Computer Coupling of Phase Diagrams and Thermochemistry 31 (2007) 125140 www.elsevier.

com/locate/calphad

A full thermodynamic optimization of the ZnFeAl system within the 420500 C temperature range
Jinichiro Nakano a, , Dmitri V. Malakhov b,1 , Shu Yamaguchi c , Gary R. Purdy b,2
a D epartement des Sciences des Mat eriaux et des Proc ed es, Universit e catholique de Louvain, IMAP, Place Sainte Barbe 2, B-1348 Louvain-la-Neuve, Belgium b Department of Materials Science and Engineering, McMaster University, 1280 Main Street West, Hamilton, Ontario, Canada L8S 4L7 c Department of Materials Engineering, University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 113-8656, Japan

Received 9 May 2006; received in revised form 23 September 2006; accepted 23 September 2006 Available online 26 October 2006

Abstract The ZnFeAl system was assessed by using the CALPHAD technique. The optimization was based on three cornerstones. Firstly, crystallographically consistent sublattice models recently proposed by Nakano et al. for all intermetallic phases in the ZnFe system made it possible to predict which sublattice(s) would be most capable of hosting aluminum. Secondly, a careful analysis of all available phase diagram data allowed identifying those investigations in which the equilibrium state of the system was unquestionably achieved. Only the results of those studies were employed for the assessment. Thirdly, the PARROT module of Thermo-Calc, which was used for the optimization, was fed with an extensive array of accurate and reliable activities of Al. The activities were derived from electromotive forces measured by Yamaguchi et al. in various two- and three-phase regions. In the past, only a fraction of data collected was published; a complete compilation is presented in this contribution. By comparing calculated quantities and their experimental counterparts, it was demonstrated that the thermodynamic model proposed for the ZnFeAl system could be relied upon within the 420500 C range, i.e. within the region important for galvanizing and galvannealing. It is difcult to speculate whether the model remains workable outside this temperature interval since almost all experimental data reported in literature were obtained within the limits specied. c 2006 Elsevier Ltd. All rights reserved.
Keywords: Sublattice model; ZnFeAl system; Crystallographic information; Galvanizing; Inhibition layer

1. Introduction Millions of tons of steel are galvanized and galvannealed annually.3 In the former case, a Zn bath may contain 0.150.2 wt% of Al; in the latter case aluminum concentration usually ranges from 0.1 to 0.4 wt%. The intended outcome of this immersion is the formation of a uniform, adherent, protective coating on the steel surface. Many years of practical
Corresponding author. Tel.: +32 10 47 23 38; fax: +32 10 47 40 28.

E-mail addresses: jinichiro@gmail.com (J. Nakano), yamaguchi@material.t.u-tokyo.ac.jp (S. Yamaguchi). 1 Tel.: +1 905 525 9140x24308; fax: +1 905 528 9295. 2 Tel.: +1 905 525 9140x24785; fax: +1 905 528 9295. 3 Galvanizing baths are maintained within specic ranges of Al levels in order to suppress the formation of ZnFe based phases. The galvannealing process adds a subsequent annealing stage designed to control the formation of these phases. 0364-5916/$ - see front matter c 2006 Elsevier Ltd. All rights reserved. doi:10.1016/j.calphad.2006.09.003

experience4 clearly indicate that quality of the protective multi-layered structure is greatly inuenced by many factors, with temperature (usually varying from 450 to 470 C), steel composition and Al concentration in a bath being the most important of them [1,2]. The purpose of Al additions to molten Zn is to suppress the formation of a multi-layered coating. An analysis of an immense array of experimental evidence suggests that thermodynamics per se cannot be used for modeling and optimizing the hot-dip galvanizing process. Kinetics of steel dissolution in the bath and kinetics of a subsequent phase formation on the substrate surface is equally if not more important. However, there are essential questions, answers to

4 Although batch galvanizing was patented in 1837, continuous hot-dip galvanizing was invented by Tadeusz Sendzimir who constructed the rst industrial-scale galvanizing unit in Poland in 1931.

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Nomenclature variables in the i th order interaction parameter of a phase phase Gm molar Gibbs energy of a phase, J/mol 0 G phase 0 phase component , G end member standard Gibbs energies of a component or an end member in a phase (e.g., lattice stabilities of elements phases), J/mol ex G phase excess molar Gibbs energy of a phase, J/mol m i L phase constituents i th order interaction parameter of a phase between constituents in a sublattice, J/mol R gas constant, J/mol/K T temperature, K phase xcomponent mole fraction of a component in a phase ycomponent site fraction of a component which can be sought on purely thermodynamic grounds. For example: 1. What is the upper limit of metastable solubility of Fe in a bath of a given composition, i.e. the solubility governed by a metastable equilibrium between the liquid and BCC phases? How does this limit depend on temperature? 2. How much dross (i.e. unwanted particles of intermetallic phases accumulating in a bath) will form from this supersaturated solution? What is the nature of precipitating intermetallics? 3. What are the interfacial concentrations of components in adjacent layers of intermetallics assuming that the local equilibrium (stable or metastable) is reached? 4. How is a total amount of Al in a bath distributed between intermetallic particles and the liquid phase? 5. What are the driving forces for the onset of precipitation of various solid phases at the steel/melt interface? If the thermodynamic properties of phases participating in galvanizing processes are so important, then one might expect that a self-consistent and reliable thermodynamic model of the ZnFeAl system, which is most important for the theory and practice of galvanizing and galvannealing, has been already proposed. Although attention of many researchers was focused on this ternary system and especially on its Zn-rich corner [310], the whole ZnFeAl system has never been assessed by using the CALPHAD method [1113]. This system was considered as challenging for optimization due to the following circumstances: 1. In contrast to abundant phase diagram data, little reliable thermodynamic information on activities or enthalpies has been published in scientic periodicals. 2. An abundance of experimental data on conditions of phase equilibria is accompanied by serious contradictions. Not only were different coordinates of corners of non-variant triangles reported in the literature, but dissimilar phase portraits within similarly located triangles were reported as well.
i a phase , i bphase , i cphase

3. It is well known that all binary phases in the ZnFe system and a majority of binary phases in the FeAl system can host Al and Zn, correspondingly. An absence of crystallographically correct sublattice models for these binary phases made the application of the CALPHAD method to the ternary system very difcult. Recently, the situation has changed for the better. Firstly, a signicant and very extensive collection of raw EMF measurements of aluminum activity in various two-phase and three-phase regions (see Appendix) became available. Secondly, it was realized that contradictions between phase diagrams reported in literature could be attributed to insufciently long homogenization times, and that the results of those studies [7,8,10] in which those times were long enough are not very dissimilar. Consequently, only these sources were used in the assessment. It is worth mentioning that only in these three investigations the ternary 2 phase, which undoubtedly exists near the Zn-rich corner, was observed. Thirdly, for the crystallographically consistent models of ZnFe intermetallics proposed in [14], it was possible to point to sublattices capable of accommodating Al. Modications to the sublattice models of Fe4 Al13 , FeAl2 and Fe2 Al5 allowed the description of the solubility of Zn in these phases. The objective of this work is to build a complete thermodynamic description of the ZnFeAl system, taking a full advantage of the new situation. 2. Previous thermodynamic modeling of a Zn-rich portion of the ZnFeAl system As Table 1 indicates, previous endeavors in modeling the ZnFeAl system were primarily focused on its Zn-rich corner. In a majority of cases, an approach based on the solubility product was utilized to model the liquidus surface. 3. Phase models None of the phases was modeled as a stoichiometric compound in this contribution. All phases were handled as solutions with either one lattice (substitutional solutions) or several sublattices. The following reference states were used: HCP for Zn, BCC for Fe, and FCC for Al. 3.1. Substitutional solutions The thermodynamic models used for describing the properties of ve substitutional solutions in the ZnFeAl system are presented in Table 2. In the absence of any experimental information about its behavior in the ternary system, the model of the Fe4 Al5 phase suggested in [15] was used without any modications. In particular, it was postulated that zinc could not dissolve in this phase. 3.2. Phases with several sublattices 3.2.1. Phases originating from ZnFe binary phases The ZnFe binary system is shown in Fig. 2. All sublattice models for , 1 , and phases proposed in [14] were claimed

