液态金属Al快凝过程中纳米级大团簇结构的形成特性模拟研究

采用分子动力学方法，对含有400000个Al原子的液态金属大系统在快凝过程中纳米级团簇结构的形成特性进行了模拟研究，并采用原子团类型指数法(CTIM)来描述各种类型的团簇结构组态。结果显示：二十面体原子团(120120)及其组合在微观结构转变中起着最重要的作用；纳米级大团簇(150个原子)是由一些中等原子团结合而成，等原子团由小原子团组成；这种结构与由其它方法获得的纳米级大团簇的结构完全不同，后者是以某一个原子为中心按八面体结构堆积起来的多壳层晶体结构。这些结果正好可以用来解释用不同方法所形成的Al的团簇结构组态之间的本质区别。     

Nin(n=2-6)原子簇的电子结构和磁性研究

采用MS—Xα方法研究了Nin(n=2—6)原子簇的电子结构和原子磁矩,发现团簇的几何对称性对原子磁矩和电子态密度的分布有重要影响．具有Oh点群对称的八面体原子簇Ni6的^3Eg轨道上存在很强的负交换耦合,呈现反铁磁耦合趋势;具有C3υ点群对称的三边金字塔结构的原子簇Ni5位于塔顶点的Ni原子与基面上的Ni原子磁矩方向相反,但大小不等,呈现出亚铁磁交换耦合特征．与金属Ni相比,有些Ni原子团簇磁性增强,有些团簇磁性减弱．这一结果能够较好地解释铁磁超微颗粒呈现出的表面磁性异常现象．     

First principles study of site substitution of ternary elements in NiAl

Site substitution of ternary elements in ordered compounds influences the electronic structure and hence the properties of compounds at the continuous level. The electronic structure and binding energy of a number of NiAl-X alloy systems (X=Ti, V, Cr, Mn, Fe, Co, Zr, Nb, Mo, Hf, Ta, W, Si, Ga, or Ge) were calculated using the discrete variational cluster method based on the local density approximation of the density functional theory. The site preference of the ternary additions to NiAl was investigated by employing the Bragg–Williams model to analyse the calculated binding energy. The results show that all the considered ternary elements possess stronger preference to the Al sublattice sites than a Ni atom does. A new method of identifying sublattice substitution of ternary additions in NiAl was proposed by comparison of the binding energies per atom of the ternary and the binary clusters involving the fourth nearest neighbours. The analysis suggests that Fe and Co atoms occupy the Ni sublattice sites, whereas Si, Ga and Ti atoms occupy the Al sublattice sites. The remaining elements may substitute for both sublattices: Mn is most likely to go for the Ni sublattice; V, Cr, Zr, Nb, Mo, Hf, Ta, W and Ge have a larger preference for the Al sublattice, but Cr and W do not show significant preference to any sublattice. The densities of states involving alloying additions of Co, Si and Cr were further investigated to clarify the site preference of the alloying additions.     

DFT research on activation of sphalerite

Activation of sphalerite ZnS, (Zn, Fe)S, (Zn, Cu)S were carried out using the density functional theory (DFT) method. The electronic structures and related properties of three kind of zinc sulfide compounds were investigated. In addition, the relation between electronic structure and flotation behavior was discussed. The results show that, ZnS has a broader band gap than (Zn,Cu)S and (Zn,Fe)S do, and it has low electrochemistry activity to react with flotation collectors to render the surface hydrophobic. When the Zn atom in ZnS is replaced by Cu atom,the band gap will be reduced, and the top valence band will be occupied by Cu 3d orbit, thus it is beneficial to the interaction between mineral surface and collector.     

