用NBSGSC计算机程序和单标样的理论α系数法分析结果

引言过去30年,人们在X射线荧光分析中试用了各种校正元素间影响的计算方法。其中所谓的“经验系数法”需要相当数量的优质标样。而所谓的“基本参数法”原则上仅需纯元素标样或单只多元标样。纯元素标样有时难以得到,而且受到所用物理常数和参数(包括质量吸收系数,荧光产额,吸收边跃迁比,原级光谱和几何因子等)不准确性的严重影响,在多数情况下结果甚差。除非手头没有多元标样,一般在基本参数法中不宜使用。而单只多元标样则可消除或减小理论的不完善性以及基本参数的不准确性,因而在基本参数法中更为可取。     

二元合金成份的无标样X光能谱定量分析

一般用电子探针对合金成份进行定量分析时都用标样进行对比。本文提出了一个不用标样的二元合金成份的定量分析方法。利用扫描电子显微镜-X光能谱分析装置同时测定二元合金(Cu-Ga,GaAs)中二元素的K_a光子数比值后,由简化的入射电子能量损失公式和X光激发截面公式并考虑了二次荧光效应后,可计算出二元合金的成份。当入射电子的过电压保持在2—3时,得到和实际成份一致的结果。利用上述简化模型对文献中不同纯元素特征X光的“仪器灵敏度”进行了计算和讨论。 关键词：     

多元合金的无标样能量色散X射线荧光分析

本文在能量色散X射线荧光分析系统的效率刻度及散射修正的基础上,用基本参数法对多元合金进行无标样X射线荧光分沂。分析结果表明,对于主成分元素,分析误差约为2%,对于次成分元素,误差低于10%。     

扩展的联立方程K值法──一种无标样X射线定量相分析方法

X射线定量相分析方法一般分为标样法和无标样法.刘沃垣[1]和Zevin[2]分别提出的无标样法和分属标样法都要求有几个样品,每个样品都包含几个物相.姚公达和郭常霖[3]针对这个问题对Zevin法作了改进,解决了缺相问题.本文也针对上述问题提出一种扩展的联立方程K值法.该法所用的参考样品的相数可以和待测样品不同,既可以缺少某些相,又可以多出其它相,且无论是缺相还是多相,只要待测样品中的(n0-1)个相在参考样品中出现过,则参考样品中未出现过的那个相可以是非晶态. 一、基本原理1.参考样品缺相的联立方程K值法 如待测样品合n0个物相,这时需要…     

X射线荧光光谱法非破坏测定二元合金薄膜的成分

一、引 言 用X射线荧光光谱法测定二元合金薄膜的组分时,通常是先制备一系列不同成分的薄膜,经化学分析标定后作为标样,以此来确定标准曲线,然后对待测薄膜进行测定、比较[1,2].近年来某些作者推荐利用单组分薄膜标样的方法[3,4].这些方法不足之处在于制备薄膜标样要增加较大的工作量.用质子背散射方法来测定薄膜组分虽具有它独特的优点,但是在测定膜主成分时其准确度常常不够满意,此外,它还要与加速器联用,因此应用上也受到限制. 本文来用 L.Bergel及 F.J.Cadieu[5]推荐的利用滤纸片标样的方法,测定了非晶态钆钴合金薄膜的原子组分比. …     

含轻元素二元合金成分的无标样X光能谱定量分析

本文对利用试样中不同元素X光强度相对比值分析成分的无标样定量分析方法提出了改进。首先对电子散射的“完全扩散”模型进行适当的修正和简化,得到标识X光的台阶状深度分布曲线,从而得到试样成分和标识X光强度的定量关系。对Cu-Si,FeS₂,NaCl和GaAs等二元合金的成分分析得到比较满意的结果。本文比较了用此法和Russ法(利用计算得到的纯元素标识X光强度因子并且经ZAF修正分析成分)得到的结果,表明用我们的方法分析的结果有所改善,计算程序也更简单。 关键词：     

