Journal of Alloys and Compounds 307 (2000) 174178

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The ternary system AuMnSn

Laila Offernes, Alexandra Neumann Torgersen, A. Kjekshus*
Department of Chemistry, University of Oslo, P.O. Box 1033, Blindern, N-0315 Oslo, Norway Received 18 February 2000; received in revised form 3 April 2000; accepted 5 April 2000

Abstract The phase relations in the AuMnSn system have been studied by powder X-ray diffraction, metallography, electron microprobe analysis, and thermal analysis. The condensed phases occurring, tie-lines and tie-triangles are presented for an isothermal section of the phase diagram at 4008C. At this temperature the solid solubility of the third component in the binary phases is generally limited to a few percent. The numerous phases in the binary AuMn system, are reected in relatively complex phase relations in certain parts of the AuMnSn system. The only genuine ternary phase, AuMnSn, has a narrow composition range between Au 35 Mn 31 Sn 34 and Au 33 Mn 35 Sn 32 and is stable up to ca. 4708C were it decomposes peritectically. 2000 Elsevier Science S.A. All rights reserved.
Keywords: AuMnSn system; Phase diagram; Limited solubility of third component; AuMnSn phase; Ternary intermetallic phase

1. Introduction This report concerns the mapping of the phase diagram for the ternary system AuMnSn, and it represents a continuation of investigations of ternary systems with Au, Sn and a transition element (T ) as the third component [15], and of our accounts of the crystal structure and ferromagnetic properties of AuMnSn [6,7]. Most of the AuT Sn (T5Pt, Cd, Cu, Ni, Co, Fe, Mn, Cr, Sc) systems studied so far have revealed genuine ternary phases with different stoichiometries and structural features [1,2,5,6,8 14]. Ternary AuT Sn systems have several points of interest, for example: (i) the components are found in electronic circuits [15]; (ii) the ternary phases that occur in such systems have interesting fundamental and / or technological applicable properties, AuMnSn may represent such an example; (iii) tin is a much used ux medium for crystal growth; (iv) knowledge of phase diagrams is essential to the engineering of materials; (v) systematic investigations of metallic systems may reveal factors governing structure and stability of intermetallic phases. As a background, it is convenient to recall relevant features of the binary phase diagrams AuMn, AuSn and MnSn. The AuMn system [16] contains nine binary phases and is relatively complex, especially in the composition range 2033.3 at.% Mn, compared to other AuT systems (T5Cu, Ni, Co, Fe, Cr) [17]. At high temperatures
*Corresponding author. Tel.: 147-22-855-560; fax: 147-22-855-565.

the solid-solution phases (Au) and (gMn) dissolves up to 31 at.% Mn (9608C) and 25 at.% Au (10958C), respectively. At 4008C, (Au) dissolves 18.5 at.% Mn and (aMn) less than 1 at.% Au. The congruently melting phase AuMn exists over the composition range 37.562.5 at.% Mn at 4008C, of which those with compositions between ca. 41 and 59 at.% Mn undergo martensitic transformations below 2428C [16]. The AuSn system [18] contains the solid phases (Au), Au 10 Sn, z, AuSn and two melt phases at 4008C. All binary phases have small or no signicant homogeneity ranges with exception of z which exists within the composition range 1216 at.% Sn at 4008C. The MnSn system [17,19] contains two Mn modications at 4008C, (aMn) and (bMn), with composition ranges 01 and 5.510 at.% Sn, respectively. In addition this system contains the phases Mn 3 Sn, Mn 3 Sn 2 , MnSn 2 and a Sn-rich melt at 4008C. Of these, Mn 3 Sn 2 and MnSn 2 are virtually stoichiometric, while Mn 3 Sn has a homogeneity range between 24 and 26 at.% Sn.

2. Experimental Samples were made by melting (heating at 1100 13008C for about 1 min under vigorous shaking) weighed amounts of 99.95% Au (Rasmussen), 99.98% Mn (Aldrich), and 99.95% Sn (Merck) in sealed, evacuated, silicaglass tubes. This initial heat treatment was concluded by quenching the samples from the molten state into water.

