TO OBTAIN,
- A LIST OF ALL THE UNARY, BINARY AND TERNARY SYSTEMS WHICH HAVE BEEN ASSESSED
- A LIST OF ALL ASSESSED PHASES IN EACH OF THE SYSTEMS
- A CALCULATED PHASE DIAGRAM FOR EACH OF THE LISTED BINARY SYSTEMS
- A CALCULATED PHASE DIAGRAM FOR EACH OF THE LISTED TERNARY SYSTEMS
- ASSISTANCE WITH PHASE SELECTION
CLICK ON "List of optimized systems and calculated binary phase diagrams."
General
The SGsold - SGTE Solder alloy phase database 2009 is based on the COST 531 project. This documentation contains as a supplement the calculation of significant ternary systems.
The 11 elements included in the database are,
Ag, Au, Bi, Cu, In, Ni, Pb, Pd, Sb, Sn, Zn
From among these elements, there are some 53 completely assessed binary alloy systems. The database also includes 20 ternary systems and a large number of special isothermal sections for which assessed parameters are available for phases of practical relevance.
The systems now incorporate approximately 67 different solution phases and 74 stoichiometric intermetallic compound phases.
This version of the SGTE Solution Database thus represents a significantly upgraded general alloy database. The database is intended to provide a sound basis for calculations relating to the production, heat treatment, constitution, and application of a wide range of alloy types.
All the assessed binary systems included in the SGTE alloy database are described over all ranges of composition and temperature, i.e. the assessed data provide a good description of the complete phase diagrams and thermodynamic properties for the binary alloy systems concerned.
Although a large number of ternary interaction parameters are included for the different phases in the database, these are in many cases associated only with phases rich in a particular metal. As such, care should be exercised in calculating phase equilibria for other composition ranges of multi-component alloys. By referring to the listing of systems and phases for which assessed parameters are available, the user can determine whether proposed calculations for a particular higher-order system will be based on a complete set of assessed binary and ternary parameters (at best) or summation of binary parameters only (at worst). Clearly the latter case, or use of incompletely assessed data sets, can lead to incorrect or unreliable results.
In a binary system, if no assessed mixing parameters are available for a particular phase, the phase will be treated as ideal. Correspondingly, the properties of a ternary or higher-order phase will be calculated applying the appropriate models used in the database. This procedure may give useful results if the alloy compositions in question are close to a pure component or to a binary edge for which assessed data are available. However, results of calculations for other composition ranges should be treated with extreme caution.
Composition Ranges
The database is intended to allow calculation over all ranges of composition, although, as mentioned above, the assessed data are often most reliable for metal-rich composition ranges.
Temperature Ranges
The database is generally most reliable for the temperature range of approximately 200oC to 2000oC, although the assessed data for some alloys containing high melting point metals are reliable to still higher temperatures.
Modeling
In the assessments, the liquid phase has been described using a simple substitutional solution approach based on the Redlich-Kister-Muggianu polynomial expression. Most of the solid phases have been described using sublattice models which include interstitials and vacancies where appropriate.
Use of the Database
The phase diagrams of all the binary and ternary systems listed above have been checked using FactSage.
If there is the possibility of a miscibility gap (or 2 miscibility gaps) occurring in the LIQUID, FCC, BCC or HCP phase, the I-option (J-option) must be used in selecting that phase for the calculations.
The I-option also needs to be used with the ordered solid solutions, B2_BCC, which are based on the BCC disordered state (see below).
With this database it is strongly recommended to always select the option permitting one-component solutions to be selected. This is done in the reactants window of the Equilib or Phase Diagram module by clicking on,
Data Search -> minimum solution components = 1
In FactSage the database has been modified to simplify the selection of species when the Equilib or Phase Diagram modules are being used. Phases which are not possibly relevant to the calculation at hand will not appear on the menu window. Furthermore, if one now simply selects all the solution phases and all the pure solid phases from SGsold which appear on the menu window, a correct calculation will result in most cases, with the I- or J-option (for possible immiscibility) automatically selected if possibly required.
References for SGsold - SGTE Solder alloy phase database 2009
Binary Systems
Ag-Au
The Ag‐Au system has a simple isomorphous phase diagram showing complete
solid solubility over the whole composition range. The data are taken from
the assessment of Hassam et al. [88Has].
References:
[88Has] Hassam, S., Gambino, M., Gaune‐Escard, M., Bros, J. P., Agren, J.: Metall.
Trans. 1988, 19A, 409‐416.
Ag-Bi
This system exhibits a simple eutectic type phase diagram with very limited
solubilities in terminal solid solutions at lower temperatures. The theoretical
description is from the assessment of Lukas [98Luk] based on Zimmermann’s
original work [76Zim].
References:
[76Zim] Zimmermann, B.: “Rechnerische und experimentelle Optimierung
von binären und ternären Systemen aus Ag, Bi, Pb und Tl”, thesis,
Universität Stuttgart, Germany, 1976.
[98Luk] Lukas, H.‐L., Zimmermann, B.: Unpublished work, 1998.
Ag-Cu
The adopted assessment for the Ag‐Cu system is an update from Lukas
[98Luk] of his earlier published assessment [77Hay].
References:
[77Hay] Hayes, F. H., Lukas, H. L., Effenberg, G., Petzow, G.: Z. Metallkde. 1986,
77, 749‐754.
[98Luk] Lukas, H.‐L.: Unpublished work, 1998.
Ag-In
Assessed data for this system were taken from [01Mos]. However, the model
used for the ‐phase (Ag In) was changed to make it compatible with that 2
utilized for the ‐phase in the Cu‐In system (CUIN_GAMMA). This was
necessary as complete solubility between the two binary phases exists in the
Ag‐Cu‐In ternary system [88Woy]. The original work of [01Mos] also ignored
the high‐temperature ‐phase (BCC_A2), which exists over a very limited
temperature range. The description of this BCC‐phase was added to
the assessment in the scope of the COST 531 Action so that the liquidus surface
could be modelled correctly. The presence of this phase leads to extra invariant
reactions at high‐temperatures that correspond to the metatectic decomposition of
BCC_A2 to the HCP_A3 phase and at the liquid and to the peritectoid reaction
FCC_A1 + BCC_A2 —> HCP_A3.
References:
[88Woy] Woychik, C. G., Massalski, T. B.: Met. Trans. A., 1988, 19A, 13‐21.
[01Mos] Moser, Z., Gasior, W., Pstrus, J., Zakulski, W., Ohnuma, I., Liu, X. J.,
Inohana, Y., Ishida, K: J. Electron. Mater., 2001, 30, 1120‐1128.
Ag-Ni
The data for this system have been critically assessed within the scope of the
COST 531 Action based on the experimental data from Tammann and Oelson
[30Tam], Stevenson and Wulff [61Ste], Borukhin and Khayutin [74Bor],
Burylev and Ivanova [74Bur], Popel and Kozhurkov [74Pop], Ladet et al. [76Lad],
Siewert and Heine [77Sie] and Xu et al. [96Xu].
Experimental work prior to 1987 has been reviewed by Singleton and Nash [87Sin].
New experimental data by Schmetterer et al. [07Sch] have yet to be incorporated.
References:
[30Tam] Tammann, G., Oelson, W.: Z. Anorg. Chem., 1930, 186, 264‐266.
[61Ste] Stevenson, D. A., Wulff, J.: Trans. Metall. Soc., AIME 1961, 221, 271‐275.
[74Bor] Borukhin, L. M., Khayutin, S. G.: Strukt. Faz. Fazovye Prevrashch.
Diagr. Sostoyaniya Met. Sist., 1974, 172‐174.
[74Bur] Burylev, B. P., Ivanova, V. D.: Tr. Krasnodar. Politekh. Inst., 1974, 63,
111‐113.
[74Pop] Popel, S. I., Kozhurkov, V. N.: Izv. Akad. Nauk SSSR, Met., 1974, 2, 49‐52.
[76Lad] Ladet, J., Beradini, J., Cabane‐Brouty, F.: Scr. Metall., 1976, 10, 195‐199.
[77Sie] Siewert, T. A., Heine, R. W.: Metall. Trans. A, 1977, 8A, 515‐518.
[87Sin] Singleton, M., Nash, P.: Bull. Alloy Phase Diagrams, 1987, 8, 119‐121.
[96Xu] Xu, J., Herr, U., Klassen, T., Averback, R. S.: J. Appl. Phys., 1996, 79,
3935‐3945.
[07Sch] Schmetterer, C., Flandorfer, H., Ipser, H.: Acta Mater. ,2008, 56, 155‐164.
