Observation and computer simulation of multicomponent chemical short-range order (MCSRO) for the bulk metallic glasses

The atomic configuration of chemical short-range order (CSRO) for the Zr-base metallic glasses was investigated by using nano-diffraction and high resolution transmission electronic microscopy (HRTEM) technology with a beam size of 0.5 nm. It is il- lustrated that the pattern of atomic configuration of CSRO might have various compound counterparts because of the chemical inter- action of bonding atoms. Some atomic configuration of MCSRO is similar to the icosahedral structure with 10-fold symmetry of very weak spots. In deed, the nano-beam technology could clearly detect the evolution of atomic configuration in nanometer scale during the transformation from the metallic melt to the primary crystallization. The local atomic configuration of CSRO is also investigated by molecular dynamics simulation (MD) for the Zr2Ni compound in a wider temperature range. The CSRO in the melt could be pic- torially demonstrated as distorted coordination polyhedron of the compound structure and/or the structure similar to cubo-octahedron analogs. The MD simulation illustrates that the atomic packing of long-range order disappears just above the melting point, but the chemical interaction of bonding atoms still exists that leads to form the various CSRO with the atomic configuration similar to stable or metastable unit cell of Zr2Ni compound. The icosahedral polyhedron became more abundance as the overheating temperature was raised.

Prediction of chemical short-range order in high-/medium-entropy alloys

Chemical short-range orders(CSROs),as the built-in sub-nanoscale entities in a high-/medium-entropy alloy(H/MEA),have aroused an ever-increasing interest.With multi-principal elements in an H/MEA to form a complex concentrated solution,a variety of sub-systems of species exist to induce the metastable ordered compounds as candidates for ultimate CSROs.The issues remain pending on the origin of CSROs as to how to judge if CSRO will form in an H/MEA and particularly,what kind of CSROs would be stably produced if there were multiple possibilities.Here,the first-principles method,along with the proposed local formation energy calculation in allusion to the atomic-scale chemical heterogeneities,is used to predict the CSRO formation based on the mechanical stability,thermodynamic formation energy,and electronic characteristics.The simulations are detailed in an equiatomic ternary VCoNi MEA with three kinds of potential compounds,i.e.,L1_(1),L1_(2),and B2,in the face-centered cubic matrix.It turns out that L1_(1)is stable but hard to grow up so as to become the final CSRO.L1_(1)is further predicted as CSROs in CrCoNi,but unable to form in FeCoNi and CrMnFeCoNi alloys.These predictions are consistent with the experimental observations.Our findings shed light on understanding the formation of CSROs.This method is applicable to other H/MEAs to design and tailor CSROs by tuning chemical species/contents and thermal processing for high performance.

Chemical short-range orders in high-/medium-entropy alloys

High(or medium)-entropy alloys(H/MEAs)are complex concentrated solid solutions prone to develop the chemical short-range orders(CSROs),as an indispensable structural constituent to make H/MEAs essentially different from the traditional alloys.The CSROs are predicted to play roles in dislocation behaviors and mechanical properties.So far,the image of CSROs is built up by the theoretical modeling and computational simulations in terms of the conventional concept,i.e.,the preference/avoidance of elemental species to satisfy the short-ranged ordering in the first and the next couple of nearest-neighbor atomic shells.In these simulated CSROs,however,the structural image is missing on the atomic scale,even though the lattice periodicity does not exist in the CSROs.Further,it is pending as to the issues if and what kind of CSRO may be formed in a specific H/MEA.All these are ascribed to the challenge of experimentally seeing the CSROs.Until recently,the breakthrough does not appear to convincingly identify the CSROs in the H/MEAs by using the state-of-the-art transmission electron microscope.To be specific,the electron diffractions provide solid evidence to doubtlessly ascertain CSROs.The structure motif of CSROs is then constructed,showing both the lattice structure and species ordering occupation,along with the stereoscopic topography of the CSRO.It is suggested that the CSROs,as the first landscape along the path of development of the local chemical ordering,offer one more route to substantially develop the ordered structure on the atomic scale in the H/MEAs,parallel to the existing grain-leveled microstructure.The findings of CSROs make a step forward to understand the CSROs-oriented relationship between the microstructure and mechanical properties.This review focuses on the recent progress mainly in the experimental aspects of the identification,structure motif,and mechanical stability in CSROs,along with the chemical medium-range orders as the growing CSROs。