合金相团簇规律及其在Zr-Al-Ni非晶体系中的应用

研究多个典型非晶形成体系合金相结构中的团簇规律,指出在合金相结构中团簇之间以不同方式共享原子的事实。共享后的有效团簇到合金相的连接方式有两种,一种是共享后的团簇成分就是相成分,无须连接原子,另一种是共享后的团簇加上连接原子才能构成空间相结构(这类相称之为团簇相)。这种方法使得对合金相的结构有了一个全新的理解。在典型的非晶形成体系Zr-Al-Ni中,团簇相有3个:AlNiZr-Fe2P结构,Al2NiZr6-InMg2结构和Al5Ni3Zr2-Mn23Th6结构。通过此项工作还提出了基于合金相结构来确定与非晶形成相关的团簇的方法,即与非晶相关的团簇一般为团簇相里出来的孤立团簇,这一结论在Zr-Al-Ni体系中得到了很好的验证。     

The density and packing fraction of binary metallic glasses

The present work develops a physical model of metallic glass structure that gives a reasonable estimate of density. The efficient cluster-packing model is used as a starting point, and is refined by a high-fidelity estimate of the size of structure-forming clusters and cluster–cluster separations. These are predicted as continuous functions of composition and relative atom radii. Predicted densities are all are within ±10% of measured densities for 200 binary metallic glasses, representing a precision in cluster–cluster separations of ±3%. New structural insights from this work include the importance of acknowledging the unique cluster topologies to estimate cluster–cluster separations; an improved ability to estimate the higher packing efficiency of unlike atoms in the first coordination shell of atomic clusters; and an improved estimate of metalloid–metalloid separations. The unusual, bilinear influence of composition on density in Fe–B glasses is explained by considering the sizes of β and γ sites in different metallic glass structures. Global atom packing fractions derived from measured densities range from about 0.62 to 0.76, and the most stable binary glasses all have packing fractions in excess of 0.70, supporting the idea that atom packing efficiency influences glass stability.     

铝元素的添加对锆基合金非晶形成能力影响的电子结构模型

通过构建非晶合金的团簇模型，利用离散变分法从电子层次研究了Al元素对Zr-Cu非晶合金中团簇稳定性的影响。结果表明，Al原子的引入提高了团簇中原子间的亲和力，并且随着Al原子数的增加，亲和力增大，导致新的团簇产生，从而破坏了非晶的团簇结构，Al含量对Zr-Al-Ni非晶合金的稳定性的影响可通过Fermi能级处的态密度大小来反映。     

Effect of copper addition on the thermal contraction of indium melt clusters

The structure of In-1%Cu and In-5%Cu (mass fraction) alloy melts were studied at different temperatures above liquidus by using a high-temperature X-ray diffractometer and were compared with that of pure In melt. Experimental results show that with the addition of 1% Cu or 5% Cu, the thermal contraction phenomenon of atom clusters occurs in melts with the temperature increasing like pure In melt. With the addition of 1% Cu, the thermal contraction of atom clusters increases and the contraction is not homogeneous in the whole measurement temperature range. The sudden change and noticeable contraction can be found in the range of 280-390℃. The temperature range of the sudden change is lower than that of pure In melt. With the addition of 5% Cu, the thermal contraction of atom clusters decreases and the contraction is not consistent in the whole measurement temperature range. The anomalous change can be measured at about 600 ℃. At the same superheating temperature, the nearest interatomic distance r1 of     

压力对L1_2-Co_3(Al,W)化合物弹性性能与电子结构的影响

基于密度泛函理论,采用第一性原理赝势平面波方法计算了不同压力下L12-Co3(Al,W)化合物的弹性性质与电子结构。计算得到零压力下的点阵常数a0与实验值和理论值相符,计算结果表明:在0~45 GPa压力范围内,L12-Co3(Al,W)化合物的弹性常数Cij(C11、C12、C44)与压力满足三阶多项式关系,体模量B、剪切模量G、本征塑性、断裂韧性随压力的增强而增加;通过引入总化学键重叠布局数,定量的计算了金属间化合物的共价键性能,结果显示压力的增加会不断增强L12-Co3(Al,W)化合物中的共价键强度;电荷差分密度分析表明,随着压力的增加,W原子得到电子,Al原子失去电子,Co-Co、Co-W原子间电荷密度明显增强,表现出更强的键合作用。     