Ag-Pb
The most recent data for this simple eutectic system come from [00Luk].
The system is characterised by a wide region of solid state immiscibility
between the two component elements, their mutual solid solubility being very
limited. This dataset is based on original work by [76Zim].
References:
[76Zim] Zimmermann, B.: “Rechnerische und experimentelle Optimierung
von binären und ternären Systemen aus Ag, Bi, Pb und Tl”, thesis,
Universität Stuttgart, Germany, 1976.
[00Luk] Lukas, H.‐L..: Unpublished work, 2000.
Ag-Pd
The data for this system are from the assessment of Ghosh et al. [99Gho]. The
Data imply a miscibility gap in the FCC_A1 phase at low temperatures.
The partial and integral enthalpies of mixing were determined at 1400 °C
by Luef et al. [05Lue] but have yet to be incorporated into the assessment.
References:
[99Gho] Ghosh, G., Kantner, C., Olson, G.‐B.: J. Phase Equilb., 1999, 20, 295‐308.
[05Lue] Luef, Ch., Paul, A., Flandorfer, H., Kodentsov, A., Ipser, H.: J. Alloys
Compd., 2005, 391, 67‐76.
Ag-Sb
The data for the Ag‐Sb system are taken from a recent assessment by Zoro et al.
[07Zor] carried out within the framework of COST 531 and based on their
new experimental data. The calculated diagram is broadly similar to that from
the earlier assessment of Oh et al. [96Oh]. The solubility of Ag in solid Sb has been
ignored.
References:
[96Oh] Oh, C. S., Shim, J. H., Lee, B. J., Lee, D. N.: J. Alloys Compd., 1996, 238,
155‐166.
[07Zor] Zoro, E., Servant, C., Legendre, B.: J. Phase Equil. Diff.: 2007, 28, 250‐257.
Ag-Sn
The data for the Ag- Sn system are taken from
the assessment of Oh et al. [96Oh].
The data for the FCC_A1 phase have been remodelled within the scope of the COST 531
project to be compatible with the adopted data for FCC_A1 (Sn) [SGTE4].
The Gibbs energy expression of the liquid phase was reoptimised using the raw enthalpy
of mixing data from Flandorfer [05Fla] in addition to the other experimental data
compiled by Chevalier [05Che].
References:
[96Oh] Oh, C.‐S., Shim, J.‐H., Lee, B.‐J., Lee, D. N.: J. Alloys Compd., 1996, 238,
155‐166.
[05Che] Chevalier, P. Y.: Unpublished work, 2005.
[05Fla] Flandorfer, H.: Unpublished work, 2005.
Ag-Zn
The data for this system are from an unpublished assessment by Fries and
Witusiewicz [02Fri]. This is a more rigorous modelling of the system than
documented in their later published data assessment [06Wit].
References:
[02Fri] Fries, S. G., Witusiewicz V. T.: Unpublished work, 2002.
[06Wit] Witusiewicz, V. T., Fries, S. G., Hecht, U., Drevermann, A., Rex, S.: Int.
J. Mater. Res., 2006, 97, 556‐568.
Au-Bi
The data for this system ara taken from a recent assessment by Servent et al. [06Ser] carried out within the framework of COST 531 using new experimental
data [05Zor]. The major difference between this assessment and that of
Chevalier [88Che] is the revised solubility of Bi in Au (FCC_A1) and the
temperature of the invariant reaction, AU2BI_C15 → FCC_A1 + RHOMBO_A7.
The new theoretical description is in better agreement with the experimental
data.
References:
[88Che] Chevalier, P. Y.: Thermochimica Acta, 1988, 130, 15‐24.
[05Zor] Zoro, E., Boa, D., Servant, C., Legendre, B.: J. Alloys. Compd., 2005, 398,
106‐112.
[06Ser] Servant, C., Zoro, E., Legendre, B.: CALPHAD, 2006, 30, 443‐448.
Au-Cu
Data for the Au‐Cu system are taken from the critical assessment of
Sundman et al. [98Sun]. The authors presented two datasets in their
publication, the first taking into account and modelling the low temperature
chemical ordering phases derived from a FCC lattice and the second dataset
ignoring the chemical ordering. The second dataset has been selected for
the COST 531 database, as this feature does not have a significant influence in
the systems for lead free solders.
References:
[98Sun] Sundman, B., Fries, S. G., Oates, W. A.: CALPHAD, 1998, 22, 335‐354.
Au-In
There are a number of assessments of this system in the scientific literature,
the major differences between them being associated with the homogeneity
range of the DHCP phase in the Au‐rich side of the system and its
decomposition with decreasing temperature. The data accepted for this work
was taken from [03Liu] in order to be compatible with experimental data
available for the Au‐In‐Sn ternary system. The phase diagram is highly complex
with many intermetallic compounds. Owing to this complexity, it was not
possible to label all phases in figure; the unlabelled phase at x(In) ∼ 0.2 is
AUIN_BETA. The AU3IN (ε) phase was modelled as a single stoichiometric
phase, whereas two variants have been reported experimentally; and the low
temperature variant ’. An ordering reaction between the two phases takes
place at approximately 339.5 °C [MAS].
References:
[03Liu] Liu, H. S., Cui, Y., Ishida, K., Jin, Z. P.: CALPHAD, 2003, 27, 27‐37.
Au-Ni
Data for the Au‐Ni system are taken from a recent
assessment by Wang et al. [05Wan].
This agrees much better with experimental data for the system than earlier
assessments [99Mor], [05Liu]. Use of the new data did not adversely affect agreement
between calculated and experimental properties for the ternary Au-Ni-Sn system which had
been based on the assessment of Liu et al. [05Liu].
References:
[99Mor] Morioka, S., Hasebe, M.: J. Phase Equil., 1999, 20, 244‐257.
[05Liu] Liu, X. J., Knaka, M., Takaku, Y., Ohnuma, I., Kainuma, R., Ishida, K.: J.
Electron. Mater., 2005, 34, 670‐679.
[05Wan] Wang, J., Lu, X.‐G., Sundman, B., Su, X.: CALPHAD, 2005, 29, 263‐268.
Au-Pb
The dataset for this system was taken from v.4.4 of the SGTE solution database
[SGTE], and the source of this data is the thesis of Nabot [86Nab]. The system
is fairly simple and contains three peritectically forming intermetallic
compounds, each one being modelled as a stoichiometric phases. According
to [MAS], there is some uncertainty as to the temperature range over which
the AUPB3 phase is stable. There are reports that it decomposes below 52 °C.
References:
[86Nab] Nabot, J.‐P.: Thesis, LTPCM, Grenoble, France, 1986.
Au-Pd
The Au‐Pd system has a simple isomorphous phase diagram showing complete
solid solubility over the whole composition range. The thermodynamic data for
this system was taken from the v.4.4 of the SGTE solution database [SGTE].
Ordering in the solid state has been confirmed at compositions of Au3Pd, AuPd
and AuPd3 [MAS], but it has not been modelled here.
Au-Sb
The data for the Au‐Sb system were taken from a recent assessment by Zoro et al.
[07Zor] which incorporated earlier assessed data from Kim et al. [02Kim].
Zoro et al. found that the assessment of Kim et al. was in better agreement with
experimental measurements of phase equilibria they had carried out than an
earlier assessment of Chevalier [89Che].
References:
[89Che] Chevalier, P. Y.: Thermochimica Acta, 1989, 155, 211‐225.
[02Kim] Kim, J. H., Jeong, S. W., Lee, H. M.: J. Electron. Mater., 2002, 31, 557‐563.
[07Zor] Zoro, E., Servant, C., Legendre, B.: J. Phase Equil. Diff., 2007, 28, 250‐257.
Au-Sn
The critically assessed data for the Au‐Sn system from Liu et al. [03Liu1] were
adopted for the COST 531 database because of their compatibility with data
selected for the Au‐In system [03Liu2] and in particular with data for the
AUIN_ALPHA phase which is isomorphous with the Au10Sn phase. The data
for the Au‐Sn system were adjusted to be consistent with adopted unary data
for Sn in the HCP_A3 and FCC_A1 phases.
References:
[03Liu1] Liu, H. S., Liu, C. L., Ishida, K., Jin, Z, P.: J. Electron. Mater., 2003, 32,
1290‐1296.
[03Liu2] Liu, H. S., Cui, Y., Ishida, K., Jin, Z. P.: CALPHAD, 2003, 27, 27‐37.