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With the exception of the more Mn-rich samples (.50 at.% Mn), the samples were then annealed for 330 days at 4008C and quenched into water. To avoid the recrystallization of the silica-glass through Mn-catalyzed formation of cristoballite, the Mn-rich samples were only partly melted in the initial heat treatment. The latter samples were subsequently crushed, resealed in evacuated silica-glass tubes and slowly melted (by gentle heating for 1015 min). After quenching in water, the samples were annealed at 6008C for 7 days to obtain equilibrium. This temperature was chosen because of the high melting temperatures in this region of the phase diagram and the existence of solid-state equilibria like the eutectoid reaction (gMn)AuMn 2 1(aMn) at 6608C [16]. Thereafter the samples were cooled from 600 to 4008C over a period of 42 days and annealed at this temperature for 21 days before quenching in water. The high partial pressure of Mn causes loss of this component and consequently a change in the nominal composition of the sample. The actual composition of the samples was therefore determined by electron microprobe analysis performed on several extended areas of metallographic cross-sections. The accuracy of this procedure clearly depends on the homogeneity of the sample. Owing to the high partial pressure of Mn and the recrystallization of the silica-glass ampoules, few samples with more than 75 at.% Mn were made, and the phase relations in certain parts of the Mn-rich region of the system should consequently be regarded more tentative. Specimens for powder X-ray diffraction (PXD) were obtained by crushing part of a given sample to a ne powder. For ductile samples ling and subsequent annealing at 3004008C for 24 h was necessary to obtain specimens suitable for PXD. All samples were checked for homogeneity and characterized by PXD using Guinier Hagg cameras with Cu Ka 1 radiation and Si as internal standard and / or Siemens AXS D5000 X-ray diffractometers. Unit-cell dimensions were obtained using the software EVA [20]. Differential thermal analysis (DTA) measurements were carried out using a PerkinElmer 7 Series Thermal Analysis System. Thirty- to 60-mg samples contained in sealed silica-glass ampoules were heated at a rate of 58C min 1 between 25 and 10008C. Metallographic cross-sections were obtained by mounting a specimen piece, selected as a vertical cross-section of the sample, in resin (Struers No. 3). Grinding was carried out under water cooling using silicon carbide paper, and polishing was done according to the Struers DP procedure. Optical microscopy was performed with a PME Olympus microscope. Composition analysis was performed using an automatic wavelength-dispersive CAMECA electron microprobe (MineralogiskGeologisk Museum, University of Oslo) tted with a LINK energy-dispersive system. Acceleration voltage of 20 keV, sample current of 20 nA and counting

time of 15 s were used. Pure metals of Au and Mn (freshly polished surface), and SnO 2 for Sn, were used as standards. Matrix corrections were performed by the PAP procedure in the CAMECA software. The analytical precision (2s ; evaluated on the basis of repeated analysis of individual grains) is better than 61%. A thin layer of carbon was evaporated on the metallographic specimens used for electron microprobe analysis.

3. Isothermal section at 4008C An illustration of the isothermal section of the AuMn Sn system at 4008C is shown in Fig. 1a with the experimentally determined (by metallography, electron microprobe analysis and / or comparisons of unit-cell dimensions) ranges of homogeneity, together with tie-lines and tie-triangles. At this temperature the system contains one ternary solid, 17 binary solid and two melt phases. Fig. 1b gives the locations of selected, relevant samples in the AuMnSn system, and different symbols are used to mark whether these are established as one-, two- or threephase samples at 4008C. The genuine ternary phase is designated AuMnSn even though it does not take the exact 1:1:1 stoichiometry at 4008C. The binary phases will be designated by their binary formulae (even though several show ranges of solid solubility in two compositional dimensions). Note that the z phase in the binary AuSn system, does not have an obvious, simple stoichiometry. The Au- and Sn-rich melt phases are designated L(Au) and L(Sn), respectively.