Mg_3N_2团簇吸附H的密度泛函理论研究

运用密度泛函理论(DFT)中的杂化密度泛函B3LYP方法在6-311G*基组水平上对Mg_3N_2H_m(m=1~4)和(Mg_3N_2)_nH_m(n=2~4,m=1~2)团簇的可能几何结构进行优化,预测了其最稳定结构,并对最稳定结构的电子结构,成键特性,电荷分布,振动特性及稳定性等进行分析。结果表明:当团簇吸附H原子少于N原子数目时,一般形成-NH基;随着团簇吸附H原子数目的增加,当所有N原子吸H形成-NH基后,才有-NH基吸附H原子形成-NH_2基;但并不是所有-NH基全部形成-NH_2基的饱和结构,此时部分H原子会吸附于Mg原子上形成MgH结构。H原子易吸附于凸出的、包含孤对电子的N原子上;由于孤对电子间的排斥作用,H原子的吸附位置呈相互远离趋势。团簇中N-H之间是共价键作用,而Mg-H间是离子键作用,-NH和-NH_2基在团簇中保持完整性,团簇可以很好地描述晶体的储氢行为。     

Comparison of the electronic states of alloys from the coherent potential approximation and an order-N calculation

For historical reasons, the coherent potential approximation was originally proposed for isomorphous models of alloys in which all the atoms of a given species are assumed to have the same charge distribution. Order-N methods for density-functional theory local-density approximation calculations of the electronic structure for clusters of hundreds or thousands of atoms demonstrate that a polymorphous model, in which each atom is different, is more realistic. The predictive ability of isomorphous coherent potential approximations is studied by comparison with order-N calculations.     

Comparison of the electronic states of alloys from the coherent potential approximation and an order-N calculation

For historical reasons, the coherent potential approximation was originally proposed for isomorphous models of alloys in which all the atoms of a given species are assumed to have the same charge distribution. Order-N methods for density-functional theory local-density approximation calculations of the electronic structure for clusters of hundreds or thousands of atoms demonstrate that a polymorphous model, in which each atom is different, is more realistic. The predictive ability of isomorphous coherent potential approximations is studied by comparison with order-N calculations.     

添加Al对Cu基合金非晶形成能力影响的团簇模型

在二元Cu-Zr合金中添加Al元素可明显提高合金的非晶形成能力.根据非晶与其晶化相存在结构遗传关系,以Cu-Zr基非晶晶化相Cu10Zr7中的Cu6Zr5阿基米德反棱柱为团簇模型,利用离散变分方法从电子层次研究了Al元素对Cu基非晶合金团簇稳定性的影响.结果表明:当团簇中加入一个Al原子时,Fermi能级处的态密度明显降低,团簇稳定性提高;但继续加入Al原子,Fermi能级处的态密度又开始上升,态密度处于较高位置,团簇稳定性下降;计算结果与实验结果相吻合.     

Influence of sulphur on the solubility of graphite in iron melts: a Monte Carlo simulation study

We report a Monte Carlo simulation study of the effect of sulphur on the solubility of graphite in iron melts in the temperature range 1400–1600°C. The atoms in the ternary Fe–C–S system were arranged on a graphitic hexagonal lattice and pairwise interactions between them were assumed to be short ranged. The simulations were carried out using a combination of canonical and grand canonical ensembles for a range of interaction strengths, carbon and sulphur concentrations and temperature. In all simulations, graphite solubility exhibited a linear decrease with increasing sulphur concentration with slopes ranging from −0.4 to −0.6. The experimental values of this slope range from −0.4 to −0.48. The strong bond between Fe and S, which is capable of distorting electron distribution around Fe atoms and affect other bonds made by it, appears to be one of the most important parameters in this model. With no distortion around an Fe atom, there is a general increase in slope values with increasing sulphur interaction strengths (S–S, S–C and S–Fe). However, with a medium or strong distortion around Fe atoms due to the Fe–S bond, the slopes no longer depend on the magnitude of various sulphur interactions and show a rather flat range. The simulated slopes also increase slightly with temperature. The effect of various carbon interactions is also discussed.     

ELECTRONIC STRUCTURE OF γ'-PHASE IN SUPERALLOY CONTAINING Mg AND W

The calculation of electronic structure of γ'-Ni_3Al phase with or without Mg and W by theRecursion and LCAO methods clarified that Mg and W atoms lose their outer electrons par-tially after they entered γ'-Ni_3Al.It causes the reduction of the radii of the atoms.So it ispreferable for Mg atom to enter γ'-phase by the substitution.The interaction between Mg andγ'-phase matrix may be strengthened and a more stable structure of γ'-phase may be formedwhile Mg and W entered γ'-Ni_3Al simultaneously.     