Au-Zn
The Au‐Zn phase diagram is exceedingly complex and is characterised by
a cascade of peritectic reactions on the zinc side of the diagram. There are
13 intermetallic phases (11 of which have been modelled) including
an ordered bcc phase (AUZN_BETA) and a γ‐brass phase (AUZN_BRASS). There
are reports that the ordered bcc phase undergoes a low temperature transition
[MAS] but this is not modelled here. The α’2 phase given in [MAS] has also been
ignored in the present work. The dataset chosen for this work comes from
[03Liu] with modifications being made to the data for the AUZN_G3 phase to
make it compatible with other hcp phases in the database, and to the data the data for the AUZN_BETA phase in order to remove a very narrow unrealistic miscibility gap that appears during calculation. Owing to the
complexity of the phase diagram, two of the intermetallics have not been
labelled. These are AU4ZN5 at x(Zn)=0.56 and AUZN6 at x(Zn)=0.85.
The crystallography of many of the intermetallic phases in this system still
remains a mystery and hence it has been convenient to model many of them
as stoichiometric compounds.
Owing to pure Zn having a different c/a ratio from other elements with the hcp
structure, it is modelled as a different phase and is labelled HCP_ZN.
References:
[03Liu] Liu, H. S., Ishida, K., Jin, Z. P., Du, Y.: Intermetallics, 2003, 11, 987‐994.
Bi-Cu
The Bi‐Cu system is a simple eutectic system showing virtually no mutual solubility
of the component elements. The thermodynamic description is taken from [89Tep].
References:
[89Tep] Teppo, O., Niemela, J., Taskinen, P.: Report TKK‐V‐B50, 1989, Helsinki
University of Technology.
Bi-In
The data from Boa and Ansara [94Boa] were accepted for most of the phases
in the system. A reassessment of the ε‐BiIn phase was necessary, as this phase
is isomorphic from the crystallographic point of view with the In‐Pb phase,
named TET‐ALPHA1 in the database. New parameters were also derived
within the scope of COST 531 Action since different unary data for the pure
elements in this phase were used by [94Boa] from those selected from the
COST 531 database. Very good agreement was reached, both in the terms of the temperatures of the invariant reaction and range of homogeneity of the
TET_ALPHA1 phase, using the old and new descriptions.
References:
[94Boa] Boa, D., Ansara. I.: Thermochim. Acta, 1998, 314, 79‐86.
Bi-Ni
Data for the Bi‐Ni system were assessed by Vassilev et al. [07Vas] within the
scope of the COST 531 Action. This assessment incorporated new experimental
data for the activity of Bi in the liquid phase and so required a re‐evaluation
of an earlier assessment [05Vas].
References:
[05Vas] Vassilev, G. P., Liu, X. J., Ishida, K.: J. Phase Equilib. Diffus., 2005, 26,
161‐168.
[07Vas] Vassilev, G. P., Romanowska, J., Wnuk, G.: Int. J. Mat. Res., 2007, 98,
468‐475.
Bi-Pb
The Bi‐Pb system exhibits both a eutectic reaction and the peritectic formation
Of an intermetallic HCP phase. A considerable amount of Bi may dissolve in
crystalline Pb but there is negligible solubility for Pb in crystalline Bi.
The thermodynamic description for this system is taken from [98Boa] quoting
private communication with H.L. Lukas.
References:
[98Boa] Boa D., Ansara, I.: Thermochim. Acta, 1998, 314, 79‐86.
Bi-Pd
Several versions of the Bi‐Pd phase diagram are available in the literature, the
main difference between them being associated with the Pd‐rich equilibria.
Little work has been carried out on this part of the system and so it is relatively
unknown. Also, no thermodynamic assessment of this system had been carried
out prior to COST 531, which made the Bi‐Pd system subject to extensive study
during the Action. According to [MAS], there are 6 intermetallic phases in the
system, 3 of which have high and low‐temperature modifications. The Bi‐rich
α,β‐Bi2Pd phase (BI2PD) has a narrow homogeneity range, and it is unclear whether
it forms congruently or peritectically from the liquid. The remaining phases
are present as line compounds apart from the γ‐phase (BI3PD5) which exists
as a ‘triangular’ phase field over approximately 6 at% but only from about
400 – 683 °C, although the lower temperature limit for this phase is uncertain.
As part of the study undertaken under COST 531, enthalpies of mixing of liquid
alloys were determined by high‐temperature solution calorimetry for
compositions from 0 – 50 at% Pd at 1028K, and enthalpies of formation of the
BI2PD and BIPD intermetallic phases were determined by ab initio methods.
Selected DTA and SEM studies were carried out on alloys in the Pd‐rich region
of the diagram in order to ascertain the phase relationships in the unknown part
of the system. The experimental data were used in conjunction with phase
diagram information taken from the literature to perform a thermodynamic
assessment of the system. Some simplifications were made in that the distinction
between high and low‐temperature modifications of the phases was ignored,
as were the Bi2Pd5 and Bi12Pd31 phases owing to uncertainties in their stability.
Reference to these two phases is found only in the work of [79Sar]. However, these phases were not found in the present experimental study, and
hence they were not included in the optimisation. The experimental details,
results and the modelling are presented in [06Vre].
The calculated phase diagram shows the ‘degenerate’ nature of the melting of BI2PD.
As a result of the experimental study, the melting of BIPD3 is now as congruent rather
than incongruent as presented in [MAS]. The y-phase (BI3PD5) has now a much larger
temperature stability range.
References:
[79Sar] Sarah, N., Schubert, K.: J. LessCommon Met., 1979, 63, P75‐P82.
[06Vre] Vřešťál, J., Pinkas, J., Watson, A., Scott, A., Houserová, J., Kroupa, A.:
CALPHAD, 2006, 30, 14‐17.
Bi-Sb
DATA for this system were assessed by Ohtani and Ishida [94Oht]. The data were
checked for consistency in the scope of the COST 531 Action and no discrepancies
were found. This system exhibits the wide mushy zone between the LIQUID and
RHOMBO_A7 phase and also a RHOMBO_A7 miscibility gap at lower temperatures.
References:
[94Oht] Ohtani, H., Ishida, K.: J. Electron. Mater., 1994, 23, 747‐755.
Bi-Sn
The existing assessed data for the system by Ohtani et al. [94Oht] and
Lee et al. [96Lee] were modified to reduce the solubility of Bi in BCT_A5 (Sn).
The previously assessed very high solubility of Bi in BCT_A5 (Sn) (approx.
10 at% of Bi) was based on old data of Nagasaki and Fujita [52Nag]. Since
then, newer experimental results [07Viz, 07Bra] indicate a significantly lower
solubility of Bi in BCT_A5 (Sn). The relevant change in the phase diagram
required a change of both LIQUID and BCT_A5 data. The new reassessment
was carried out in the scope of the COST 531 Action and published in [07Viz].
References:
[52Nag] Nagasaki, S., Fujita, E.: J. Jpn. Inst. Met., 1952, 16, 317.
[58Oel] Oelsen, W., Golücke, K. F.: Arch. Eisenhüttenw., 1958, 29, 689.
[94Oht] Ohtani, H., Ishida, K.: J. Electron. Mater., 1994, 23, 747.
[96Lee] Lee, B. J., Oh, C. S., Shim, J. H.: J. Electron. Mater., 1996, 25, 983.
[07Bra] Braga, M. H., Vízdal, J., Kroupa, A., Ferreira, J., Soares, D., Malheiros,
L. F.: CALPHAD, 2007, 31, 468‐478.
[07Viz] Vízdal, J., Braga, M. H., Kroupa, A., Richter, K. W., Soares, D., Malheiros,
L. F., Ferreira, J.: CALPHAD, 2007, 31, 438‐448.
Bi-Zn
Several authors have assessed the Bi‐Zn system – e.g. Malakhov [00Mal],
Oleari et al. [55Ole], Bale et al. [77Bal], Girard [85Gir] and Wang et al. [93Wan]. Kim and Sanders [03Kim] attempted to describe proberly the segregation region in the
liquid, using two L interaction parameters only instead of six used by Malakhov.
Unfortunately, their des descriptions are not mutually consistent. The data from
Malakhov [00Mal] were used for this system, based on the conformity were with experimental data.
Some unary parameters are not consistent with the [SGTE4] database and therefor
changes were introduced and new value of unary data for Bi in HCP_ZN phase from
work of Moelans [03Moe] was accepted. The phase diagram was reassessed by Vízdal et al. [07Viz].
References:
[55Ole] Oleari, L., Fiorani, M., Valenti, V.: La Metallurgia Italiana, 1955, 46,
773.