3.1. The terminal Au and Mn phases

(Au) dissolves at most ca. 18.5 at.% Mn and ca. 7.5 at.% Sn, (aMn) less than 1 at.% of each of Au and Sn and (bMn) less than 1 at.% Au. The (Au) phase takes the Cu-type f.c.c. structure, while at 4008C the (Mn) phases take the cubic aMn- and bMn-type structures [21]. The solid-solubility range of the terminal phases also increases with increasing temperature into the ternary dimension.

3.2. The AuSn phases

Generally the binary AuSn phases show little solid solubility of Mn. At 4008C Au 10 Sn, z and AuSn dissolves 3, 4 and less than 1 at.% Mn, respectively. The hexagonal Ni 3 Ti- and Mg-type structures of Au 10 Sn and z are closely related [4]. The AuSn phase takes the NiAs-type structure [4]. There are some uncertainty concerning the phase relations in the surrounding of the phases Au 10 Sn and z, owing to the similarity of the two crystal structures and their closeness in chemical composition. Two characteristic reections from Au 10 Sn are, e.g. not observed in the PXD diagram for a three-phase sample with nominal composition Au 820 Mn 040 Sn 140 . In addition to (Au) and

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Fig. 1. (a) Isothermal cross-section of the AuMnSn system at (or near) 4008C. One-phase regions are shown as black areas, two-phase regions by tie lines and three-phase elds are represented by open tie triangles. The ternary phase, AuMnSn, is marked A, whereas several of the binary AuMn phases are not named on the illustration in order to facilitate its readability. (b) Locations of selected (relevant) samples in the AuMnSn system. Black, grey and open circles represent samples containing one, two, and three phases, respectively, after annealing at 4008C.

L(Au) this sample is therefore assumed to contain z as the third phase. Since this result are not unambiguous the phase relations in this region of the phase diagram (Fig. 1) have been indicated by broken lines.

3.3. The AuMn phases

Generally the binary AuMn phases show little solid solubility of Sn. The phases Au 4 Mn, Au 33 Mn 9 , Au 13 Mn 4 and Au 3 Mn all dissolve ca. 2 at.% Sn and AuMn 2 dissolves ca. 1 at.% Sn. The symmetries of the structures of these phases are tetragonal (MoNi 4 type), monoclinic, orthorhombic, orthorhombic and tetragonal (MoSi 2 type), respectively [16]. The AuMn phase takes the CsCl-type structure [16], and this phase dissolves up to 5 at.% Sn at 4008C. Spot checks indicate that AuMn dissolves considerably more Sn at higher temperatures. DTA conrms the expected drop in liquidus temperature from the congruently melting AuMn phase to the terminal Sn phase. A two-phase eld exist above ca. 4708C between AuMn and L(Sn), extending to ca. 65 at.% Sn. Fig. 2 shows a blow-up of the Au-rich region of the AuMnSn system.

Sn phase diagram at 4008C (Fig. 1a), dissolve little Au (at most 1 at.%). As indicated by the broken lines in Fig. 1, the composition ranges of these phases and the phase relations in the Mn-rich region of the AuMnSn phase diagram should be regarded as more tentative than the rest of the diagram.

3.5. The melt phases

Two separate melt phases occur in the AuMnSn system at 4008C (Fig. 1); L(Au) which extends from 26 to 45 at.% Sn in the AuSn dimension, and L(Sn), extending from 56 to 100 at.% Sn in the AuSn dimension and from 95 to 100 at.% Sn in the MnSn dimension [17,18]. L(Au) dissolves less than 1 at.% Mn, while the Mn content in L(Sn) decreases gradually from 5 at.% Mn at the Sn-rich end to 0 at.% Mn at the Sn-poor end. The extensions of the melt regions were determined by metallography and electron microprobe analysis on

3.4. The MnSn phases

The MnSn 2 and Mn 3 Sn 2 phases show a solid solubility of ca. 1 at.% Au and take the tetragonal Al 2 Cu-type and the orthorhombic Co 3 Sn 2 -type structures, respectively [19,22]. The Mn 3 Sn phase dissolves up to 5 at.% Au at 4008C and takes the hexagonal Ni 3 Sn-type structure [23]. The composition range in the MnSn dimension declines gradually with increasing Au content. The two Mn modications, (aMn) and (bMn), which occur in the AuMn

Fig. 2. A blow up of the Au-rich part of the AuMnSn system at 4008C.

