternation is not in all directions of space; the investigations of the frequency band gap with desired accuracy are not practical by analytical methods. Also, the frequency dispersion of dielectric rods is an effective parameter in photonic crystals, which this effect in our calculations has been considered. Due to the high capabilities of the BEM, the transmitted wave spectrum in the photonic crystal is calculated by changing the geometrical and optical parameters of the photonic crystal and applying more alternation in its structure and the position and width of the frequency band gap is investigated. Then, it is assumed that the photonic crystal with an arbitrary angle is rotated around the axis which is perpendicular on the crystal cross section and then, it is irradiated with a plan wave. The band gap of the photonic crystals with the desired structure, desired rotation angle and multiple alternations have been solved. Very low information volume, high speed and accuracy during the calculation and useable for any desired structures are the characteristics of this method.