Characterization of local chemical ordering and deformation behavior in high entropy alloys by transmission electron microscopy

Short-range ordering(SRO)is one of the most important structural features of high entropy alloys(HEAs).However,the chemical and structural analyses of SROs are very difficult due to their small size,complexed compositions,and varied locations.Transmission electron microscopy(TEM)as well as its aberration correction techniques are powerful for characterizing SROs in these compositionally complex alloys.In this short communication,we summarized recent progresses regarding characterization of SROs using TEM in the field of HEAs.By using advanced TEM techniques,not only the existence of SROs was confirmed,but also the effect of SROs on the deformation mechanism was clarified.Moreover,the perspective related to application of TEM techniques in HEAs are also discussed.

The chemical environment and structural ordering in liquid Mg-Y-Zn system:An ab-initio molecular dynamics investigation of melt for the formation mechanism of LPSO structure

In an effort to clarify the formation mechanism of LPSO structure in Mg-Y-Zn alloy,the chemical environment and structural ordering in liquid Mg-rich Mg-Y-Zn system are investigated with the aid of ab-initio molecular dynamics simulation.In liquid Mg-rich Mg-Y alloys,the strong Mg-Y interaction is determined,which promotes the formation of fivefold symmetric local structure.For Mg-Zn alloys,the weak Mg-Zn interaction results in the fivefold symmetry weakening in the liquid structure.Due to the coexistence of Y and Zn,the strong attractive interaction is introduced in liquid Mg-Y-Zn ternary alloy,and contributes to the clustering of Mg,Y,Zn launched from Zn.What is more,the distribution of local structures becomes closer to that in pure Mg compared with that in binary Mg-Y and Mg-Zn alloys.These results should relate to the origins of the Y/Zn segregation zone and close-packed stacking mode in LPSO structure,which provides a new insight into the formation mechanism of LPSO structure at atomic level.

Chemical short-range order domain in bulk amorphous alloy and the prediction of glass forming ability

Short-range order domains of face central cubic Zr2Ni (F-Zr2Ni) and tetragonal Zr2Ni (T-Zr2Ni) type structure with a size about 1–3 nanometers were observed in bulk amorphous Zr52.5Cu17.9Ni14.6Al10Ti5 alloy by using HREM and nano-beam electron diffraction technique. A new thermodynamic model was formulated based on the concept of chemical short-range order (SCRO). The molar fractions of CSRO and thermodynamic properties in Ni?Zr, Cu?Zr, Al?Zr, Al?Ni, Zr?Ni?Al and Zr?Ni?Cu were calculated. According to the principle of maximum ΔG CSRO, the optimum glass forming ability (GFA) compositions were predicted in binary and ternary alloys. These results were proved to be valid by the experimental data of crystallizing activation energy, ΔT x and XRD patterns. The TTT curves of Zr?Ni?Cu alloys calculated based on CSRO model shows that the lowest critical cooling rate GFA is in the order of 100 K/s, which is close to the practical cooling rate for the preparation of Zr-based BMG alloys.

Chemically Radiative MHD Flow of a Micropolar Nanofluid over a Stretching/ Shrinking Sheet with a Heat Source or Sink

This study examines the behavior of a micropolar nanofluidflowing over a sheet in the presence of a transverse magneticfield and thermal effects.In addition,chemical(first-order homogeneous)reactions are taken into account.A similarity transformation is used to reduce the system of governing coupled non-linear partial differ-ential equations(PDEs),which account for the transport of mass,momentum,angular momentum,energy and species,to a set of non-linear ordinary differential equations(ODEs).The Runge-Kutta method along with shoot-ing method is used to solve them.The impact of several parameters is evaluated.It is shown that the micro-rota-tional velocity of thefluid rises with the micropolar factor.Moreover,the radiation parameter can have a remarkable influence on theflow and temperature profiles and on the angular momentum distribution.

