Ordering in alloys

Abstract

The continuous ordering process can be viewed as a development and a gradual amplification of concentration modulations with wave lengths of the order of a few lattice spacings. How the development of different concentration modulaltions leads to different superlattice structures in cubic systems is explained with the help of some illustrative examples. The importance of concentration modulations with special point wave vectors in the stability of the various coherent superlattice structures is discussed. Experimental evidences for such continuous ordering is cited from recent results on ordering in Ni-Mo alloys.

The evolution of ordering in some systems can also be viewed as progressively tiling the disordered lattice by superlattice tiles. When more than one type of coherent superlattice tiles compete, juxtaposition of different types of tiles can occur during the course of ordering. The transitional states between the short range and the long range ordered Ni-Mo alloys indeed exhibit such structures where different types of superlattice tiles decorate the fcc lattice. The role of special point concentration waves in the development of such structures will be discussed in relation to the secondary ordering processes involving two perpendicular ?1 ½ 0? waves and a combination of an ?1 ½ 0? and an appropriate ?100? wave.     

Ordering phenomena in cooling granular mixtures

We report two phenomena, induced by dynamical correlations, that occur during the free cooling of a two-dimensional mixture of inelastic hard disks. First, we show that, due to the onset of velocity correlations, the ratio of the kinetic energies associated with the two species changes from the value corresponding to the homogeneous cooling state to a value approximately given by the mass ratio m(1)/m(2) of the two species. Second, we report a novel segregation effect that occurs in the late stage of cooling, where interconnected domains appear. Spectral analysis of the composition field reveals the emergence of a growing characteristic length.     

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.     

液态Ga-In合金中的团簇分离现象

与以往试验及模拟计算方法不同,文章利用从头计算分子动力学研究了液态Ga, In及Ga-In合金的偏结构. 发现合金偏双体相关函数gGaGa(r), gInIn(r)的第一峰的位置分别与液态纯Ga和纯In的第一峰 位置接近, gGaIn(r)第一峰位置大于纯Ga和纯In第一峰位置的平均值,说明液态Ga-In合金中异类原子 呈现排斥倾向, Ga-Ga, In-In团簇更容易出现.在纯Ga, 纯In中占据最高含量的1311键对在液态合金中占主导 地位,说明Ga-Ga, In-In团簇共存于液态Ga-In合金中. Voronoi多面体分析发现,随着In含量的增加, 在Ga_100-xIn_x(30 ≤x≤qslant 50 at.% ) 区域内, Ga原子周围主配位数出现突变,由12降为10,证明Ga-Ga和In-In团簇倾向于分离.该研究结果不同于 通常的微观不均匀模型,揭示了液态Ga-In合金中团簇分离的机制.     

Ordering of ternary alloys in the self-consistent field approximation

In the self-consistent field approximation, without allowance for correlation, a static theory of the ordering of ternary alloys is constructed which makes it possible to take into account the long-range nature of the interatomic interaction forces in substitutional and interstitial alloys. The theory enables one to take into account the possible existence in the alloy of two subsets of points differing by the species of atoms that occupy them. The stability of the disordered state in such alloys is analyzed and an expression obtained for the temperature at which the disordered state loses stability.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 11, pp. 61–64, November, 1980.     

Ordering kinetics in bcc alloys with allowance for diffusion processes

The kinetics of inhomogeneous ordering in binary bcc substitution alloys of arbitrary stoichiometry is considered with the account for for diffusion processes. A system of kinetic equations describing the joint evolution of the occupancies of two sublattices of a bcc lattice is derived using a phenomenological approach. It is shown that, even within the mean-field approximation, this approach allows one to describe simultaneously the processes of establishment of the long-range order and diffusion of the alloy components. Numerical analysis of the obtained system of equations showed that quick onset of long-range order first occurs, which is followed by slow diffusion of the alloy components.     

Uncommon corrosion phenomena of archaeological bronze alloys

In the framework of the EFESTUS project (funded by the European Commission, contract No. ICA3-CT-2002-10030) the corrosion products of a large number of archaeological bronze artefacts are investigated by means of the combined use of scanning electron microscopy (SEM), energy dispersive spectrometry (EDS), X-ray diffraction (XRD) and optical microscopy (OM) and tentative correlation of their nature with the chemical composition of the artefacts and the burial context is proposed.The results provide good insight into the corrosion layers and evidence in some bronze Roman coins and artefacts; the occurrence of uncommon corrosion phenomena that give rise to the formation of a yellowish-green complex chlorine-phosphate of lead (pyromorphite, (PbCl)Pb₄(PO₄)₃) and of a gold-like thick layer of an iron and copper sulphide (chalcopyrite, CuFeS₂). The micro-chemical and micro-structural results show that the coins were buried in a soil enriched in phosphorus for the accidental presence of a large amount of decomposing fragments of bones or in an anaerobic and humus rich soil where the chalcopyrite layer has been produced via the interaction between the iron of the soil, the copper of the coin and the sulphur produced by the decomposition of organic matter in an almost oxygen free environment. Finally, some unusual periodic corrosion phenomena occurring in high tin bronze mirrors found at Zama (Tunisia) are described. PACS 68.55Jk; 68.35 Dv; 68.37Hk; 68.55 Nq; 81.05 Bx     

Ordering of substitutional ternary alloys with an fcc lattice

The possible types of ordering diagrams of ternary substutional alloys with an fcc lattice are analyzed, taking account of interactions in two coordination spheres.Ural Polytechnic Institute. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 12, pp. 38–41, December, 1992.     