J. Nakano et al. / Computer Coupling of Phase Diagrams and Thermochemistry 31 (2007) 125140 Table 1 Previous applications of computational thermodynamics to the ZnFeAl system T ( C) 447480 450485 450465 450480 450480 450 450 450480 450, 460 430480 Fe (wt%) 00.08 00.1 01 00.08 00.06 00.04 0100 00.06 00.04 00.06 Al (wt%) 00.5 00.3 010 00.14 0.10.3 00.4 0100 00.25 00.4 00.25 Entity modeled Liquidus Liquidus Liquidus Liquidus Liquidus Liquidus Whole system Liquidus Liquidus Liquidus Method of modeling Solubility product Solubility product Extrapolation from binaries Solubility product CALPHAD CALPHAD Extrapolation from binaries Solubility product CALPHAD Kohlers geometric model Data used [2629] [18] [15,30,31] [20] [15,20,31,32] [5,7,8,19,33] [15,31,32] [21] [5,7,8,19,3235] [23,36,37]

127

Reference [33] [38] [35] [20] [39] [40] [41] [21] [42] [43]

Table 2 Models used for substitutional solutions Phase LIQUID BCC FCC HCP Fe4 Al5 Model (Al, Fe, Zn)1 (Al, Fe, Zn)1 (Va)3 (Al, Fe, Zn)1 (Va)1 (Al, Fe, Zn)1 (Va)0.5 (Al, Fe)1

Fig. 2. The ZnFe phase diagram [14].

Fig. 1. A calculated 450 C section of the ZnFeAl phase diagram.

to be crystallographically consistent. Based on coordination numbers and point symmetries, some of the sublattices were identied as potential hosts for aluminum. For instance, the following sublattice model was suggested for the phase [14]: (Fe, Zn)0.154 (Fe, Zn)0.154 (Fe, Zn)0.231 Zn0.461 . (1)

Based on crystallographic data, fragmentary information on site occupancies and an experimentally seen width of the homogeneity region demonstrated by the phase, it was speculated that the rst and the third sublattices would likely accommodate aluminum [14]: (Al, Fe, Zn)0.154 (Fe, Zn)0.154 (Al, Fe, Zn)0.231 Zn0.461 . (2)

Gibbs energies of formation of compounds are to be found in the course of optimization. In addition to these unknown quantities, at least seven interaction parameters should be considered: 0 L Al,Fe:::Zn , 0 L Al,Zn:::Zn , 0 L Fe,Zn:::Zn , 0 L :Fe,Zn::Zn , 0 0 0L ::Al,Fe::Zn , L ::Al,Zn::Zn and L ::Fe,Zn::Zn . It is worth remembering that the Gibbs energies of formation and the interaction parameters may depend on temperature and that a total number of adjustable parameters in the expression for the total Gibbs energy of the phase to be evaluated may be forbiddingly large. This large number of coefcients does not constitute a problem if one has representative arrays of reliable thermodynamic data (activities, enthalpies, etc.) and conditions of phase equilibria (tie-lines, locations of invariant triangles, etc.) the phase participates in, and if these arrays are mutually consistent. In our case, available thermodynamic data are not so accurate, and agreement between the various phase diagrams proposed is not so perfect that one can hope to derive a large number of adjustable coefcients without strong correlations among them. But if the models parameters are strongly correlated, then an alternative model with a fewer number of parameters should be considered. Let us analyze what happens with the thermodynamic model for the phase if either the rst sublattice or the third sublattice (but not both!) hosts aluminum. Version 1: (Al, Fe, Zn)0.154 (Fe, Zn)0.154 (Fe, Zn)0.231 Zn0.461 (3)

The total number of end-members in the model (2) is equal to 3 2 3 = 18. Since a total number of end-members in the model (1) is equal to 2 2 2 = 8, as many as 18 8 = 10 new

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Table 3 Sublattice models of ternary phases originating from ZnFe binary phases 1 Model proposed in [14] Model used in this work Model proposed in [14] Model used in this work Model proposed in [14] Model used in this work Model proposed in [14] Model used in this work (Al, Fe, Zn)0.154 (Fe, Zn)0.154 (Al, Fe, Zn)0.231 Zn0.461 (Fe, Zn)0.154 (Fe, Zn)0.154 (Al, Fe, Zn)0.231 Zn0.461 Fe0.137 (Al, Fe, Zn)0.118 Zn0.745 Fe0.058 (Al, Fe, Zn)0.180 Zn0.525 (Al, Zn)0.237 Fe0.058 (Al, Fe, Zn)0.180 Zn0.525 Zn0.237 (Al, Fe, Va)0.072 (Al, Zn, Va)0.072 Zn0.856 (Fe, Va)0.072 (Al, Zn, Va)0.072 (Al, Zn)0.856 Table 4 Sublattice models of ternary phases stemming from FeAl binary phases Phase Fe4 Al13 FeAl2 Fe2 Al5 Seierstens model Al0.6275 Fe0.235 (Al, Va)0.1375 Fe1 Al2 Fe2 Al5 Model used in this work Al0.6275 Fe0.235 (Al, Zn, Va)0.1375 Fe1 Al2 (Zn, Va)0.035 Fe2 Al5 (Zn, Va)3

Version 2: (Fe, Zn)0.154 (Fe, Zn)0.154 (Al, Fe, Zn)0.231 Zn0.461 . (4) The number of new Gibbs energies of compounds is equal to 4 for both models. The models (3) and (4) have the same minimal number of interaction parameters. An important distinction between these models is that they predict different upper limits of the Al solubility: 15.4 at.% for the model (3) and 23.1 at.% for the model (4). However, both upper limits by far exceed an experimentally established solubility of Al in the phase (1.4 at.% Al [7]). Which model (3) or (4) should preference be given to? The assessment of the ZnFeAl system was tried with both models. After it had been found that the model (4) provided a better match with experimental quantities, this model was adopted as the model for the phase. That choice should not be misinterpreted! It is not claimed that if the optimization is easier to carry out with a particular phase model, then this model is more physically feasible in comparison with other possible models. Let us recall that the models (3) and (4) have the same number of adjustable parameters. Although the upper limits of Al solubility predicted by the models are different (see above), this difference is immaterial because the solubility of aluminum in the phase is only a few percent. Moreover, a lack of data on site occupancies does not allow one to make a choice: before the optimization, both models are equally reasonable. A quality of assessment is a non-physical criterion, but at least it is a criterion. The same reasoning was employed for choosing the sublattice models for the rest of ternary phases originated from the binary ZnFe phases. These models are presented in Table 3. A possibility of having two modications of the phase [16] deserves a special experimental inquiry. When and if evidence that two polymorphic modications exist, the thermodynamic descriptions of the ZnFe and ZnFeAl systems will need to be rened. The present assessment was performed assuming that a single phase existed. 3.2.2. Phases stemming from FeAl binary phases All phases in the FeAl system except Fe4 Al5 were allowed to dissolve zinc. Consequently, the phase models suggested by Seiersten [15] are to be modied. An alteration made is based on experimental observations that FeAl2 and Fe2 Al5 are line phases originating from corresponding binary FeAl phases and always aiming at the Zn corner of the concentration triangle [7]. To reect this behavior, the models proposed for FeAl2 and Fe2 Al5 in [15] were artlessly modied

Fig. 3. The FeAl phase diagram [15].