热力学方法在处理XRF数据中的应用

应用热力学方法处理X-射线荧光光谱分析(XRF)数据是1983年文献[1]首次提出。XRF中相对强度R被视为表观活度(即有效浓度),R/X比(相对强度/重量分数)视为表观活度系数γ。应用了lgγ_(B,A)/X_A~(?)=β形式的亚正规溶液方程式来描述和计算A-B二元体系表观活度系数随成份X_A变化的关系。多元体系中XRF的R/X比可根据以下关系式由二元体系已知表观活度系数计算: γ_(A,B,C)……=γ_(A,B)·γ_(A,C)……γ_(B,A,C)……=γ_(B,A)·γ_(B,C)……我们采用文献[2],[3]二元体系数据计算三元系参数,计算结果表明上述关系在允许误差范围内基本能满足要求。由三元系试样的相对强度R和二元系数据计算三元体系未知组分的成分可以用迭代的方法借助微型计算机来实现。为了进一步验证热力学方法处理XRF数据的可行性,我们研制了Cu-Ni-Fe-Zn粉末压片的二元,三元,四元系,含量范围较宽的样品,并测定了各组分的相对强度R。计算结果表明亚正规溶液模型对二元体系获得的结果最好。为了满足分析化学对准确度的要求,我们进一步提出了以下的修正数模(TM-3): 根据上述关系式,用实验数据计算的结果与人工配料组成相比的符合程是令人满意的,且与C-Q方程计算的结果一致。(见表1和表2)     

相场法模拟多元合金过冷熔体中的枝晶生长

在二元合金相场模型研究的基础上，进行扩展获得了多元合金相场模型.以Al-Si-Mg三元合金为例，采用该相场模型实现了逼真地模拟多元合金凝固过程的等轴枝晶生长，得到了二次或更高次晶臂生长等复杂的枝晶形貌.随着第三组元Mg含量的减少，枝晶的二次枝晶越发达，枝晶中溶质的偏析越严重，枝晶尖端的生长速率和半径越大，与丁二腈-丙酮体系中枝晶尖端生长速率、半径随溶质浓度变化关系的理论计算和实验结果相符合.另外，枝晶初生晶臂中心的溶质浓度最低，在被二次晶臂包围的界面区域的溶质浓度最高；固液界面区域具有较大的浓度梯度，其中枝晶尖端前沿的梯度最大. 关键词： 相场法 多元合金 凝固过程 枝晶生长     

用NBSGSC计算机程序和单标样的理论a系数法分析结果

经验系数法根据所用的经验校正方程类型和所希望分析的组分范围,一般需要相当多的优质多元标样。与此相比基本参数法则原则上仅需纯元素标样或单只多元标样。因为在有些情况下难于获得纯元素标样,加之若用单只多元标样可以消除或减少理论公式的不完善性从及基本参数的不准确性,因此使用单只多元标样更可取     

基于改进元胞自动机模型的三元合金枝晶生长的数值模拟

在二元合金元胞自动机模型的基础上,通过耦合多元合金热力学相平衡求解器PanEngine, 建立了三元合金改进的元胞自动机模型,可模拟初生相枝晶的生长过程. 模型考虑了曲率过冷和成分过冷对界面平衡溶质成分的影响,通过不同组元的无量纲溶质过饱和度方程和界面溶质守恒方程之间的耦合来求解界面生长速率,并通过PanEngine计算界面处的液相线温度. 采用本模型模拟了Al-7%Si-xMg三元合金自由枝晶的生长形态, 结果表明Mg含量的增加会抑制枝晶一次臂的生长和二次臂的产生.同时模拟了不同抽拉速度下 Al-7%Si-0.5%Mg合金柱状枝晶的竞争生长过程,随着抽拉速度的增大,柱状枝晶一次枝晶臂间距逐渐减小, 与Hunt理论模型符合较好.     