[77Bal] Bale, C. W., Pelton, A. D., Rigaud, M.: Z. Metallkd., 1977, 68, 69‐74.
[85Gir] Girard, C.: “Fonctions d’exces et diagrammes d’equilibre des phase de
quatre systemes metalliques ternaires“, Ph.D. Thesis, Universite de
Provence, Marseille, 1985.
[93Wan] Wang, Z. C., Yu, S. K., Sommer, F.: J. Chimie Phys. PhysicoChimie Biol.,
1993, 90, 379‐385.
[00Mal] Malakhov, D. V.: CALPHAD, 2000, 24, 1‐14.
[03Kim] Kim, S. S., Sanders, T. H. Jr.: Z. Metallkd., 2003, 94, 390‐395.
[03Moe] Moelans, N., Kumar, K. C. H., Wollants, P.: J. Alloy. Compd., 2003, 360,
98‐106.
[07Viz] Vízdal, J., Braga, M. H., Kroupa, A., Richter, K. W., Soares, D., Malheiros,
L. F., Ferreira, J.: CALPHAD, 2007, 31, 438‐448.
Cu-In
The Cu‐In system as presented in [MAS] is quite complex containing
9 intermetallic phases, all of which appear at In contents of less than 50 at%.
The most complex of these is the ‘η’ phase, which is shown as a cascade, or
bundle of polymorphs. More recent experimental work undertaken by [93Bol],
reduced this collection of phases to just two, which were labelled as η (CUIN_ETAP), the low temperature variant, and η ’(CUIN_ETA) being stable
over a higher temperature range. The thermodynamic description of this
system was taken from the ternary assessment of the Cu‐In‐Sn system
presented by [01Liu] (although the Cu‐In binary assessment was published
later in [02Liu]. For some reason, the order of the two phase names were
switched in [01Liu] with respect to [02Liu]; the high temperature phase in the
former work being labelled η , whereas in the latter work (and also in [93Bol])
it was labelled η’. In the modelling, the higher temperature variant is described
by a 3 sublattice model giving the phase a homogeneity range, unlike the lower
temperature phase which is treated as a line compound. For the purposes
of simplification, the η‐phase (CUIN_DELTA) is also treated as a line compound
here, despite it having a measured homogeneity range of about 1.5 at% [MAS].
References:
[93Bol] Bolcavage, A., Chen, S.W., Kao, C.R., Chang, Y.A.: J. Phase Equilib., 1993,
14, 14‐21.
[01Liu] Liu, X.J., Liu, H.S., Ohnuma, I., Kainuma, R., Ishida, K., Itabashi, S.,
Kameda, K., Yamaguchi, K.: J. Electron. Mater., 2001, 30, 1093‐1103.
[02Liu] Liu, H.S., Liu, X.J., Cui, Y., Wang, C.P., Ohnuma, I., Kainuma, R., Jin, J.P.,
Ishida, K.: J. Phase Equilib., 2002, 23, 409‐415.
Cu-Ni
The data for this system from the assessment of an Mey, published in the
COST507 database [92Mey], were accepted for the COST 531 database. The
theoretical dataset was tested for the consistency and no disagreement was
found. A miscibility gap exists in the FCC_A1 phase in this system.
References:
[92Mey] an Mey, S.: CALPHAD, 1992, 16(3), 255‐260.
Cu-Pb
The most prominent feature of the Cu‐Pb phase diagram is the monotectic reaction
leading to phase separation in the liquid phase. There is negligible mutual solid
solubility between Cu and Pb. The dataset used here is taken from [86Hay].
As Cu and Pb have the same crystal structure, they have been treated with
a single Gibbs energy expression.
References:
[86Hay] Hayes, F.H., Lukas, H.‐L., Effenberg, G., Petzow, G.: Z. Metallkde., 1986,
77, 749‐754.
Cu-Pd
The Cu‐Pd system is a simple isomorphous system showing complete solid solubility for all compositions across the phase diagram. The thermodynamic
parameters for this system were taken from [91Sub], with minor modifications
being made to improve the agreement between the calculated and
experimentally determined phase boundaries.
References:
[91Sub] Subramanian, P.R., Laughlin, D.E.: J. Phase Equilib.: 1991, 12, 231‐243.
Cu-Sb
The data for the Cu‐Sb system are from the assessment of Liu et al. [00Liu].
This assessment represents a significant change from earlier assessments
[91Nit] and [91Tep] in that the β phase has been treated as a disordered bcc
phase (BCC_A2). Further modification to the data will probably be necessary to
remodel the γ phase (CUSB_GAMMA in [00Liu]) using the model for the
HCP_A3 phase, which corresponds to the real crystallographic structure over a
range of homogeneity.
References:
[91Nit] Nitsche, R., an Mey, S., Hack, K., Spencer, P. J.: Z. Metallkde., 1991, 82,
67‐72.
[91Tep] Teppo, O., Taskinen, P.: Scand. J. Metall., 1991, 20, 174‐182.
[00Liu] Liu, X. J., Wang, C. P., Ohnuma, I., Kainuma, R., Ishida, K.: J. Phase
Equilib., 2000, 21, 432‐442.
Cu-Sn
The data for the Cu‐Sn system from the assessment of Liu et al. [01Liu] were
accepted for the database. This assessment is an extension of earlier work
of Shim et al. [96Shi]. Also, the binary FCC_A1 solution data were modified
by Lee [04Lee] to be consistent with the new data for FCC_A1 (Sn) adopted
in the SGTE unary database v4.4 [SGTE4].
Several further modifications were necessary to assure consistency with other
systems in the COST 531 database. According to Liu et. al. [01Liu], there is
a complex ordering reaction around 700 °C and 0.2 Sn, which is not yet
completely understood, described as BCC_A2 → B2 → D03 or BCC_A2→ D03.
Because of remaining uncertainties about the real nature of the reactions, and
to be able to model the ternary Cu‐Ni‐Sn system where there is mutual
solubility between this bcc/γ (BCC_A2/D03 ) phase and Ni3Sn phase originating
in the Ni‐Sn system, the high‐temperature Cu‐rich phase was modelled as simple
disordered BCC_A2 phase. Also the high temperature modification of the Cu6Sn5 phase
had to be remodelled as CuIn‐η phase because of complete solubility between these two phases found experimentally in the Cu‐In‐Sn system.
The liquid phase data have also been modified within the scope of COST 531
Action to take into account the latest enthalpy of mixing data from Vienna [08Fla].
References:
[96Shi] Shim, J. H., Oh, C. S., Lee, B. J., Lee, D. N.: Z. Metallkde, 1996, 87, 205‐212.
[01Liu] Liu, X. J., Liu, H. S., Ohnuma, I., Kainuma, R., Ishida, K., Itabashi, S.,
Kameda, K., Yamaguchi, K.: J. Electron. Mater., 2001, 30, 1093‐1103.
[04Lee] Lee, B. J.: Unpublished work, 2004.
[08Fla] Flandorfer, H., Luef, Ch., Saeed ,U.: J. NonCryst. Solids, 2008, in print.
Cu-Zn
The critically assessed data for this system are from the assessment of Kowalski and Spencer
[93Kow] which reproduces well all the experimental data for the system. The dataset includes data for both the ordered B2_BCC phase and the associated disordered BCC_A2 phase.
The δ(CuZn3) phase was modelled as BCC_A2 in agreement with the result of [49Sch].
The ordering temperature BCC_A2--> B2_BCC is concentration dependent and lies between
454 - 467°C.
References:
[49Sch] Schubert, K., Wall, E.:Z. Metallkde.,1949, 40, 383‐385.
[93Kow] Kowalski, M., Spencer, P. J.: J. Phase Equilib., 1993, 14, 432‐438.
In-Ni
This system contains a number of intermetallic phases, 5 of which are treated
as stoichiometric in the modelling of the system. On the other hand, the
δ (INNI_DELTA) and ζ(INNI_CHI) phases show reasonable homogeneity ranges;
~7 and 10 at%, respectively, although both of these phases are stable over
only a limited temperature range. The source of the thermodynamic
parameters for this system is [02Wal]. In the original work, the modelling
included a description for the gas phase. However, thegas phase is not
included in the COST 531 thermodynamic database and hence data for the
In‐Ni gas was removed from the dataset. This resulted in the reappearance of
some of the compound phases at temperatures much higher than their true
stability ranges. In the course of the compilation of the COST 531 database,
modifications to the thermodynamic parameters for these compounds were
made in order to ensure that the phases did not appear at higher temperatures
below 3500K, the upper temperature limit of the COST 531 database.