Fig. 4. The ZnAl phase diagram [31].

by using an additional sublattice accommodating Zn and vacancies (Table 4). The phase diagram of the FeAl system resulting from the Seiersten model is presented in Fig. 3. As seen from Fig. 4, there are no intermediate phases in the ZnAl system [31].

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3.3. The ternary 2 phase It is pertinent to start this section with addressing a terminological issue. Perrot et al. [7] named the ternary phase existing in the ZnFeAl system the 2 phase. In contrast, Tang [10] named this phase the T phase, which seems more justied since the phase is a ternary one and since the phase discovered in the ZnFeNi system with the same crystal structure had been named the T phase. In this work, it was decided to use the 2 designation for emphasizing that this ternary phase is isomorphic with the binary 1 phase in the ZnFe system. Another reason for giving preference to 2 is that a crystallographically different ternary phase in the AlFeSi system was referred to as the tau phase [44]. If a thermodynamic description of the ZnFeAlSi system is constructed, it would be disadvantageous to have two different phases having the same name. Although the 2 phase is presumably isomorphic with the 1 phase, they are always separated by a two-phase region, i.e. they never form a solid solution whatever the temperature (420500 C). It is justiable to deem that 2 and 1 are two composition sets of the same phase having a miscibility gap. Consequently, one can try to construct a single analytical expression for the Gibbs energy of this phase instead of two separate models, one for 2 and another for 1 . Let us recall that in the ZnFe system, the 1 phase was described by the model Fe0.137 (Fe, Zn)0.118 Zn0.745 and that an excess term was not needed in the expression for its Gibbs energy. An absence of the excess term means that the 1 phase does not tend to decompose. When 2 was considered as an individual phase and when the model (Al, Fe, Zn)0.255 Zn0.745 was ascribed to it, optimization results clearly indicated that this phase was also not prone to decomposition since all eigenvalues of the Hessian of its Gibbs energies were positive within the xFe xAl T volume enveloping 2 . Since the 2 and 1 phases are situated not far from each other, it is difcult to model them as two composition sets of one phase without making use of absurdly huge positive interaction parameter(s). Due to these reasons, the 2 phase is considered in the present work as an individual phase, whose sublattice model resembled that of the 1 phase. It should be mentioned that there is no agreement in the literature as to whether the 2 phase is formed in a bath or not. A difference of opinion may be caused by the fact that the composition of the 2 phase is not very different from the composition of the phase when it dissolves a signicant amount of Al. In other words, an identication based on a chemical analysis is not very suitable for specifying intermetallics presented in the bath. If it is believed that the 2 phase does not appear due to kinetic reasons, then it should be excluded from a list of possible phases before starting thermodynamic calculations. For example, the equilibrium diagram shown in Fig. 14 corresponds to the case when the 2 phase participates in equilibria. Isothermal sections presented in Figs. 912 are metastable in the sense that the 2 phase was not taken into account. If the formation of this phase is kinetically impeded, then the latter diagrams are more useful from the technological viewpoint.

4. Mathematical model 4.1. Substitutional solutions The molar free energy of each substitutional phase was described on the same basis as the binary case [14] except that in the ZnFeAl system, ternary interaction parameters may be required. For example, the molar Gibbs free energy for the ternary LIQUID phase can be described as G LIQ m = x Al
LIQ 0

G Al + xFe
LIQ LIQ

LIQ

LIQ 0 LIQ

G Fe + xZn
LIQ

LIQ

LIQ 0 LIQ

G Zn

LIQ

+ RT (xAl ln xAl + xFe ln xFe + xZn ln xZn ) + ex G LIQ m where

ex n i i =0 n i i =0 n i i =0 LIQ LIQ LIQ LIQ + xAl xFe xZn L Al,Fe,Zn . LIQ

(5)

G LIQ m = x Fe x Zn

LIQ LIQ

L Fe,Zn (xFe xZn )i L Al,Zn (xAl xZn )i L Al,Fe (xAl xFe )i (6)
LIQ LIQ LIQ LIQ LIQ LIQ

LIQ

LIQ

LIQ

+ xAl xZn + xAl xFe

LIQ LIQ

LIQ LIQ

The interaction parameter L may be temperature dependent:

i

L Fe,Zn = i a

LIQ

LIQ

+ ib

LIQ

T + ic

LIQ

T ln T . . . .

(7)

The lattice stabilities of elements phases were taken from SGTE5 data for pure elements [45]. The order of elements LIQ LIQ LIQ LIQ LIQ LIQ in (xFe xZn )i , (xAl xZn )i and (xAl xFe )i must be treated carefully as the sign of Eq. (6) is affected when LIQ i = odd integer. The ternary interaction parameter L Al,Fe,Zn can be expressed as L Al,Fe,Zn = xAl
LIQ LIQ 0 LIQ LIQ LIQ L Al,Fe,Zn + xFe 1 L Al,Fe,Zn LIQ 2 LIQ L Al,Fe,Zn

+ xZn
LIQ

(8)

where k L Al,Fe,Zn may be temperature-dependent. During the later stages of the optimization process, it was found that the ternary interaction parameters were not necessary for any of the substitutional phases; they are therefore not included in the present model. 4.2. Intermediate phases The same basic procedures described in [14] were followed except that additional terms were required for the third component. For example, with the sublattice model (Fe)0.137 (Al, Fe, Zn)0.118 (Zn)0.745 , the 1 phase in ZnFeAl is described as
5 Scientic Group Thermodata Europe (http://www.sgte.org).