二元化合物成分的X射线能谱无标样定量分析

常规的X射线能谱无标样定量分析采用Russ法。最近吴自勤等人又提出X射线能谱无标样定量分析的直接法。本文仍采用直接法,但吸收了Russ法中的优点。用常规的ZAF修正中使用的物理公式,推出X射线能谱另一种无标样定量分析的方法,它更便于计算。对NaCl,NaI,KCl,AgI,ZnS和GaAs样品的实验分析,证明用本文方法的分析结果优于用Russ法的分析结果。特别是对含有低原子序数元素的样品更为明显。 关键词：     

Role of electronic structure in the formation of the properties and characteristics of interatomic interaction in alloys of iron with chromium and vanadium

In this work, the electronic structure and the magnetic state of Fe-Cr, Fe-V, and Fe-Cr-V alloys are investigated by the method of coherent potential in the approximation of Hartree-Fock. The effective fields on the nuclei of Fe of the ternary alloys are calculated using the results that have been obtained. The effective fields on Fe nuclei in Fe-Cr-V alloys have been experimentally measured. Comparison with the experimental results shows that the electronic and magnetic states of both the binary and ternary alloys are reasonably described by the coherent potential method. Analysis of the available results allows one to explain the differences existing in the phase diagrams of binary alloys as well as to reach conclusions about the shape of the equilibrium phase diagram of the ternary alloy.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 12, pp. 77–83, December, 1988.     

Charge transfer in binary alloys and to impurities in iron

The energy density formalism in the Thomas-Fermi-Dirac approximation was used to study charge transfer in equiatomic binary ordered alloys and in dilute iron alloys. This method was applied outside of a core region around each nucleus; the inner region was treated by taking the electron density to be that given by free atom wave functions.The results for the equivolume charge transfer in binary alloys agreed satisfactorily with existing KKR-selfconsislent field calculations.For metalloid impurities in iron, the charge transfer to the impurity, and the variation of lattice parameter with concentration was computed. The latter compared fairly well with experiments.The theory explicitly displays the role of the electron density at the cell boundary in alloy formation and charge transfer effects. Alloy formation is visualized as a process in which atomic cells of the pure metals are expanded or compressed to the equilibrium cell volume of the alloy, bringing the cells together to form the alloy, and then allowing the electron distribution to relax.The general conclusion of this work is that modifying the TFD theory by using it only in regions where the electron density does not vary too rapidly, and using quantum theory results for the density close to the nuclei. provides a satisfactory method for studying charge transfer.     

Ordering in binary FCC alloys

A new method of approximation for studying the order-disorder transition in binary alloys is presented. The formulation is in terms of face-centered cubic alloys, although the method can also be applied to other structures. The technique is essentially a generalization of the constant-coupling approximation. We have applied the principles of that method to derive the free energy of the alloy using a tetrahedral cluster of nearest neighbouring sites as the basic unit of the calculation. We only consider the case of nearest neighbour pair interactions, but show how the method can be generalized to include many body and second neighbour interactions. Numerical results are presented and comparison of these results is made with results of cluster variation calculations on the same system and with experimental results on the copper-gold alloy system.     

X射线发射深度分布φ(ρz)计算与电子探针定量分析

本文利用Monte Carlo方法和修改了的原子散射总截面公式,计算了在合金中产生X射线的深度分布φ(ρz),并用于电子探针定量分析。对12种二元合金、一种三元合金和碳化硅中的碳作了计算,结果比ZAF方法和Shimizu方法好。尤其对碳的计算结果比ZAF方法更好,表明本文的计算方法用于轻元素定量分析是可行的。 关键词：     