Electronic structures and physical properties of pure Cr,Mo and W

1　INTRODUCTIONIntheframeworkofthemetallicmaterialssys tematicscience[1] ,therearethreescientifictheorysystems :puremetalsystematicscience ,alloysphysicsandchemistry ,andalloysstatisticalthermodynamics .Thecoreofthepuremetalsystema ticscienceistheoneatomtheory (OA ) [2 5] ,andthatofthealloysphysicsandchemistryandalloysstatisticalthermody namicsisthecharacteristiccrystaltheory(CC) .Inordertomakethematerialsdesignstepfromempiricaltoscientificundertheguidanceofthemetallicmateri alssystemati…     

电脉冲孕育处理对Al-5%Cu合金液态结构的影响

利用高温X射线衍射仪对经电脉冲孕育处理的Al?5%Cu合金液态结构进行表征。结果表明：在经电脉冲孕育处理的熔体中,含 Cu 的铝团簇数量明显增加,由于相关原子半径和配位数的减小而使这些团簇呈现某种热收缩状态。这种液相结构将使最终的凝固组织中富Cu相更趋于均匀分布。DSC测试表明,经电脉冲孕育处理的液相在结晶过程中,其过冷度是未处理液相的2.36倍。可以确定,电脉冲处理后的Al?5%Cu熔体中原子团簇的变化与先前提出的纯金属电脉冲孕育处理机理模型存在明显差异。     

ASPS技术制备微纳结构FeS固体润滑渗硫层的研究

利用可移动活性屏低温离子渗流技术(简称ASPS技术),考察了工艺参数对渗硫层形貌、结构等的影响,制备了具有微纳结构的FeS固体润滑渗硫层。研究发现,渗硫温度比保温时间对FeS固体润滑渗硫层的形貌和组成结构影响更大。当渗硫温度230℃、保温2 h时,渗硫层以FeS为主,但含少量的FeS2,渗硫层中S/Fe原子摩尔百分比值接近1。渗硫层由微纳米量级的硫化物颗粒堆积而成,表层为富S层、次表层为FeS层,在渗硫层和基体之间存在厚度约400 nm的扩散层。     

异构片层结构304不锈钢的制备及其力学性能

采用形变诱导马氏体退火逆转变工艺制备了异构片层结构(HLS)的304奥氏体不锈钢。通过扫描电镜和X射线衍射仪分析了304奥氏体不锈钢的显微组织和物相组成,并采用室温拉伸试验研究了其力学性能。结果表明,通过变形量为34%的热轧、75%的冷轧以及700 ℃退火12 min后,试验钢中的马氏体相逆转变为奥氏体相,部分残留奥氏体发生再结晶,获得了由微米再结晶晶粒与超细晶/纳米晶晶粒以及残留奥氏体晶粒组成的异构片层结构,微米再结晶晶粒和残留奥氏体被超细晶/纳米晶晶粒所包围。异构片层结构304奥氏体不锈钢的屈服强度为940.1 MPa,断裂总延伸率为43.1%,获得了良好的强度-塑性匹配。     

Study of thioureas derivatives synthesized from a green route as corrosion inhibitors for mild steel in HCl solution

The behaviour of 1,3-dibenzylthiourea (DBTU) and 1-benzyl-3-diisopropylthiourea (DPTU) have been investigated as carbon steel corrosion inhibitors in HCl solution by weight loss measurements, potentiodynamic polarization curves, electrochemical impedance and scanning electron microscopy analysis. Quantum chemical calculation was applied to correlate electronic structure parameters of thiourea derivatives with their inhibition performances. DPTU results were slightly superior to those obtained in the presence of DBTU, showing that the replacement of one benzyl group for two isopropyl groups enhances the inhibitory properties. The 1,3-dibenzylurea derivative has also been studied in order to assess the importance of the sulphur atom to the inhibitory effect.