References:
[02Wal] Waldner, P., Ipser, H.: Z. Metallkde., 2002, 93, 825‐832.
In-Pb
The data for the In-Pb system are from an unpublished assessment of
Bolcavage [95Bol] reported by Boa and Ansara [98Boa].
The data for the tetragonal phase were remodelled within the framework of
COST 531 using revised unary data for In consistent with data used for the
In‐Sn system.
References:
[95Bol] Bolcavage, A., Kao, C. R., Chen, S. L., Chang, Y. A.: Proc. Conf.
“Applications of Thermodynamics in the Synthesis and Processing of
Materials”, P. Nash and B. Sundman (eds.), The Minerals, Metals and
Materials Society, 1995.
[98Boa] Boa, D., Ansara, I.: Thermochim. Acta, 1998, 314, 79‐86.
In-Pd
The data from the assessment of Jiang and Liu [02Jia] were accepted for the
COST 531 database. This system is very complex, exhibiting many intermetallic
phases with high and low temperature variations. As there are insufficient
experimental data, all the intermetallic phases are modelled as stoichiometric,
except for InPd phase, which has an ordered BCC_B2 structure.
As there is no ordering reaction in this system, the ordered phase was
modelled using a two‐sublattice model with the sublattice ratio 0.5:0.5. The
data are not related to those for the disordered bcc phase. The crystallographic
structure for many of the intermetallic phases is uncertain.
References:
[02Jia] Jiang, Ch., Liu, Z. K.: Metall. Mater. Trans., 2002, 33A, 3597‐3603.
In-Sb
The original data for the In‐Sb system from Anderson were reported by Ansara
et al. [94Ans] and referred to as a private communication. Small modification
to data for the original α‐InSb phase was made. The phase was remodelled and
renamed ZINCBLENDE_B3 to provide compatibility with the general model for the
the crystallographic structure of this phase.
References:
[94Ans] Ansara, I., Chatillon, C., Lukas, H. L., Nishizawa, T., Ohtani, H., Ishida,
K., Hillert, M., Sundman, B., Argent, B. B., Watson, A., Chart, T. G.,
Anderson, T.: CALPHAD, 1994, 18, 177‐222.
In-Sn
This system has been modelled by several authors e. g. [96Lee, 99Ans,03Mo3].
The complete assessment of this system of Lee et al. [96Lee] was later amended
by [03Moe] who reassessed the InSn‐β phase (TET_ALPHA1).
Neither [96Lee] nor [03Moe] used unary data consistent with COST 531
Database in their assessments and therefore the data from Ansara et al. [99Ans]
were used as their dataset is consistent concerning the unary data. Small formal changes were made in the scope of the COST 531 Action. The name
of the InSn‐β phase was changed to TET_ALPHA1 and remodelled to maintain consistency with ternary systems since a phase with the same crystallographic
structure exists in the In‐Pb and Bi‐In systems.
There is significant discrepancy in the experimental data in the literature
concerning the composition ranges of the (INSN_GAMMA + BCT_A5) and
(TETRAG_A6 + TET_ALPHA1) two phase fields. The agreement of the assessment from [99Ans] with currently accepted experimental phase diagram
from [MAS] is very good.
References:
[96Lee] Lee, B.‐J., Oh, C.‐S., Shim, J.‐H.: J. Electron. Mater.: 1996, 25, 983‐991.
[99Ans] Ansara, I., Fries, S. G, Lukas, H. L: Unpublished work, 1999.
[03Moe] Moelans, N., Kumar, K. C. H., Wollants, P.: J. Alloys Compd., 2003, 360, 98-106.
In-Zn
The data from the critical assessment of Lee [96Lee] were used in the
COST 531 database. There is significant disagreement in the eutectic
concentration (in the range of 3.1‐8 wt.% of Zn) between various authors
e.g. [44Rhi, 56Oel, 50Car]. The theoretical assessment is in very good agreement with the experimental data accepted by [MAS].
References:
[44Rhi] Rhines, F.N., Grobe, A.H.: Trans. Met. Soc. AIME, 1944, 156, 156.
[50Car] Carapela Jr., S.C., Piretti, E.A.: Trans. Met. Soc. AIME, 1950, 188, 890.
[56Oel] Oelsen,W., Zühlke, P.: Arch. Eisenhüttenwes.,1956, 27, 743‐752.
[96Lee] Lee, B. J.: CALPHAD, 1996, 20, 471‐480.
Ni-Pb
The main feature of the phase diagram of this system is a monotectic reaction
occurring at 1340 °C leading to a miscibility gap in the liquid phase. With little
mutual solid solubility between the elements, a wide FCC_A1+FCC_A1 region is
also present at lower temperatures. The eutectic point is very close to the
melting point of Pb, and so the compositions of the phases involved are
virtually pure Ni and pure Pb. The source of the thermodynamic model
parameters for this system is [00Wan].
References:
[00Wan] Wang, C.P., Liu, X.J., Ohnuma, I., Kainuma, R., Ishida, K.: CALPHAD,
2000, 24, 149‐167.
Ni-Pd
The Ni‐Pd system has a simple isomorphous phase diagram, there being complete solid solubility at all compositions. The liquidus and solidus exhibit a
minimum at about 1238 °C and x =0.4. The thermodynamic description for Pd
this system is taken from [99Gho], although calculation using these data results
in the presence of a miscibility gap in the solid phase at low temperatures;
a feature that is absent in the original publication. There would seem to be no
experimental justification for this at this time and it would therefore warrant
further study.
References:
[99Gho] Ghosh, G., Kantner, C., Olson, G.B.: J. Phase Equilib., 1999, 20, 295‐308.
Ni-Sn
In order to maintain consistency between the thermodynamic data for the different binary systems, the adopted data for the Ni-Sn system [04Liu] required modification.
This was carried out within the scope of the COST 531 Action. The high temperature
Ni3Sn phase having the D03 structure has been observed in the Ni‐Sn system.
In the ternary Cu‐Ni‐Sn system, a continuous solubility region is observed between
the high‐temperature BCC_A2 phase originating in the Cu‐Sn binary and this Ni3Sn phase. Therefore, it was necessary to unify the models used for both phases
in order to be able to model that region as a single phase. It was decided to reassess
the Ni3Sn phase as having the BCC_A2 structure to be consistent with the simplified model
selected for the relevant phase in the Cu‐Sn system.
It was also necessary to remodel the Ni3Sn (NI3SN2) phase to make it compatible
with the Au‐Ni‐Sn assessment already present in the COST 531 database.
A new 3‐sublattice model, (Ni,Sn)0.5(Ni)0.25(Ni)0.25, taking into the account the
homogeneity range of NI3SN2, has been employed.
References:
[04Liu] Liu, H. S., Wang, J., Jin, Z. P.: CALPHAD, 2004, 28, 363‐370.
Ni-Zn
The data for the Ni‐Zn system are taken from the assessment of Miettinen [03Mie] which
is itself a modified version of the critically assessed data of Vassilev et al. [00Vas]. The major
difference between the two datasets relates to the modelling of the high temperature
β phase which has a chemically ordered CsCl BCC_B2 structure. The assessment adopted
for the database modelled this phase as a disordered BCC_A2 structure. The original
assessment of Vassilev used a compound energy model with vacancies introduced onto
the second sublattice.
References:
[00Vas] Vassilev, G. P., Gomez‐Acebo, T., Tedenac, J.‐C.: J. Phase Equilib., 2000, 21, 287‐301.
[03Mie] Miettinen, J.: CALPHAD, 2003, 27, 263-274.
Pb-Pd
Despite Pb and Pd having the same crystal structure, their mutual solubility is limited. Pd will
dissolve up to about 20 at% Pb, whereas the solubility of Pd in Pb is negligible.
The thermodynamic description for this system is taken from [99Gho].
There are a number of intermetallic phases in the system, some of which have a number
of polymorphs. According to [MAS], both the Pb9Pd13 and the Pb3Pd5 phases exist in α, β
and γ forms. In the modelling, however, the description of Pb9Pd13 is simplified, the phase
being treated as a single stoichiometric phase PD13PB9.
The PD5PB3_BETA phase at approx. x(Pd)=0.66 has not been labelled in figure for clarity.
References:
[99Gho] Ghosh, G.: J. Phase Equilib., 1999, 20, 309‐315.
Pb-Sb
The Pb‐Sb is a simple eutectic system. There is only limited mutual solid solubility of
the component elements. The thermodynamic description for this systems is taken
from [95Oht].
References:
[95Oht] Ohtani, H., Okuda, K., Ishida, K.: J. Phase Equilib., 1995, 16, 416‐429.