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0 1 0 1 0 1 1 G m = yAl G Fe:Al:Zn + yFe G Fe:Fe:Zn + yZn G Fe:Zn:Zn

+ 0.118 RT ( yAl ln yAl + yFe ln yFe + yZn ln yZn )

n

+ yAl yFe
i =0 n

1 i L Fe :Al,Fe:Zn ( yAl yFe )

i 1 L Fe:Al,Zn:Zn ( yAl yZn ) i 1 L Fe:Fe,Zn:Zn ( yFe yZn )

+ yAl yZn
i =0 n

+ yFe yZn
i =0

(9)

Additional liquidus data [22] with more temperature variations (450480 C) were also utilized. The composition of the solution was varied from 0.09 to 0.24 wt% Al and 0.006 to 0.042 wt% Fe. The errors in these compositions were estimated to be 5% of the amount present. It should be noted that this liquidus was measured after 2 h of equilibration, which was much longer than the typical galvanizing practice (3 s) but not long enough to attain true global equilibrium where the 2 phase nucleates in the system. The data were therefore treated as metastable and 2 was suppressed during the related optimization. 5.2. EMF data Raw EMF data were obtained using the Al sensor technique. The activities were measured both by varying Al content in LIQUID while keeping the temperature, and by varying temperature while keeping the composition of LIQUID constant. The detailed experimental procedures are explained in the previous reports [8,23]. Phase diagram data were also measured along with activities under the same conditions. This set of activities and compositional data is therefore uniquely valuable and it was primarily used for optimization related to any equilibrium with LIQUID. EMF and activity values are presented in Appendix. 6. Optimization: Results and discussion The optimization was carried out by using the PARROT module of Thermo-Calc. It is worth mentioning that statistical weights assigned to experimental points remained intact in the course of assessment. Since this work is not devoted to particularities and peculiarities of using the PARROT module of ThermoCalc, a detailed description of steps leading to a successful optimization of the ZnFeAl system would not be appropriate. Instead, let us briey discuss how activities of aluminum calculated from EMF data were made use of. Let us recall that these activities were measured in either two- or three-phase regions. For the latter case, an overall composition is immaterial since aAl remains constant within an invariant triangle. If it is known which three phases are in equilibrium, then the following should be added to a POP le, i.e. the le containing experimental data: @@ Example: LIQUID, ZETA @@ and GAMMA2 are in equilibrium CREATE NEW EQUILIBRIUM 1 1 CHANGE STATUS PHASE LIQUID = FIXED 1 CHANGE STATUS PHASE ZETA = FIXED 1 CHANGE STATUS PHASE GAMMA2 = FIXED 1 SET REFERENCE STATE AL FCC * 1E5 SET CONDITION P=1E5 SET CONDITION T=698.75:1 EXPERIMENT ACR(AL)=0.0144:0.005 In addition to EMF data, Yamaguchi et al. estimated the concentration of aluminum in the liquid phase coexisting with

where the total number of all the sublattice sites is equal to unity.6 The excess terms may or may not be needed depending on complexity of related equilibria and a model description of the phase. This can only be determined during optimization. The molar Gibbs energies of the rest of the intermediate phases were described in the same fashion. For phases that were approximated as stoichiometric (FeAl2 and Fe2 Al5 ), no interaction parameters were required. It is now worth recalling that one of the major objectives of this modeling exercise was to keep the number of interaction parameters as small as possible by utilizing physical consistency of the model. As demonstrated with the binary assessment in the previous chapter, this is effectively achievable by basing sublattice models on crystallographic information. 5. Survey of experimental data used in the optimization 5.1. Phase diagram data Among all the phase diagram evaluations previously reported for the ZnFeAl system [310], only three Perrot et al., Yamaguchi et al. and Tang et al. [7,8,10] included the ternary phase 2 at the Zn-rich corner. In each case, these investigators utilized long equilibration times: 1000 h, 1000 h and 360 h, respectively. Since these investigators seem more likely to attain equilibrium, their works were primarily utilized for this study. Perrot et al. and Tang et al. investigated the entire isotherms at 450 C and 435 C, respectively. Perrot et al. pursued their investigation by immersing Al-containing Fe samples in ZnAl baths. Three-phase equilibria are reported after Energy Dispersive Spectroscopy (EDS) analyses with an error of 0.2 at.% for compositions. Tang et al. carried out their work by synthesizing each alloy of interest. Both two-phase and three-phase equilibria are reported from EDS analyses. Errors associated with compositions are estimated as being from 0.1 to 0.8 at.%. The liquidus has been studied for decades, particularly in the temperature range relevant to galvanizing practices [1721]. In the work of McDermid et al. [21], dross particles were physically ltered out and then the liquid portion was chemically analyzed. Their data were primarily used for optimization related to liquidus, along with others [1720].
6 0.137 + 0.118 + 0.745 = 1.

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two other phases. This important extra piece of information can and should be reected: EXPERIMENT W(LIQUID,AL)=0.094E-2:0.06E-2 The situation becomes quite different in a two-phase region, in which a measurement of the electromotive force is useless if nothing is known about the compositions of two coexisting phases or about the overall composition of the system. Since the concentration of aluminum in the liquid phase was evaluated by Yamaguchi et al., the following fragment in the POP le reects experimental conditions and results: @@ Example: LIQUID and ZETA are in equilibrium CREATE NEW EQUILIBRIUM 2 1 CHANGE STATUS PHASE LIQUID = FIXED 1 CHANGE STATUS PHASE ZETA = FIXED 1 SET REFERENCE STATE AL FCC * 1E5 SET CONDITION P=1E5 SET CONDITION T=698.75:1 SET CONDITION W(LIQUID,AL)=0.0005:0.0006 EXPERIMENT ACR(AL)=0.0133:0.005 Sometimes, not only Al concentration, but Fe concentration as well was measured at the phase boundary separating the liquid phase from a two-phase region. While this additional knowledge cannot be used in setting conditions (for a ternary system exactly ve conditions are needed), it can be reected in an extra EXPERIMENT line. In the course of the assessment, signicant difculties were encountered. More specically, post-optimization artifacts were observed. Since the problem of unexpected equilibria is important from both methodological and practical angles, it is deemed pertinent to discuss the complications the optimization stumbled upon in some detail. The rst artifact is an inverted miscibility gap in the liquid phase predicted by the model at elevated temperatures. This shortcoming is inherited from a thermodynamic model for the binary ZnFe melt proposed in [14]. According to that description, the minimum of an actually nonexisting inverted two-phase liquid+liquid cupola is located at xZn 0.835 and T 1802 K. Although the presence of this artifact is awkward, it does serve to caution that the thermodynamic model of the ZnFeAl system presented in this work should never be used so far beyond the 420500 C range. An artifact of another kind was detected when a thermodynamic description of the whole ZnFeAl system was used for constructing three binary diagrams. It is worth emphasizing that from a precision viewpoint (i.e. from a formal viewpoint), the assessment of the ternary system was a success: almost all experimental observations had been accurately reproduced. In spite of this conrmation of accuracy, the 2 phase unexpectedly appeared in the ZnFe and ZnAl systems. Moreover, at low temperatures, pure Zn having the 2 structure was found to be more thermodynamically stable than Zn possessing the HCP structure! To understand this, let us recall that the sublattice model used for this phase was (Al, Fe, Zn)0.255 Zn0.745 . Let us also realize that statistically optimal Gibbs energies of three end-members and interaction parameters were derived from experimental information related