Chemical short-range-order induced multiscale strengthening in refractory medium entropy alloys

High/medium entropy alloys(H/MEAs)are generally possible to exhibit chemical short-range order(SRO).However,the complex role of SRO on mechanical properties from nano-scale to meso-scale is still challenging so far.Here,we study the strengthening mechanism and deformation behavior in a model body-centered-cubic HfNbTa MEA by using atomic-scale molecular dynamics,micro-scale dislocation dynamics,and meso-scale crystal plasticity finite element.The SRO inhibits dislocation nucleation at the atomic scale,improving the flow stress.The SRO-induced ultrastrong local stress fluctuation greatly improves the micro-scale dislocation-based strength by the significant dislocation forest strengthening.Moreover,the Ta-rich locally ordered structure leads to an obvious heterogeneous strain and stress partitioning,which forms a strong strain gradient in the adjacent grain interiors and contributes to the strong back-stress-induced strain hardening.

Generalization properties of restricted Boltzmann machine for short-range order

A biased sampling algorithm for the restricted Boltzmann machine(RBM) is proposed, which allows generating configurations with a conserved quantity. To validate the method, a study of the short-range order in binary alloys with positive and negative exchange interactions is carried out. The network is trained on the data collected by Monte–Carlo simulations for a simple Ising-like binary alloy model and used to calculate the Warren–Cowley short-range order parameter and other thermodynamic properties. We demonstrate that the proposed method allows us not only to correctly reproduce the order parameters for the alloy concentration at which the network was trained, but can also predict them for any other concentrations.

Effect of Cerium on Chemical Short Range Order of Al-Fe-Ce Amorphous Alloy

The chemical short-range order of Al-Fe-Ce amorphous alloy was studied by means of X-ray diffraction (XRD) and differential scanning calorimetry (DSC). It is found that the prepeak position in X-ray diffraction intensity curve shifts to higher angles as the content of Fe increases, but it shifts to smaller angles as the content of Ce increases. The crystallization character of the amorphous alloy changes with the variation of the content of Fe and Ce. Ce can improve the interaction between atoms and the capacity of compound formation, so it is favorable to Al-based glass formability.

Effect of the interaction between the chemical and the magnetic ordering on the phase equilibria of iron base alloys

It is well known that the magnetic properties such as the Curie temperature Tmag <sub>C and the mean magnetic moment β of ordered compounds have different values from those of the disordered solutions. For instance, both Tmag c and β of the Ni3Pt （L12） and NiPt （L10） and Tmag <sub>c of the CoPt （L10） and CoPt3 （L12） ordered compounds are strongly depressed due to the ordering compared with those of the metastable disordered Ni-Pt and Co-Pt alloys. On the other hand, the γ’-FeNi3 （L12） and the α’-FeCo （B2） ordered compounds have higher Tmag <sub>c and β values comparing with the disordered solution phases, γ （A1） and α （A2）, respectively. In consequence, the stability of the ordered phase is depressed or enhanced due to the interaction between the chemical and magnetic ordering caused by the decrease or increase of Tmag <sub>c and β values. The purpose of this study is to investigate the effect of the interaction between the chemical and the magnetic ordering on the phase equilibria in the Fe-X（X=Al, Co, Ni, Rh, Si） binary systems.The Gibbs energy of the α（A2）, γ（A1） and liquid phases is described by a sub-regular solution approximation. The ordering contribution to the Gibbs energy ,ΔGorder <sub>m, and deviations of magnetic properties, ΔTmag <sub>c and Δβ, of the ordered compounds, FeAl （B2）, Fe3Al （D03）, FeCo （B2）, FeRh （B2）, FeSi （B2）, Fe3Si （D03） and FeNi3 （L12） is introduced by the split compound energy formalism. Effect of the interaction between the chemical ordering, B2, D03 and L12 and the magnetic ordering on the phase equilibria will be discussed according to the calculated phase diagrams of the Fe-X binary systems.

Chemically Modified Ordered Mesoporous Carbon/Polyaniline Composites for Electrochemical Capacitors

Chemically modified ordered mesoporous carbon CMK-3 materials were prepared by means of an easy wet-oxidative method in 2 mol/L nitric acid aqueous solution. A large amount of oxygen-containing functional groups were introduced onto the CMK-3 surface. Modified CMK-3（m-CMK-3） and aniline monomer were polymerized via an in situ chemical oxidative polymerization method. Morphological characterizations of m-CMK-3/PANI （polyaniline） composites were carried out via field emission scanning electron microscopy（SEM）. Their electrochemical properties were investigated with cyclic voltammetry, galvanostatic charge-discharge, and electrochemical impedance spectroscopy. The m-CMK-3/PANI composites have excellent properties in capacitance, and the highest specific capacitance（SC） value was up to 489 F/g, suggesting their potential application in the electrode material for electrochemical capacitors.