Pb-Sn
Data for the Pb‐Sn system are from the assessment of Ohtani and Ishida [95Oht].
The data for the FCC_A1 and LIQUID phases were modified within the framework of
COST 531 to take account of new unary data for Sn in the metastable FCC_A1
structure [SGTE4].
References:
[95Oht] Ohtani, H., Ishida, K.: J. Phase Equilib., 1995, 16, 416‐429.
Pb-Zn
The Pb‐Zn system shows negligible mutual solid solubility of the component elements
and no intermetallic phases. It is dominated by a syntectic reaction resulting from
a large miscibility gap in the liquid phase. A eutectic reaction is present at a slightly
lower temperature. The thermodynamic description for this system comes from [93Sri].
References:
[93Sri] Srivastava, M., Sharma, R.C.: J. Phase Equilib., 1993, 14, 700‐709.
Pd-Sn
The original assessment for the Pd‐Sn system was made by Ghosh [99Gho] using
different unary parameters from those used in the scope of the COST 531 Action
[SGTE4]. The main difference was found in the description of the Gibbs energy
of pure Sn in the metastable FCC_A1 phase. Therefore, the dataset has been
modified to take account of the revised value. The phase boundary shift,
resulting from using new unary data, was corrected. The rest of the diagram
was accepted without change.
The phase diagram is very complicated, containing many intermetallic phases
with high and low‐temperature modifications. Because of the lack of
experimental data most of them were modelled as stoichiometric compounds.
The detail of the phase diagram with very complex phase coexistence in the
region around 0.4 Pd is shown in the figures.
References:
[99Gho] Ghosh, G.: Metall. Mat. Trans. A, 1999, 30A, 5‐18.
Pd-Zn
This system was assessed by [06Viz] within the scope of the COST 531 Action.
They used the thermodynamic data from the work of Kou et al. [75Kou] and
Chiang et al. [77Chi]. As there is a lack of experimental phase data for this
system the authors utilised their own experimental results [06Viz] as well as
the phase data estimated from [MAS] and [58Han]. The experimental results
from [06Viz] led to the confirmation of the η phase, identified by [51Now],
and not accepted by [MAS], as the stable phase. They also found a different
invariant reaction in the Zn‐rich region in comparison with [58Han] and
[MAS]. A eutectic was identified instead of a peritectic reaction.
References:
[51Now] Nowotny, H., Bauer, E., Stempfl, A.: Monatsh. Chem., 1951, 82, 1086‐
1093.
[58Han] Hansen, M., Anderko, K.: Constitution of Binary Alloys, McGraw‐Hill,
New York, 1958, 1130‐1133.
[75Kou] Kou, S., Chang, Y. A.: Acta Metall., 1975, 23, 1185‐1190.
[77Chi] Chiang, T., Ipser, H., Chang, Y. A.: Z. Metallkd., 1977, 68, 141‐147.
[06Viz] Vízdal, J., Kroupa, A., Popovic, J., Zemanová, A.: Adv. Eng. Mat., 2006, 8,
164‐176.
Sb-Sn
Existing literature assessments had to be reassessed as they used different unary
data for pure Sb in the hypothetical BCT_A5 structure. The dataset from
Oh et al. [96Oh] was used as the base for the further work and DSC data of
Vassilev et al. [01Vas], and also data newly obtained in the scope of the COST
531 project [04Vas], were taken into account. The reassessment of the system
was carried out by Kroupa and Vízdal [07Kro].
References:
[96Oh] Oh, C. S., Shim, J.H., Lee, B.J., Lee, D. N.: J. Alloys Compd., 1996, 238, 155-166.
[01Vas] Vassiliev, V., Feutelais, Y., Sghaier, M., Legendre, B. : J. Alloy. Compd.,
2001, 314, 198‐205.
[04Vas] Vassilev, G.P.: Unpublished work, 2004.
[07Kro] Kroupa, A., Vízdal, J.: Defect and Diffusion Forum, 2007, 263, 99‐104.
Sb-Zn
The data for the Sb‐Zn system are from the critical assessment of Liu et al. [00Liu].
The authors obtained good agreement between calculated and experimental
values for a wide range of properties.
References:
[00Liu] Liu, X. J., Wang, C. P., Ohnuma, I., Kainuma, R., Ishida, K.: J. Phase
Equilib., 2000, 21, 432‐442.
Sn-Zn
The Sn‐Zn system was assessed by several authors [96Lee, 99Oht, 02Fri],
which differ in the unary data used and also in the temperature dependence of
the solubility of Zn in pure Sn. It was difficult to evaluate the reliability of particular
assessments as there is a limited number of experimental data in this region.
Therefore the consistency of the unary data was taken as an important criterion
and the theoretical data for the Sn‐Zn system from the critical assessment of
Fries [02Fri] published as part of the COST507 database [98Ans] were accepted.
References:
[96Lee] Lee, B.‐J.: CALPHAD, 1996, 20, 471‐480.
[98Ans] Ansara, I., Dinsdale, A. T., Rand, M. H.: Thermochemical database for
light metal alloys, EUR18499, July 1998, 2, 288‐289.
[99Oht] Ohtani, H., Miyashita, M., Ishida, K.: J. Jpn. Inst. Met., 1999, 63, 685‐694.
[02Fri] Fries, S. G.: Unpublished work, 2002.
Ternary systems
Ag-Au-Bi
The data for the Ag‐Au‐Bi system were taken from a recent assessment by Zoro
et al. [07Zor1], [07Zor2] undertaken within the framework of the COST 531
Action. The assessment is based on their own experimental study of four
isopleths by X‐ray diffraction, differential calorimetry and electron probe
microanalysis [05Zor1] and measurements of the enthalpies of mixing in the
liquid phase [05Zor2].
References:
[05Zor1] Zoro, E., Dichi, E., Servant, C., Legendre, B.: J. Alloys Comp., 2005, 400, 209-215.
[05Zor2] Zoro, E., Boa, D., Servant, C., Legendre, B.: J. Alloys Comp., 2005, 398, 106-112.
[07Zor1] Zoro, E., Servant, C., Legendre, B.: J. Thermal Anal. Calor., 2007, 90, 347-353.
[07Zor2] Zoro, E., Servant, C., Legendre, B.: CALPHAD 2007, 31, 89‐94.
Ag-Au-Sb
The data for the Ag‐Au‐Sb system were taken from a recent asssessment by Zoro et al.
[07Zor1], [07Zor2] undertaken within the framework of the COST 531 Action.
The assessment is based on their own experimental study of phase equilibria across
seven isopleths and measurements of the enthalpies of mixing in the liquid phase.
References:
[07Zor1] Zoro, E., Servant, C., Legendre, B.: J. Phase Equilib. Diffus., 2007, 28, 250-257.
[07Zor2] Zoro, E., Servant, C., Legendre, B.: J. Thermal Anal. Calor., 2007, 90, 347-353.
Ag-Bi-Sn
The data for this system were a revision of an assessment of Garzel et al. [06Gar] based
on the new experimental electromotive force (emf) data [06Gar, 07Li] obtained in the scope of COST 531 Action. The revision was necessary because of the change to the
data for the Ag‐Sn and Bi‐Sn systems and is in very good agreement with all available data. These replaced the previous assessment of Ohtani et al. [04Oht].
References:
[04Oht] Ohtani, H.: Materials Transactions, 2004, 42, 722‐731.
[06Gar] Garzel, G., Zabdyr, L. A.: J. Phase Equil., 2006, 24, 140‐144.
[07Li] Li, Z., Knott, S., Mikula, A.: J. Electron. Mat., 2007, 36, 40‐44.
Ag-Cu-In
This system had not been assessed prior to COST 531. The only experimental
information on this system was presented by [88Woy] which gave an
isothermal section for 505 °C. An interesting feature of this section is what
would seem at first sight to be a ternary compound lying along at approximately
30 at% In. At closer inspection, this ‘ternary’ compound is in fact the
CUIN_GAMMA phase which exists as a complete series of solid solutions from
CUIN_GAMMA, which is a high‐temperature phase in the Cu‐In binary system,
to Ag2In, which is a low temperature phase in the Ag‐In binary system.
Because of the differing temperature stabilities of the binary variants of the
phase, it is not seen as a complete series of solid solutions at any one
temperature.
As part of the experimental work of COST 531, a programme of study was initiated
by the IMMS‐PAS at Krakow, Poland, to determine the thermodynamic properties
of the liquid phase (enthalpies of mixing (in conjunction with the University of
Leeds, UK) and the activity of In in the liquid [08Wie]) and the liquidus surface
along three sections of the ternary system [06Wie].