Ordering processes and activation energy in Ni3Fe-based ternary alloys

The measurement of electrical resistance () has been used, to study the kinetics of isothermal ordering in the range 200 °–545 ° C in Ni₃(FeMn) alloy quenched from 970 ° C, and the kinetics of ordering at 390 ° C in the alloy quenched from various temperatures in the 600 °–800 ° C range. The sections method and the gradient of the (t) curves were used to find the activation energy for migration and vacancy formation in this alloy on the assumption that the excess vacancies frozen in the alloy by quenching at temperatures above T_c are responsible for ordering. The activation energies for vacancy formation and migration were respectively U₀ = 33 ± 3 kilocal/mole and U_m = 39 ± 4 kilocal/mole, which in total give the activation energy for diffusion Q = 72 ± 7 kilocal/mole in the alloy studied; this approximates to the activation energy for diffusion in pure nickel.     

Ordering energy and effective pair interaction in ordering alloys of noble metals

The energy characteristics of ordering alloys formed between two noble metals are considered by adopting the representation of interion paired interaction and the pseudopotential method proposed in an earlier paper. The asymptotic form of the potential associated with the indirect interaction of different pairs of ions is calculated for an alloy in which oscillations differing from those of the Friedel type occur. Expressions are obtained for the Fourier transform of the ordering energy of a binary alloy of noble metals and also for its asymptotic form.     

Ordering phenomena in C<Subscript>60</Subscript>-tetraphenylphosphonium bromide

The fulleride salt C₆₀-tetraphenylphosphonium bromide is investigated as a function of temperature by single crystal X-ray diffuse scattering and diffraction. At room temperature, the C₆₀ orientational disorder is found to be more complex than previously expected. Moreover, a structural phase transition, due to the C₆₀ orientational ordering, is evidenced around 120 K. Its relation with the stabilization of a static Jahn-Teller effect is discussed. Received 3 November 1999     

Antiferromagnetic Ordering of Magnetic Clusters Units in Nb6F15

We have studied the magnetic cluster compound Nb₆F₁₅ which has an odd number of 15 valence electrons per (Nb₆F₁₂)³⁺ cluster core, as a function of temperature using nuclear magnetic resonance, magnetic susceptibility, electron magnetic resonance and neutron powder diffraction. Nuclear magnetic resonance of the ¹⁹F nuclei shows two lines corresponding to the apical F^a?a nucleus, and to the inner Fⁱ nuclei. The temperature dependence of the signal from the Fⁱ nuclei reveals an antiferromagnetic ordering at T < 5 K, with a hyperfine field of ~2 mT. Magnetic susceptibility exhibits a Curie–Weiss behavior with T _N ~5 K, and μ _eff ~1.57 μ_B close to the expected theoretical value for one unpaired electron (1.73 μ_B). Electron magnetic resonance linewidth shows a transition at 5 K. Upon cooling from 10 to 1.4 K, the neutron diffraction shows a decrease in the intensity of the low-angle diffuse scattering below Q ~0.27 Å^?1. This decrease is consistent with emergence of magnetic order of large magnetic objects (clusters). This study shows that Nb₆F₁₅ is paramagnetic at RT and undergoes a transition to antiferromagnetic order at 5 K. This unique antiferromagnetic ordering results from the interaction between magnetic spins delocalized over each entire (Nb₆F ₁₂ ⁱ )³⁺ cluster core, rather than the common magnetic ordering.     

Electric field gradients at V,Nb and Ta in A15 alloys

The efg at V, Nb and Ta in all existing binary alloys with A15 structure has been calculated with the FLAPW technique. It is generally a result of counteracting p- and d-contributions from the conduction band, with a significant effect also of semicore states. For virtually all V and Nb compounds where experimental data are available, these are well reproduced, with the exception of Nb₃Sb. A critical test would be a measurement of the quadrupole interaction in the Ta alloys. This revised version was published online in August 2006 with corrections to the Cover Date.     

Magnetization of dilute Ag-Mn alloys: Ordering and absence of Kondo state

The magnetization of Ag-Mn alloys containing 100 ppm-4 ppm of Mn has been measured from 0.5 K down to 10 mK. For the high concentrations, ordering sets in at a temperature proportional to impurity concentration; there is no evidence for a spin-compensated Kondo state.