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solidied melts. When a sample, which is partly molten at 4008C, is quenched, the melt solidies as a nely grained matrix which is detectable by optical and electron microscopy. The matrix representing the L(Au) phase was easily identied. However, quenched samples containing the L(Sn) phase, show less difference between the primary disengaged crystals and the solidied melt phase. This reduces the analytical precision.

3.6. The AuMnSn phase

At 4008C the ternary phase AuMnSn has a narrow composition range between Au 35 Mn 31 Sn 34 and Au 33 Mn 35 Sn 32 . DTA measurements show that AuMnSn is stable up to ca. 4708C were it decomposes peritectically to AuMn and L(Sn). AuMnSn takes the cubic AlLiSi-type ] structure with space group F43 m and a5632.33(1) pm at 150(2) K and a5633.8(1) pm at 298 K [6]. Furthermore AuMnSn is a typical soft ferromagnetic material with a saturation moment of 3.8 mB per Mn atom at 5 K [6,7] and a relatively poor metallic-type conductor (L. Offernes, A.N. Torgersen, J. Snyder, A. Kjekshus, unpublished data).

rather incomplete. The partial phase diagrams for AuMn Sb [26,34] and PtMnSn [27] show narrow homogeneity ranges for the ternary 1:1:1 phase, similar to the ndings for AuMnSn. Moreover, also AuMnSb and PtMnSn take the AlLiSi-type structure [26,27,35]. Compared to the binary gold systems with Cr, Fe, Co, Ni and Cu, which are relatively simple with few binary phases, the AuMn system is comparatively complex and more similar to gold systems with Mg, Ca, Zn and Cd which contain several binary phases including a high- and congruently melting 1:1 phase [17]. It may not be accidental that Heuslerrelated 1:1:1 phases of these lled shell elements (in relation to the half-lled d shell of Mn) are found in the AuMgSn and AuCdSn systems [9,14].

Acknowledgements The authors are grateful to Dr. Muriel Erambert and Dr. Haakon Austrheim (both at Mineralogisk-Geologisk Museum, University of Oslo) for assistance with the microprobe analysis. A.N.T. appreciates the nancial support from the Research Council of Norway.

4. Concluding considerations At 4008C the ternary AuMnSn system is characterized by one genuine ternary phase, several binary phases and two melt phases with narrow composition ranges. The binary phases show only a minor degree of solid solubility for the third element. The size difference between the three elements is relatively large (atomic radii [CN512] for Au, Mn and Sn are 144.2, 126.4 and 154.5 pm, respectively [24]), and this alone can explain the limited mutual solid solubility. However, the AuMnSn system contains two NiAs-related phases; AuSn (NiAs-type structure) and Mn 3 Sn 2 (Co 3 Sn 2 -type structure). NiAs-type and NiAsrelated structures are known to tolerate large degrees of non-stoichiometry and solid solubility. In the systems Au CuSn, AuNiSn and AuCoSn there are found full or partial (the latter system) solid solubility between AuSn and Cu 6 Sn 5 , Ni 3 Sn 2 and Co 3 Sn 2 , respectively [1,3,4]. The lack of appreciable solid solubility between AuSn and Mn 3 Sn 2 thus deviates from this pattern. This cannot be explained as a size effect since the atomic radius of Mn (CN512) is of the same size as the radii of Cu, Ni and Co and neither can it be an electronegativity effect. However, the difference in metallic valences between Mn on the one hand and Cu, Ni and Co on the other could provide a reason for the distinction. Since the AuMnSn phase belongs to a class of Mn-based Heusler-related alloys with general formula T MnX (X5Sb, Sn) [2533], it would be natural to compare the AuMn Sn phase diagram with the phase diagrams of other T MnX systems. However, few of such systems have been systematically studied and the available phase diagrams are References
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