exclusively to the interior of the concentration triangle. It should also be remembered that experimental data were obtained within the 420500 C region. The optimization 0 G HCP 3967.04 + 6 T 2 procedure resulted in 0 G Zn:Zn = Zn:Zn as the best temperature dependency of the Gibbs energy of 2 the Zn0.255 Zn0.745 end-member. With this 0 G Zn :Zn ( T ) and other parameters the procedure led to, various isothermal and isoplethal section can be calculated. Inside the 420500 C range, they all look very reasonably and conform well to what 0 HCP 2 is known from experiments. However, 0 G Zn:Zn < G Zn:Zn if T < 388.02 C, which is absurd. The interaction parameter 0 L 2 = 9502.85 suggested by the optimization Zn,Fe:Zn procedure is negative, which implies that 2 would possess a noticeable homogeneity region in the ZnFe system, i.e. in the system in which it does not exist! After the problem had been detected and its implications had been realized, the thermodynamic model of the ZnFeAl system was rened. It is now guaranteed that the only remaining artifact is the inverted miscibility gap transferred from a thermodynamic description of the liquid phase in the ZnFe system. The optimized parameters for the ZnFeAl system are shown in Table 5. Note that compound energies and interaction parameters not shown in Table 5 are zero. A Thermo-Calc compatible database (a TDB le) that the assessment resulted in is available upon request. The calculated activities of Al in three-phase regions with respect to temperature are presented in Fig. 5 along with experimental measurements. Boundaries between two-phase elds correspond to three-phase equilibria. Evidently, the present model accurately reproduces all three-phase equilibria seen in reality. EMF values measured in various two-phase regions were reproduced with a great deal of accuracy. The maximal absolute value of the weighted deviation is less than 0.12. Weighted residuals for all EMF measurements (i.e., corresponding to both two- and three-phase elds) are shown in Fig. 6. Although the negative tail is a bit heavy, the histogram has a characteristic bell shape pointing to the normal distribution of weighted deviations. The whole isothermal section of the ZnFeAl system at 450 C is computed and shown in Fig. 1. Experimentally found coordinates of corners of invariant triangles are compared with computed quantities in isothermal sections presented in Figs. 7 and 8. In these gures, each calculated corner is marked with a letter. In the gure and in a corresponding legend, experimental points related to a particular corner are shown by using easily distinguishable symbols. In the legend, these symbols are situated below the letter used for marking the corner. The closer the symbols are located to the letter, the better the accuracy the position of the corner is reproduced by the model. Due to an abundance of experimental data and complexity of the isothermal sections, Figs. 7 and 8 are not easy to analyze. Note that points evaluated from experimental phase diagram assessment [10] are also shown in the gures. However, along with Table 6, these gures suggest that phase equilibria were described reasonably accurately. However, several exceptions deserve explanation.

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J. Nakano et al. / Computer Coupling of Phase Diagrams and Thermochemistry 31 (2007) 125140 Table 5 (continued) : (Fe, Zn)0.154 (Fe, Zn)0.154 (Al, Fe, Zn)0.231 Zn0.461
0 G 0 FCC 0 BCC 0 HCP Fe:Fe:Al:Zn 0.231 GAl 0.308 GFe 0.461 GZn = 0 0 G 0 FCC 0 BCC 0 HCP Fe:Zn:Al:Zn 0.231 GAl 0.154 GFe 0.615 GZn

Table 5 Analytical descriptions of the thermodynamic properties of phases in the ZnFeAl system (0 G and i L are in J/mol, quantities evaluated in this work are in bold) LIQUID: (Al, Fe, Zn)1
0 LLIQ = +58 088 23.665T Fe,Zn 1 LLIQ = +92 219 55.584T Fe,Zn 2 LLIQ = +13 570 Fe,Zn 0 L LIQ = 91 976.5 + 22.1314T a Al,Fe 1 L LIQ = 5672.58 + 4.8728T a Al,Fe 2 L LIQ = +121.9a Al,Fe 0 L LIQ = +10 465.55 3.39259T b Al,Zn

= 2000 3.5T
0 G 0 BCC 0 HCP Fe:Zn:Fe:Zn 0.385 GFe 0.615 GZn = 5900.8 + 2.406T 0 G 0 BCC 0 HCP Fe:Zn:Zn:Zn 0.154 GFe 0.846 GZn = 2959.6 0.448T 0 G 0 FCC 0 BCC 0 HCP Zn:Fe:Al:Zn 0.231 GAl 0.154 GFe 0.615 GZn = 0 0 G 0 FCC 0 HCP Zn:Zn:Al:Zn 0.231 GAl 0.769 GZn = 0 0 G 0 BCC 0 HCP Zn:Zn:Fe:Zn 0.231 GFe 0.769 GZn = +793 + 4.782T 0 G 0 HCP Zn:Zn:Zn:Zn GZn = +6602.65 8.157T 0 L Fe:Zn:Al,Fe:Zn = 15 000 4T 0 L Fe:Zn:Al,Zn:Zn = 100 12T 0 L Fe:Zn:Fe,Zn:Zn = 10 394.77 + 12.1876T

BCC: (Al, Fe, Zn)1 (Va)3

0 LBCC Fe,Zn:Va = 10 494 + 18.299T 1 LBCC Fe,Zn:Va = +15 513 12.608T

TcBCC Fe:Va = +1043.85 TcBCC Fe,Zn:Va = +504.3

0 L BCC a Al,Fe:Va = 122 960 + 7.9972T 1 L BCC a Al,Fe:Va = +2945.2 a T cBCC Al,Fe:Va = +504

1 : Fe0.137 (Al, Fe, Zn)0.118 Zn0.745

0 G 1 0 FCC 0 BCC 0 HCP Fe:Al:Zn 0.118 GAl 0.137 GFe 0.745 GZn = 6900 0 G 1 0 BCC 0 HCP Fe:Fe:Zn 0.255 GFe 0.745 GZn = 8609.4 + 5.4T 0 G 1 0 BCC 0 HCP Fe:Zn:Zn 0.137 GFe 0.863 GZn = 5089.67 + 1.898T 0 L 1 Fe:Al,Fe:Zn = 5300 0 L 1 Fe:Al,Zn:Zn = 2500

FCC: (Al, Fe, Zn)1 (Va)1

0 LFCC Fe,Zn:Va = +6934.7 + 4.212T 1 LFCC Fe,Zn:Va = +691 0 L FCC a Al,Fe:Va = 76 066.1 + 18.6758T 1 L FCC a Al,Fe:Va = +21 164.4 + 1.3398T 0 L FCC b Al,Zn:Va = +7297.48 + 0.47512T 1 L FCC b Al,Zn:Va = +6612.88 4.5911T 2 L FCC b Al,Zn:Va = 3097.19 + 3.30635T

2 : (Al, Fe, Zn)0.255 Zn0.745

0 G 2 0.255 0 GFCC 0.745 0 GHCP = +7370.454 Zn Al:Zn Al 0 G 2 0 BCC 0 HCP Fe:Zn 0.255 GFe 0.745 GZn = 0 0 G 2 0 HCP Zn:Zn GZn = +2665.3728 0 L 2 Al,Fe:Zn = 32 689.0355 0 L 2 Al,Zn:Zn = 16 069.1316 + 0.781T 0 L 2 Fe,Zn:Zn = 12 561.3751 0 L 2 Al,Fe,Zn:Zn = 15 588.2333

HCP: (Al, Fe, Zn)1 (Va)0.5

0 LHCP Fe,Zn:Va = +12 786 0 L HCP a Al,Fe:Va = 106 903 + 20T 0 L HCP b Al,Zn:Va = +18 820.95 8.95255T 1 L HCP b Al,Zn:Va = +1000 000 2 L HCP b Al,Zn:Va = +1000 000 3 L HCP b Al,Zn:Va = 702.79

: Fe0.058 (Al, Fe, Zn)0.180 Zn0.525 Zn0.237

0 G 0 FCC 0 BCC 0 HCP Fe:Al:Zn:Zn 0.18 GAl 0.058 GFe 0.762 GZn

= +10 919 10.5T

0 G 0 BCC 0 HCP Fe:Fe:Zn:Zn 0.238 GFe 0.762 GZn = 3886 + 1.365T 0 G 0 BCC 0 HCP Fe:Zn:Zn:Zn 0.058 GFe 0.942 GZn = 3072 + 0.893T 0 L Fe:Al,Fe:Zn:Zn = 23 514 0 L Fe:Al,Zn:Zn:Zn = 12 317