Preferred sputtering on binary alloy surfaces of the AlPdSi system

Auger spectroscopy has been used to investigate the behavior of preferred sputtering on surfaces of homogeneous AlPd, SiPd and AlSi alloy films. These combinations of alloys were chosen for studying the effects of mass and bonding differences on preferred sputtering. Experiments have been carried out using a 1 keV Ar ion beam over a range of alloy compositions. Our results can be summarized as follows: (a) The preferred sputtering of these binary alloys cannot be predicted according to the sputter yields of individual elements, e.g. both Al and Si have been observed to be removed preferentially relative to Pd although pure Pd has a higher sputter yield, (b) In the alloys studied, mass difference appears to dominate over bonding difference in controlling the preferred sputtering behavior since the extent of preferred sputtering of Al and Si relative to Pd is about the same. This observation is interpreted on the basis of the binary alloy sputtering theory formulated by Andersen and Sigmund. (c) Judging from the composition change of the sputtered surface, there is no evidence for formation of compounds with specific compositions as a result of preferred sputtering in the AlPd and SiPd alloys investigated.     

基于机器学习的合金催化剂表面吸附能预测

近年来,机器学习方法逐渐成为多相催化中的一种关键研究手段. 二元合金材料作为重要的催化剂之一,在双功能催化剂的筛选中受到了广泛的关注. 本文提出了一个将机器学习方法应用在预测催化性质上的整体框架,从而快速预测原子、分子在金属和二元合金表面的吸附能. 通过测试不同的机器学习方法来评估它们对于该问题的适用性,并将树集成的方法与压缩感知方法相结合,利用约6×10⁴个吸附能数据构建了预测模型. 相对于线性比例关系,该方法可以更准确地预测大量合金上的吸附能(预测的均方根误差降低一半),并且更通用地预测各种吸附物的能量,为发现新的双金属催化剂铺平了道路.     

Total electronic energy of a noble metal ordered alloy in the pseudopotential method

Application of the pseudopotential method to noble metal ordered alloys is considered in this paper. Expressions are obtained for the Fourier components of the crystal potential and for the total electronic energy of the alloy. The pseudopotential matrix elements are factorized, and the possibility of transforming to a pair interaction representation is shown. Expressions are obtained for the pair potential of indirect interionic interactions in a noble metal binary ordered alloy.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 8, pp. 21–28, August, 1973.     

Ti,Nb, Al及其二元合金状态方程的第一原理计算及其应用

金属状态方程对于探究金属及合金原子的相互作用中起到了至关重要的作用.本文使用第一原理计算了Ti, Nb, Al及其二元合金能量与原子间距关系(E-r关系),并使用得到的E-r关系计算了金属及合金的体弹性模量,结果与实验值吻合的很好.计算结果表明,使用不同的赝势,计算不同金属表现出不同的适用性;二元合金的E-r曲线处于对应合金化元素曲线之间;并且合金的E-r曲线会更靠近合金内含量较高的元素的E-r曲线;并发现合金E-r关系可通过组成合金的纯金属的E-r关系计算获得,且用该方法计算材料的体弹性模量与实验值非常符合.     

Melting point trends in intermetallic alloys

We have examined the melting points of approximately 500 intermetallic binary alloys. We attempted to correlate the melting point behavior of the binary (1:1) alloys with a number of elemental variables including electron number, atomic size, orbital radii, electronegativity, etc. We find that a “Vegards's Law” of melting points works very well for predicting the melting points of binary transition metal alloys, i.e. the melting point of the alloy correlates with the linear average of the elementary melting points. However, this “law” works only moderately well for alloys involving simple metals. In addition, we find that transition metal alloys tend to have melting points below the averaged elemental melting points. This finding is in sharp contrast to simple metal alloys where the opposite trend is observed and it is indicative of fundamental differences between transition metal and simple metal binding. Finally, we have attempted to correlate deviations from a Vegard's law of melting with elemental variables. We found no strong correlation with elemental variables (or the heats of formation of the alloy in question) with the possible exception being a correlation with elemental volume changes upon alloying. The consequences of this correlation upon alloy design and metallic alloy formation are briefly discussed.