The modelling of this system is quite challenging. The enthalpies of mixing in the
Ag-Cu system are positive whereas those for the Ag-In system are negative, and
extrapolation of the binary systems into the ternary predicts a miscibility gap in
the liquid phase that is not seen experimentally.
The experimental data generated as part of COST 531 have been used in
an attempt to model the ternary system. As a first step in this modelling it was
necessary to remodel the Ag2In phase to make it compatible with the
CUIN_GAMMA phase in the Cu‐In system (see binary systems section, Ag‐In).
The diagrams below represent the current state of the modelling of this system
but it should be stressed that it is still under refinement. Although the
experimental thermodynamic properties are reproduced reasonably well there is
still disagreement between the experimental and calculated liquidus surface.
These features are more likely an artefact of the calculations and it is envisaged that in the
final version of the model, the phase separation will not be present resulting in the
loss of one of the invariant reactions. There are a number of invariant
reactions occuring in the In‐corner of the diagram, which are seen more clearly
in a magnified portion of the liquidus.
It can be seen how the CUIN_GAMMA phase lies across the section but without
being stable in either of the Cu‐In and Ag‐In binaries at this temperature.
Even though the modelling still requires work, the fit between the calculated
and experimental data is good.
References:
[88Woy] Woychik, C.G., Massalski, T.B.: Met. Trans., 1988, 19A, 13‐21.
[06Wie] Wierzbicka, A., Czeppe, T, Zabdyr, L.A.: Arch. Met. Mater., 2006, 51,
377‐387.
[08Wie] Wierzbicka, A., Watson, A., Zabdyr, L.A.: to be submitted to J. Alloys
Compd, 2008.
Ag-Cu-Ni
Measurements on the Ag‐Cu‐Ni system were first reported by de Cesaries [13deC] who
provided a plot of the liquidus surface and some solidus points. The system was studied again
by Guertler and Bergmann [33Gue]. Siewert and Heine [77Sie] studied phase equilibria at
800 °C and 900 °C and the liquidus surface while more recently Luo and Chen [96Luo] studied
phase equilibria at 700 °C, 795 °C and 860 °C. Calculations were carried out within the
framework of COST 531 to explore the agreement between the current database and the
limited experimental data for this system. No ternary interactions were found to be necessary. Experimental data published prior to the COST Action have been added to calculated
isothermal sections to demonstrate validity of critically assessed data.
References:
[13deC] de Cesaris, P.: Gazz. Chim. Ital., 1913, 25, 365‐79.
[33Gue] Guertler, W., Bergmann, A.: Z. Metallkde., 1933, 25, 53‐57.
[77Sie] Siewert, T.A., Heien, R.W.: Metall. Trans. A, 1977, 8A. 515‐518.
Ag-Cu-Pb
The data for this system was accepted from the well established assessment of [86Hay] which
is in very good agreement with the experimental data. Only one invariant reaction very close
to the Pb‐rich corner in this system. Three FCC_A1 phases with very limited solubility of
other elements are the result of the reaction.
References:
[86Hay] Hayes, F., Lukas, H. L., Effenberg, G., Petzow, G.: Z. Metallkde., 1986, 77, 749-754.
Ag-Cu-Sn
The data for the Ag‐Cu‐Sn system were taken from an unpublished assessment of Gisby and
Dinsdale carried out prior the COST 531 Action. Recent measurments of the enthalpies of mixing and emf in the liquid phase by Flandorfer and Zabdyr respectively undertaken within
the COST 531 Action have not been taken into account. The assessment was based on
calorimetry data of Shen et al. [69She1, 69She2], studies of the solubility of Cu in Ag‐Sn
liquids by [99Cha] and studies of phase equilibria for various isopleths in the ternary system
[59Geb, 81Fed, 82Fed, 94Mil, 00Loo, 00Moo].
This system has a great importance for the industry.
References:
[59Geb] Gebhardt, R. E. G., Petzow, G.: Z. Metallkde, 1959, 50, 597‐605.
[69She1] Shen, S. S.: Ph.D. Thesis, 1969, University of Denver.
[69She2] Shen, S. S., Spencer, P. J., Pool, M. J.: Trans. AIME, 1969, 245, 603‐606.
[81Fed] Fedorov, V. N., Osinchev, O. E., Yushkina, E. T.: Fazovye Ravnovesiya
Met. Splavakh, 1981, 42‐49.
[82Fed] Fedorov, V. N., Osinchev, O. E., Yushkina, E. T.: in Phase Diagrams of Metallic
Systems, 1982, Ed. Ageev, N. V., Petrova, L. A., 26, 149‐150.
[94Mil] Miller, C. M., Anderson, I. E., Smith, J. F.: J. Electron. Mat., 1994, 23, 595‐601.
[99Cha] Chada, S., Laub, W., Fournelle, R. A., Shangguan, D.: J. Electron. Mat., 1999, 26,
1194‐1202.
[00Loo] Loomans, M. E., Fine, M. E.: Metall. Mater. Trans. A, 2000, 31A, 11551162.
[00Moo] Moon, K. W., Boettinger, W. J., Kattner, U. R., Biancaniello
Ag-In-Sn
The critically assessed data of Liu et al. [02Liu] were adopted and when used with the COST 531binary data give very good agreement with experimental information. The liquidus surface is very complex close to the In‐Sn binary system and the side projection
of the liquidus lines is very useful to indicate the position of particular invariant reactions.
References:
[02Liu] Liu, X., Inohana, Y., Takaku, Y., Ohnuma, I., Kainuma, R., Ishida, K., Moser,
Z., Gasior, W., Pstrus, J.: J. Electron. Mater., 2002, 31, 1139-1151.
Ag-Ni-Sn
There are very few published experimental data for this system. More recently extensive
studies of the phase diagram have been undertaken by Schmetterer [07Sch]. Ternary
interaction data for the liquid phase have been introduced in the scope of COST 531 Action andthese give reasonable agreement with experimental properties measured by [07Sch].
The liquidus projection of this system is very complex owing to the properties of the binary
Ag-Ni system. It is unusual as it exhibits both liquid and solid phase immiscibility.
This leads to the presence of two monotectic reactions in the binary phase diagram, and
these have a great effect on the equilibria in the ternary Ag‐Ni‐Sn system. The ternary phase
diagram is dominated by a large region of liquid immiscibility that extends from the binary
Ag‐Ni system. Associated with this miscibility gap are two decomposition reactions.
References:
[07Sch] Schmetterer, C.: "Interactions of Sn‐containing solders with Ni(P) substrates ‐ phase equilibria and thermodynamics", thesis, University of Vienna, 2007.
Au-Bi-Sb
Data from the critical assessment of [07Wan] were adopted after checking for consistency with the unary and binary data used in the scope of COST 531 Action. Good agreement was found in comparison with experimental data published in [07Wan].
References:
[07Wan] Wang, J., Meng, F. G., Liu, H. S., Liu, L. B., Jin, Z. P.: J. Electron Mater., 2007, 36, 568‐577.
Au-In-Sb
Data from the critical assessment of Liu et al. [03Liu] were adopted after modification in the scope of COST 531 Action. This system exhibits a very complex liquidus surface, which is shown in detail in the diagrams. In particular the T‐x projection gives an excellent overview of the invariant points.
References:
[03Liu] Liu, H. S., Liu, C. L., Wang, C., Ishida, K.: J. Electron. Mater., 2003, 32, 81-88.
Au-In-Sn
This system had not been assessed prior to COST 531. Phase diagram data for the system are sparse. Therefore, a full experimental determination of the system was undertaken under the Action comprising a series of phase diagram studies to confirm previous observations of the phase relationships, DTA and DSC studies to fully characterise the melting behaviour of the ternary AU4IN3SN3 compound, determination of the enthalpy of formation of the ternary compound by direct and tin‐solution calorimetry and measurement of the enthalpies of mixing of liquid alloys. The experimental results were used in a CALPHAD assessment of the system, which will be published, along with the experimental data in a series of publications to be submitted to the CALPHAD journal [08Bor, 08Wat, 08Cac].
The ternary compound was found to melt incongruently, contradicting earlier work. The liquidus surface is deceptively complex, as can be realised from the T‐X(In) projection, partly owing to primary solidification surfaces for AU7IN3 and the ternary compound in the ternary system. There are 11 transition reactions, two ternary peritectic reactions and 2 ternary eutectics.
References:
[08Bor] Borzone, G., Cacciamani, G., Watson, A.: to be submitted to CALPHAD, 2008.