J. Nakano et al. / Computer Coupling of Phase Diagrams and Thermochemistry 31 (2007) 125140 Table 5 (continued)
1 L Fe:Al,Zn:Zn:Zn = 4318 0 L Fe:Fe,Zn:Zn:Zn = 5742.666 + 3.755T

133

: (Fe, Va)0.072 (Al, Zn, Va)0.072 (Al, Zn)0.856

0 G 0 HCP 0 BCC 0 FCC Fe:Al:Zn 0.856 GZn 0.072 GFe 0.072 GAl = +1023 7.6T 0 G 0 BCC 0 HCP Fe:Va:Zn 0.072 GFe 0.856 GZn = +700.31 2.562T 0 G 0 BCC 0 HCP Fe:Zn:Zn 0.072 GFe 0.928 GZn = 3861.9 + 1.152T 0 G 0 FCC 0 HCP Va:Al:Zn 0.072 GAl 0.856 GZn = +100 0 G 0 HCP Va:Va:Zn 0.856 GZn = +14T 0 G Va:Zn:Al = +2000 0 G 0 HCP Va:Zn:Zn 0.928 GZn = +808.7 0.102T

Fe4 Al13 : Al0.6275 (Fe, Zn)0.235 (Al, Zn, Va)0.1375 c

0 GFe4 Al13 0.6275 0 GFCC 0.235 0 GBCC 0.1375 0 GHCP = 23 500 Fe Zn Al:Fe:Zn Al 0 GFe4 Al13 0.765 0 GFCC 0.235 0 GHCP = +3147 Zn Al:Zn:Al Al 0 GFe4 Al13 0.6275 0 GFCC 0.235 0 GHCP = +2000 Zn Al:Zn:Va Al 0 GFe4 Al13 0.6275 0 GFCC 0.3725 0 GHCP = 0 Zn Al:Zn:Zn Al 0 G Fe4 Al13 0.765 0 G FCC 0.235 0 G BCC = 30 714.3 + 7.44T a Fe Al:Fe:Al Al 0 G Fe4 Al13 0.6275 0 G FCC 0.235 0 G BCC = 27 781.3 + 7.2566T a Fe Al:Fe:Va Al

Fig. 5. Calculate activities of aluminum in three-phase regions (lines) with experimental data superimposed.

Fe2 Al5 : Fe2 Al5 (Zn, Va)3 c

0 GFe2 Al5 5 0 GFCC 2 0 GBCC 3 0 GHCP = 277 947 + 121.95T Fe Zn Fe:Al:Zn Al 0 G Fe2 Al5 5 0 G FCC 2 0 G BCC = 228 576 + 48.99503T a Fe Al Fe:Al:Va

FeAl2 : Fe1 Al2 (Zn, Va)0.035 c

0 GFeAl2 0 FCC 0 BCC 0 HCP Fe:Al:Zn 2 GAl GFe GZn = 96 068 + 16T 0 G FeAl2 2 0 G FCC 0 G BCC = 98 096.9 + 18.7503T a Fe Fe:Al:Va Al

Fig. 6. Weighted residuals for EMF measurements in two- and three-phase regions.

Fe4 Al5 : (Al, Fe)1 c

0 G Fe4 Al5 0 G FCC = +12 178.9 4.813T a Al Al 0 G Fe4 Al5 0 G BCC = +5009.03a Fe Fe 0 L Fe4 Al5 = 131 649 + 29.4833T a Al,Fe 1 L Fe4 Al5 = 18 619.5a Al,Fe a Parameters adopted from [15]. b Parameters adopted from [31]. c Sublattice models adopted or extended from [15].

Firstly, the solubility of Zn in Fe2 Al5 slightly exceeds that experimentally observed. This can likely be attributed to the

fact that the sublattice model used for this phase is not a crystallographically consistent one. This excessive solubility has virtually no effect upon equilibria in the Zn-rich corner of the diagram. Secondly, a homogeneity region of Fe4 Al13 has an unusual shape, which, however, is consistent with the Schreinemakers rule [24]. Thirdly, the BCC position of the invariant + Fe2 Al5 + BCC triangle does not conform well to its experimentally found location. This is a direct consequence of adopting the description of the FeAl system proposed in [15]. A better match with experiment can hardly be achieved without revisiting the Seierstens model, which is beyond the scope of the present contribution. The present model is focused on

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J. Nakano et al. / Computer Coupling of Phase Diagrams and Thermochemistry 31 (2007) 125140

Fig. 7. A zinc-rich portion of a calculated 450 C section with experimental data points superimposed.

Fig. 9. A near-Zn fragment of a calculated 450 C section with experimental data superimposed.

Fig. 8. A portion of a calculated 450 C section with experimental data points superimposed.

Fig. 10. A zinc-rich corner of a 460 C section with experimental data superimposed.

the Zn-rich corner of the ZnFeAl system at galvanizing temperatures, which has been well reproduced. It is worth emphasizing that the 2 phase behaves exactly as experimental observations suggest: being an entity whose presence is crucial for the analysis of phase equilibria in the Zn-rich corner at relatively low temperatures, this phase ceases to exist slightly above 460 C. Isothermal sections depicted in Figs. 912 demonstrate that liquidus data were reproduced with a great deal of accuracy from 450 to 480 C. For comparing experimental and calculated quantities, it was necessary to disallow the 2 phase to participate in equilibria. The reason is that 2 was not seen in those investigations [18,2022] that are compared with the results of present modeling. With the existence of 2 , the phase is no longer in equilibrium with Fe2 Al5 in LIQUID (Fig. 14).

A projection of the liquidus surface with areas of primary solidication identied is shown in Fig. 13. This gure stipulates that even a small uctuation of process parameters (e.g., temperature) is important for ne-tuning the galvanizing process. Despite some minor disagreements with phase diagram data, the thermodynamic description of the ZnFeAl system proposed in this work and summarized in Table 5 conforms very well to an overwhelming majority of experimental observations. It is worth reiterating that the model reproduces very accurately activities of Al in two- and three-phase mixtures. Although it has not been proven or even demonstrated that the model remains workable above 500 C, it is denitely valid within a region important for the theory and practice of galvanizing and galvannealing. From this perspective, it is not surprising that the model was successfully used for nding