Effect of chemical ordering annealing on superelasticity of Ni-Mn-Ga-Fe ferromagnetic shape memory alloy microwires

Ni50Mn25Ga20Fe5 ferromagnetic shape memory alloy microwires with diameters of^30-50μm and grain sizes of^2-5μm were prepared by melt-extraction technique.A step-wise chemical ordering annealing was carried out to improve the superelasticity strain and recovery ratio which were hampered by the internal stress,compositional inhomogeneity,and high-density defects in the as-extracted Ni50Mn25Ga20Fe5 microwires.The annealed microwires exhibited enhanced atomic ordering degree,narrow thermal hysteresis,and high saturation magnetization under a low magnetic field.As a result,the annealed microwire showed decreased superelastic critical stress,improved reversibility,and a high superelastic strain(1.9%)with a large recovery ratio(>96%).This kind of filamentous material with superior superelastic effects may be promising materials for minor-devices.

SHORT-RANGE ORDER STRUCTURES OF Fe-Ge AMORPHOUS THIN FILMS

The short-range order structures of Fe_xGe_(1-x) amorphous thin films,(x=8.7,19.1 and 28.5%)have been studied by means of X-ray absorption spectrum.The nearest neighbors around a Ge or an Fe atom are constituted by two coordinate sub-shells with a very short dis- tance,In two films with lower Fe content,structural parameters of the nearest neighbors around a Ge atom are very near to that in amorphous germanium,and the positions of Fe at- oms are randomly substitutional.But when x=28.5%,some great changes occur on the short-range order structure of a-Fe_xGe_(1-x) film:its structure deviates from continuous ran- dora network and tends toward dense random packing of atoms.Meanwhile,there is a strong- er interaction between near neighboring Fe-Ge atoms in a-Fe_xGe_(1-x) films.

A theoretical study on chemical ordering of 38-atom trimetallic Pd-Ag-Pt nanoalloys

In this study,truncated octahedron(TO)structure is selected for further analysis and we focus on 38-atom Pd-Pt-Ag trimetallic nanoalloys.The best chemical ordering structures of PdnAg32-nPt6 trimetallic nanoalloys are obtained at Gupta level.The structures with the lowest energy at Gupta level are then re-optimized by density functional theory(DFT)relaxations and DFT results confirm the Gupta level calculations with small shifts on bond lengths indicating TO structure is favorable for 38-atom of PdnAg32-nPt6 trimetallic nanoalloys.The DFT excess energy analysis shows that Pd8Ag24Pt6 composition has the lowest excess energy value in common with excess energy analysis at Gupta level.In Pd8Ag24Pt6 composition,eight Pd atoms are central sites of 8(111)hexagonal facets of TO,24 Ag atoms locate on surface,and 6 Pt atoms locate at the core of the structure.It is also obtained that all of the compositions except Pd18Ag14Pt6 and Pd20Ag12Pt6 exhibit a octahedral Pt core.Besides,it is observed that there is a clear tendency for Ag atoms to segregate to the surface and also Pt atoms prefer to locate at core due to order parameter(R)variations.

Electrical Resistivity due to Short-range Order in Ni_2Cr

Residual electrical resistivity of Ni2Cr alloy due to short-range order (SRO) has been calculated at a temperature which is above the transition temperature, Tc, from long-range order to shortrange order. The atomic form factors for Ni and Cr are calculated in the pseudopotential formalism. We discuss the result of our calculations indicating a decrease in the value of residual electrical resistivity due to SRO in the light of experimental resistivity studies done on Ni72.5Cr27.5 and Ni65Cr35.