[08Wat] Watson, A., Borzone, G., Cacciamani, G.: to be submitted to CALPHAD, 2008.
[08Cac] Cacciamani, G., Watson, A., Borzone, G.: to be submitted to CALPHAD, 2008.
Au-Ni-Sn
Liu et. al. [05Liu] has published an assessment of the data for this system. Slight corrections were made to obtain agreement with the published data and to accommodate the adopted COST 531 binary data.
The liquidus surface is quite complex with many invariant reactions. In addition to the primary solidificaton fields, there is also a very small DHCP primary liquidus surface at the Au‐Sn binary edge at a composition x(Sn) of about 0.21.
References:
[05Liu] Liu, X.‐J., Kinaka, M., Takaku, Y., Ohnuma, I., Kainuma, R., Ishida, K.: J. Electr. Mater.; 2005, 34, 670‐679.
Bi-In-Sn
This ternary system was assessed by [99Yoo], but because of changes to the binary data (Bi‐In, Bi‐Sn, see binary systems) it was necessary to reassess the system in the scope of COST 531 Action. The liquidus surfaces in two different projections are shown here, together with selected isothermal sections (near the eutectic temperature) and a set of isopleths (with different ratios of Bi and In near the invariant points) were calculated. The agreement with the experimental data and the previous assessment is very good. Some discrepancies with [99Yoo] can be found at the lowest temperatures (below 50 °C), where no experimental data exist.
References:
[99Yoo] Yoon, S. W., Rho, B.‐S., Lee, H. M., Kim, C.‐U., Lee, B.‐J.: Metall. Mater. Trans., 1999,
30A, 1503‐1515.
Bi-Sb-Sn
Although Ohtani and Ishida [94Oht] optimized thermodynamic parameters in this ternary system, a critical evaluation of the literature data in the frame of the COST 531 program as well as new experimental thermodynamic results [01Vas, 05Kat] created a need for reassessment of data for the Bi‐Sb‐Sn system. The results of the modelling of phase equilibria are compared with experimental results from [07Man] and from other literature sources. Also, experimentally obtained activities and experimentally based excess Gibbs energy functions from the literature [01Vas, 05Kat] were used for the optimization of the thermodynamic parameters.
References:
[94Oht] Ohtani, H., Ishida, K.: J. Electron. Mater., 1994, 23, 747‐755.
[01Vas] Vassilev, V., Feutelais, Y., Sghaier, M., Legendre, B.: J. Alloys Comp., 2001, 314, 198‐205.
[05Kat] Katayama, I., Živković, D., Manasijević, D., Tanaka, T.,. Živković, Ž., Yamashita, H.: Netsu Sokutei, 2005, 32, 40‐44.
[07Man] Manasievič, D., Vřešťál, J., Minič, D., Kroupa, A., Živkovič, D., Živkovič,
Ž.: J. Alloys Comp., 2007, 438, 150‐157.
Bi-Sn-Zn
The ternary Bi‐Sn‐Zn system was assessed by Malakhov et al. [00Mal] and Moelans et al. [03Moe]. Both assessments are based on the experimental work of Muzaffar [23Muz] and both authors introduced ternary corrections for the liquid phase only. The assessments of this system are unfortunately not mutually consistent, as the authors used different unary data and also binary data for Bi‐Sn systems ([94Oht], [96Lee]). As both Malakhov et al. [00Mal] and Moelans et al. [03Moe] have used the older thermodynamic description of the Bi‐Sn system for their assessments, it was necessary to reassess the Bi‐Sn‐Zn system using the newly assessed Bi‐Sn system [07Viz]. Recently, Luef et al. [06Lue] published experimentally measured enthalpies of liquid and DSC data in Sn‐rich part of the system. Braga et al. [07Bra] published new significant experimental results focusing on the miscibility gap and also the Sn‐rich part of the phase diagram. These data were also utilized for the reassessment of the ternary system [07Viz].
References:
[23Muz] Muzaffar, S. D.: J. Chem. Soc., 1923, 123, 2341.
[94Oht] Ohtani, H., Ishida, K.: J. Electron. Mater., 1994, 23, 747‐755.
[96Lee] Lee, B.‐J., Oh, C.‐S., Shim, J.‐H.: J. Electron Mater., 1996, 25, 983‐991.
[00Mal] Malakhov, D. V., Liu, X. J., Ohnuma, I., Ishida, K.: J. Ph. Equil., 2000, 21, 514‐520.
[03Moe] Moelans, N., Kumar, K. C. H., Wollants, P.: J. All. Comp., 2003, 360, 98106.
[06Lue] Luef, C., Paul, A., Vízdal, J., Kroupa, A., Kodentsov, A. Ipser, H.: Monatsh. Chem., 2006,
137, 381‐395.
[07Bra] Braga, M. H., Vízdal, J., Kroupa, A., Ferreira, J., Soares, D., Malheiros, L. F.: CALPHAD,
2007, 31, 468‐478.
[07Viz] Vízdal, J., Braga, M. H., Kroupa, A., Richter, K. W., Soares, D., Malheiros, L. F., Ferreira, J.:
CALPHAD, 2007, 31, 438‐448.
Cu-In-Sn
The data from Liu et al. [01Liu] were modified and incorporated into the database. This reassessment is based on new phase equilibrium data from [07Dra1, 07Dra2], and new thermodynamic data from [06Pop, 06Li].
References:
[01Liu] Liu, X. J., Liu, H. S., Ohnuma, I., Kainuma, R., Ishida, K., Itabashi, S.,
Kameda, K., Yamaguchi, K.: J. Electron. Mater., 2001, 30(9) 1093.
[06Pop] Popovič, A., Bencze, L.: Int. J. of Mass Spectrometry, 2006, 257, 41‐49.
[06Li] Li, Z., Knott, S., Qiao, Z., Mikula, A.: Mater. Trans. A, 2006, 47(8), 20252032.
[07Dra1] Drápala, J., Burkovič, R., Kozelková, R, Smetana, B., Dočekalová, S., Dudek, R.,
Zlatohlávek, P., Vřešťál, J., Kroupa, A.: Acta Metallurgica Slovaca, 2007, 13(1),
670‐673.
[07Dra2] Drápala, J., Kubíček, P., Vřešťál, J., Losertová, M.: Defect and Diffusion Forum,
Trans. Tech. Publication, Switzerland, 2007, 263, 231‐236.
Cu-Ni-Sn
The data for this ternary system were based on the work of Miettinen [03Mie]. In the assessment of [03Mie] different unary data and different descriptions of the relevant binary systems were used from those adopted for the COST 531 database. In addition, the high‐temperature Ni3Sn‐γ phase was modelled as D03 and the ordering reaction in the Cu‐Sn system was modelled in as BCC_A2→D03. Therefore, it was necessary to reassess this system to ensure compatibility with the adopted unary and binary data in the COST 531 thermodynamic database. The data for this system were derived in the scope of COST 531 Action, also using new experimental data from [08Sch].
References:
[03Mie] Miettinnen, J.: CALPHAD, 2003, 27, 309‐318.
[08Sch] Schmetterer, C., Flandorfer, H., Luef, C., Ipser H., submitted to J. Electron. Mater.
In-Sb-Sn
Ishihara et al. [99Ish] have already provided optimized thermodynamic parameters for this ternary system. Nevertheless a critical evaluation of the literature data carried out within the framework of the COST 531 Action was necessary in view of the new thermodynamic assessment of the Sb‐Sn binary system [07Kro] and experimental results from [06Man]. These formed the basis for the reassessment of the data for this system by [06Man]. The results of thermodynamic modelling of ternary In‐Sb‐Sn system were compared with their own experimental results and literature data.
References:
[99Ish] Ishihara, S., Ohtani, H., Saito, T., Ishida, K.: J. Japan Inst. Metals, 1999, 63(6) 695‐701.
[06Man] Manasijevič, D., Vřešťál, J., Minič, D., Kroupa, A., Živkovič, D., Živkovič, Ž: J. Alloys
Compd., 2006, 438, 150‐157.
[07Kro] Kroupa, A., Vízdal, J.: Defect and Diffusion Forum, 2007, 263, 99‐104.
In-Sn-Zn
The data from Cui et al. [01Cui] when combined with the current binary data were found to give good agreement with experimental data and were therefore adopted for the COST 531 database.
References:
[01Cui] Cui, Y., Liu, X. J., Ohnuma, I., Kainuma, R., Ohtani, H., Ishida, K.: J. Alloys and
Compounds, 2001, 320, 234‐241.