J. Nakano et al. / Computer Coupling of Phase Diagrams and Thermochemistry 31 (2007) 125140

135

Table 6 Characteristics of invariant equilibria in the ZnFeAl system Equilibrium Phase (letters in Figs. 7 and 8) Reference Exp. Cal. Present (b) [5] [6] [7] Present -Fe2 Al5 BCC Fe2 Al5 (p) [5] [6] [7] Present BCC (l) [5] [6] [7] Present 2 (g) [7] [10] Present 2 Fe2 Al5 (c) [7] [10] Present Fe2 Al5 (p) [7] [10] BCC (k) BCC1 1 (a) BCC 1 BCC (j) Fe4 Al13 (q) [7] Present 2 (i) 2 Fe2 Al5 LIQ Fe2 Al5 (p) [7] [10] [7] [10] Present Present Present [7] Present [10] Present [10] Present [10] Present Present Present Present Present 11.3 8.4 1 9.0 0.6 10.4 0.2 35.1 42.9 1 36.0 0.6 36.3 0.2 74.3 69.1 2 63.7 1.5 63.4 0.2 7.0 6.9 8.6 0.2 8.6 0.4 7.3 7.0 8.9 0.2 10.4 0.4 33.7 33.3 36.3 0.2 33.6 0.5 74.7 79.1 0.8 15.3 13.6 0.5 11.3 10.4 0.4 85.30 91.15 0.2 37.3 37.6 0.2 6.6 6.3 6.4 0.2 6.9 0.4 33.6 33.2 36.3 0.2 34.8 0.5 1.8 3.4 1 2.8 0.3 1.3 0.2 42.4 43.73 1 43.1 1.1 45.0 0.2 25.0 18.9 2 34.3 0.6 32.39 0.2 2.8 2.8 2.9 0.2 3.2 0.3 1.5 1.3 1.7 0.2 1.5 0.4 40.7 40.3 45.0 0.2 45.9 0.6 24.7 11.2 0.6 2.5 2.8 0.1 1.7 1.5 0.4 14.1 4 0.2 54.0 54.8 0.2 2.8 2.8 3.8 0.2 3.2 0.3 40.5 40.1 45.0 0.2 44.8 0.6 450 450 450 450 450 450 450 450 450 450 450 450 450 435 450 435 450 435 450 435 450 435 450 435 438 435 438 435 438 435 450 450 450 450 450 435 450 435 450 435 450 435 Fe (wt%) Al (wt%) T ( C)

Fe4 Al13 Fe2 Al5 LIQ

(continued on next page)

136 Table 6 (continued) Equilibrium

J. Nakano et al. / Computer Coupling of Phase Diagrams and Thermochemistry 31 (2007) 125140

Phase (letters in Figs. 7 and 8)

Reference Exp. Cal. Present [7] Present [7] Present [7] Present [7] Present

Fe (wt%)

Al (wt%)

T ( C)

2 2 LIQ (h) (d) (e) LIQ (f)

6.7 6.6 0.2 6.8 6.6 0.2 6.7 6.8 0.2 5.8 6.0 0.2 0.032 0.03 <0.0010 0.037 5% 0.024 0.03 <0.0010 0.027 5%

2.8 2.1 0.2 1.4 1.8 0.2 1.1 1.0 0.2 0.6 0.8 0.2 0.057 0.10 <0.0020 0.067 5% 0.137 0.135 <0.0020 0.136 5%

450 450 450 450 450 450 450 450 460 460 460 460 460 460

LIQ

[20] [43] Present

-Fe2 Al5 LIQ (metastable)

LIQ

[20] [43]

Fig. 11. A comparison of a calculated 470 C section with experimental data.

Fig. 12. A zinc-rich corner at 480 C with experimental data.

ways to minimize dross formation in galvanizing baths, for a thermodynamic explanation of the inhibition layer breakdown as well as for revealing the effect of the silicon content in the bath on the properties of the nal product [25]. 7. Conclusion With the aid of ternary activity data and new information on the ternary liquidus surface, a thermodynamic description for the system ZnFeAl has been constructed on the foundation of the ZnFe binary model [14]. The present model is considered valid from 420 to 500 C, the temperature range of most relevance to galvanizing practice. Good agreement has been

demonstrated between the predictions of the model and the best available experimental data, thereby helping to conrm the extensibility of the crystallographically-consistent binary model to higher order systems. Acknowledgements The authors are grateful to Professor Joseph R. McDermid for providing his unpublished data on liquidus used in the optimization, and to the referees for their constructive criticism of an earlier version of this manuscript. Financial support from the McMaster Steel Research Centre is gratefully acknowledged.

J. Nakano et al. / Computer Coupling of Phase Diagrams and Thermochemistry 31 (2007) 125140 Table A.1 Temperature +L 423.2 427.7 428.1 432.9 434.9 442.8 443.2 448.1 458.0 458.0 +L 487.1 492.5 475.4 487.3 497.0 471.8 472.3 479.6 482.2 492.1 506.7 464.7 467.5 472.9 477.8 482.5 492.4 502.3 462.6 464.7 467.7 469.9 473.2 477.0 482.2 502.0 451.7 454.5 457.4 467.7 477.4 487.5 447.5 449.7 462.9 482.2 501.6 444.9 444.5 449.7 459.2 468.7 479.8 498.0 2 + L 427.7 430.3 432.1 435.2 0.108 0.107 0.103 0.103 83.01 83.78 84.95 85.65 0.023 0.023 0.039 0.040 0.040 0.049 0.048 0.048 0.048 0.048 0.050 0.058 0.059 0.059 0.060 0.059 0.059 0.058 0.066 0.067 0.067 0.066 0.067 0.067 0.068 0.068 0.079 0.078 0.078 0.077 0.078 0.079 0.088 0.087 0.088 0.089 0.093 0.101 0.101 0.104 0.103 0.104 0.108 0.110 130.10 131.55 115.60 118.06 120.51 109.80 110.37 112.17 112.81 115.26 117.95 104.47 104.79 106.09 106.91 108.40 110.79 113.56 101.23 101.41 102.13 102.97 103.43 104.34 105.25 109.94 94.89 95.81 96.49 99.16 101.15 103.23 91.68 92.42 95.22 99.41 102.88 88.24 88.15 88.71 91.05 92.99 94.67 98.33 0.080 0.074 0.074 0.080 0.074 0.073 0.032 0.053 0.031 0.052 88.01 90.62 90.72 90.26 92.31 94.45 111.52 102.33 116.02 105.15 Wt% of Al in the liquid phase EMF

137

aAl

0.0123 0.0110 0.0111 0.0117 0.0106 0.0101 0.0044 0.0072 0.0040 0.0066

Fig. 13. Liquidus projections and primary solidication elds of ZnFeAl (2 is suspended).

Fig. 14. A Zn-rich portion of the ZnFeAl phase diagram at full equilibrium (450 C).

Appendix. Experimental values of activity of Al with respect to FCC Electromotive forces presented in this appendix were measured by using the following concentration cell: Pure solid Al Saturated solution of NaCl in molten AlCl3 Two-phase or three-phase mixture

0.0026 0.0025 0.0047 0.0045 0.0043 0.0059 0.0058 0.0055 0.0055 0.0053 0.0051 0.0072 0.0072 0.0071 0.0070 0.0068 0.0065 0.0061 0.0082 0.0084 0.0083 0.0080 0.0080 0.0079 0.0078 0.0071 0.0104 0.0103 0.0101 0.0095 0.0092 0.0089 0.0119 0.0117 0.0111 0.0103 0.0098 0.0139 0.0138 0.0139 0.0132 0.0128 0.0125 0.0118

A portion of experimental data was reported in [8,23]. A method used for estimating the concentration of Al in the liquid phase is explained elsewhere [8]. In Table A.1, experimental quantities are characterized by the following estimations of errors: T = 1 C , WAl = 0.06%, EMF = 5 mV. An error associated with the calculated activities of aluminum does not exceed 0.005.