Soil Biological and Biochemical Responses to Cd Exposure

Heavy metals can stimulate the activity of soil enzymes in smaller amounts, but act as inhibitors if present in high concentrations. Natural and anthropogenic heavy metal contamination and its disturbances on soils can be evaluated by using enzymatic activities as sensors. To study the effects of Cd, soil added with known Cd concentrations (0, 10, 20, 50,100 and 200 mg/kg soil) were incubated for a period of 30 days at 28℃. At intervals of 0, 5, 10, 20 and 30 days samples were withdrawn for enzyme assays like dehydrogenase (DHA), catalase (CAT), phenol oxidase (PHE), and peroxidise (PER). In a separate experiment the effect of Cd on active microbial biomass carbon (AMBC), basal soil respiration (BSR), and metabolic quotient were studied. AMBC showed a reduction trend with increase in Cd concentration, and a maximum reduction of 47% was observed at 30th day for 200 mg/kg treatment. BSR also has got the same trend, with a maximum decrease of 42% at the 30th day. With the rate of Cd amendments and treatment period, DHA has shown an inhibition trend;whereas maximum decrease was observed for 200 mg/kg treatment at 30th day. CAT, PER, and PHE were found to be increased with Cd addition and remained at higher levels than in the control soil. These changes can be attributed to the effect of Cd on microbial activities. Based on cluster analysis, AMBC appears to be the sensitive indicators for the soil exposed to Cd contamination.

Interrelation of Chemical Elements Content in Plants underConditions of Primary Soil Formation

It is presented the results of a long-term and intensive experiment, which models the processes of primary soil formation under controlled agro-ecosystems. The influence of mineral substrate transformation is analyzed on the content of chemical elements in plants tomato, and wheat. For the first time have been established dynamic synergistic and antagonistic interrelations between the chemical elements in a various bodies of the plant (roots, reproductive bodies, stems, and leaves). Using methods of the theory of information was revealed dynamics of collective state of chemical elements in the plants. It is shown that the collective states of the chemical elements which defined by the information function is strictly differentiated for different plant bodies, and have hierarchic order. We analyzed the following chemical elements Si, Al, Fe, Mg, Ca, K, P, S, Cl, Na, Mn, Zn.

CONVERGENCE ANALYSIS OF MIXED VOLUME ELEMENT-CHARACTERISTIC MIXED VOLUME ELEMENT FOR THREE-DIMENSIONAL CHEMICAL OIL-RECOVERY SEEPAGE COUPLED PROBLEM

The physical model is described by a seepage coupled system for simulating numerically three-dimensional chemical oil recovery, whose mathematical description includes three equations to interpret main concepts. The pressure equation is a nonlinear parabolic equation, the concentration is defined by a convection-diffusion equation and the saturations of different components are stated by nonlinear convection-diffusion equations. The transport pressure appears in the concentration equation and saturation equations in the form of Darcy velocity, and controls their processes. The flow equation is solved by the conservative mixed volume element and the accuracy is improved one order for approximating Darcy velocity. The method of characteristic mixed volume element is applied to solve the concentration, where the diffusion is discretized by a mixed volume element method and the convection is treated by the method of characteristics. The characteristics can confirm strong computational stability at sharp fronts and it can avoid numerical dispersion and nonphysical oscillation. The scheme can adopt a large step while its numerical results have small time-truncation error and high order of accuracy. The mixed volume element method has the law of conservation on every element for the diffusion and it can obtain numerical solutions of the concentration and adjoint vectors. It is most important in numerical simulation to ensure the physical conservative nature. The saturation different components are obtained by the method of characteristic fractional step difference. The computational work is shortened greatly by decomposing a three-dimensional problem into three successive one-dimensional problems and it is completed easily by using the algorithm of speedup. Using the theory and technique of a priori estimates of differential equations, we derive an optimal second order estimates in 12 norm. Numerical examples are given to show the effectiveness and practicability and the method is testified as a powerful tool to solve the important problems.

“两性一度”背景下化工热力学实验教学进阶式探索与实践

在化工热力学实验教学中,通过设置进阶训练思考题,激励学生进行探索与实践。以第二维里系数的测定实验为例,倡导学生独立思考与构建高阶维里系数的方法,引导其分析比较国内外学者处理问题的策略与方法,而后辅导其通过双向检验证明所做实验数据的准确性、验证所构建方法的合理性、分析所得结果的有效性,最后指导学生理清数据处理方法的发展脉络,对其所构建的方法进行准确定位与评价。本教学实践通过强化实验教学项目的设计性与综合性,探索提升实验类课程高阶性的途径,践行“两性一度”的要求。