0.0162 0.0158 0.0150 0.0149

(continued on next page)

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J. Nakano et al. / Computer Coupling of Phase Diagrams and Thermochemistry 31 (2007) 125140

Table A.1 (continued) Temperature + Fe2 Al5 + L 459.5 459.5 459.5 460.2 462.1 465.1 465.4 469.8 469.8 470.0 470.1 470.8 471.9 479.4 479.6 479.7 480.4 480.5 482.0 482.0 489.4 489.4 489.7 489.9 490.2 490.6 491.6 499.5 499.5 500.0 500.0 500.2 500.5 500.7 501.7 511.1 + 2 + L 440.0 440.8 442.8 443.2 443.6 444.1 444.1 445.0 445.4 445.8 446.2 449.3 449.7 450.0 450.1 450.6 450.9 451.0 451.9 452.5 453.0 455.2 455.9 457.2 0.110 0.104 0.111 0.107 0.112 0.081 0.111 0.112 0.116 0.111 0.113 0.111 0.084 0.119 0.117 0.115 0.122 0.124 0.116 0.115 0.118 0.126 0.130 0.129 85.38 86.71 85.82 86.67 85.82 92.61 86.11 86.13 85.49 86.49 86.21 87.27 93.15 85.98 86.36 86.83 85.66 85.35 86.93 87.25 86.82 85.93 85.43 85.88 0.0155 0.0146 0.0154 0.0148 0.0154 0.0111 0.0153 0.0153 0.0158 0.0151 0.0154 0.0149 0.0112 0.0159 0.0157 0.0153 0.0162 0.0165 0.0154 0.0152 0.0156 0.0164 0.0169 0.0166 0.155 0.148 0.138 0.143 0.151 0.144 0.139 0.139 0.139 0.143 0.143 0.149 0.144 0.150 0.142 0.149 0.142 0.147 0.148 0.154 0.151 0.139 0.150 0.143 0.143 0.146 0.151 0.138 0.150 0.146 0.153 0.154 0.156 0.141 0.150 0.150 82.51 83.49 84.96 84.36 83.62 85.27 86.09 87.04 87.04 86.48 86.50 85.77 86.74 87.47 88.70 87.68 88.87 88.14 88.32 87.46 89.47 91.28 89.68 90.77 90.83 90.46 89.94 93.63 91.78 92.49 91.45 91.34 91.12 93.41 92.25 94.27 0.0198 0.0189 0.0176 0.0182 0.0191 0.0179 0.0173 0.0169 0.0169 0.0174 0.0174 0.0180 0.0174 0.0175 0.0165 0.0173 0.0165 0.0170 0.0170 0.0177 0.0168 0.0155 0.0167 0.0159 0.0159 0.0162 0.0166 0.0147 0.0160 0.0155 0.0163 0.0163 0.0165 0.0149 0.0158 0.0152 Wt% of Al in the liquid phase EMF aAl

Table A.1 (continued) Temperature 459.1 459.9 460.3 462.7 Wt% of Al in the liquid phase 0.138 0.138 0.143 0.095 EMF 84.87 85.05 84.38 93.55 aAl 0.0176 0.0176 0.0182 0.0120

Fe4 Al13 + Fe2 Al5 + L 421.6 430.5 431.4 441.0 450.3 460.1 460.8 459.2 460.1 469.7 480.2 480.2 480.2 489.3 499.8 499.8 2 + Fe2 Al5 + L 425.0 425.7 430.7 435.7 439.3 439.5 439.7 440.1 445.6 449.1 450.0 454.2 455.2 ++L 438.5 440.0 440.0 441.2 442.0 443.0 444.0 444.4 445.0 446.1 447.7 449.8 449.8 450.0 450.0 450.0 450.4 453.0 453.2 455.0 455.1 455.1 455.1 455.7 0.088 0.105 0.104 0.086 0.102 0.104 0.098 0.081 0.103 0.094 0.073 0.070 0.072 0.107 0.099 0.099 0.085 0.067 0.071 0.103 0.081 0.067 0.069 0.065 89.61 86.34 86.53 90.71 87.38 87.21 88.66 92.68 87.86 90.00 95.60 96.96 96.38 88.19 89.81 89.81 93.07 98.64 97.47 90.11 95.16 99.13 98.52 99.91 0.0125 0.0148 0.0146 0.0120 0.0142 0.0144 0.0135 0.0111 0.0141 0.0128 0.0099 0.0094 0.0096 0.0143 0.0133 0.0133 0.0113 0.0088 0.0093 0.0134 0.0105 0.0087 0.0090 0.0085 0.137 0.137 0.139 0.141 0.142 0.142 0.143 0.140 0.142 0.141 0.141 0.140 0.141 77.63 77.78 78.57 79.36 80.00 80.04 79.94 80.46 81.36 82.26 82.45 83.51 83.58 0.0208 0.0208 0.0205 0.0202 0.0200 0.0200 0.0201 0.0197 0.0194 0.0189 0.0188 0.0183 0.0184 1.297 1.280 1.222 1.276 1.274 1.170 1.270 1.281 1.341 1.276 1.300 1.251 1.227 1.259 1.258 1.234 32.00 33.62 34.70 35.29 36.74 40.03 38.41 37.99 37.16 39.67 40.87 41.71 42.13 42.96 44.59 45.02 0.2011 0.1894 0.1800 0.1789 0.1706 0.1493 0.1616 0.1642 0.1712 0.1557 0.1511 0.1454 0.1426 0.1405 0.1341 0.1316

J. Nakano et al. / Computer Coupling of Phase Diagrams and Thermochemistry 31 (2007) 125140 Table A.1 (continued) Temperature 455.9 456.3 457.7 457.8 458.9 460.3 460.4 460.4 460.4 460.5 460.8 461.8 462.9 463.0 463.2 465.4 465.4 466.4 467.3 467.9 469.6 470.5 471.3 473.0 473.6 475.8 477.2 477.6 482.2 485.0 490.1 + 2 + L 422.1 422.3 425.0 425.6 426.1 428.0 429.6 430.0 430.0 430.0 430.2 430.3 432.2 434.1 439.2 0.094 0.093 0.095 0.095 0.097 0.096 0.100 0.102 0.096 0.100 0.102 0.097 0.096 0.101 0.106 84.53 84.79 84.98 85.11 84.81 85.45 84.99 84.68 85.90 85.08 84.72 85.76 86.40 85.80 85.96 0.0145 0.0143 0.0144 0.0144 0.0146 0.0143 0.0148 0.0151 0.0142 0.0148 0.0150 0.0143 0.0141 0.0146 0.0149 Wt% of Al in the liquid phase 0.065 0.069 0.077 0.062 0.063 0.074 0.098 0.068 0.078 0.102 0.058 0.058 0.055 0.072 0.073 0.069 0.053 0.069 0.047 0.064 0.041 0.060 0.055 0.058 0.055 0.052 0.046 0.031 0.024 0.034 0.027 EMF 99.96 98.80 96.83 101.41 101.33 98.27 92.37 100.08 97.19 91.55 103.53 103.77 105.16 99.49 99.24 100.96 106.56 101.19 109.58 103.15 113.06 105.15 107.21 106.48 107.76 109.51 112.49 121.11 127.86 121.02 127.39 aAl 0.0085 0.0089 0.0099 0.0080 0.0080 0.0094 0.0124 0.0086 0.0099 0.0130 0.0073 0.0073 0.0069 0.0090 0.0091 0.0085 0.0066 0.0085 0.0058 0.0078 0.0050 0.0073 0.0066 0.0070 0.0066 0.0061 0.0054 0.0036 0.0028 0.0039 0.0030

139

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