Density and Viscosity of Molten Zn-Al Alloys

Y.H. LIU Different Zn-Al alloys were applied in various hot-dip coating processes, such as galvanizing, GALFAN, GALVALUME, and aluminizing, for corrosion protection. Density and viscosity are two important parameters of the molten alloys in many studies, especially those involving uid mechanics. However, the experimental data of these two important properties are scarce. Interpolation and extrapolation of experimental data are often necessary. Models that can describe the entire system are needed for the prediction of these properties at different temperatures and with different alloy compositions. Various thermodynamic models were examined in the current study, and the one that provided the best t to the experimental data of the Zn-Al binary system was introduced. I. INTRODUCTION

DIFFERENT Zn-Al alloys are applied in various hot-dip coating processes to offer steel a combination of sacricial and barrier protection against corrosion. The most common process is galvanizing, which uses a Zn-based alloy containing about 0.2 pct Al (weight percentage is used throughout the article). GALFAN,* a proprietary process
*GALFAN is a trademark of International Lead Zinc Research Organization, Research Triangle Park, NC.

promoted by the International Lead Zinc Research Organization, uses the eutectic Zn-Al alloy containing 5 pct Al. GALVALUME,** a patented process invented by Bethlehem
**GALVALUME is a trademark of BIEC International, Inc., Vancouver, WA.

Steel, employs an alloy with a composition of 55 pct Al, 43 pct Zn, and 1.6 pct Si. Processes using Zn-Al alloys with other compositions have also been developed to serve special purposes. Aluminizing, on the other hand, uses pure Al with or without the addition of Si. Density and viscosity are two material properties important to many studies involving uid mechanics. Examples of these studies include the computer simulation of ows in galvanizing baths and mathematical modeling in coating weight control using impinging air jets. Density and viscosity are also important to die casting studies. There is clearly a need in the industry for a means to predict these two properties of Zn-Al alloys at various compositions and temperatures.[1] Unfortunately, experimental measurements of the viscosity of Zn-Al alloys are scarce. The most systematic studies were carried out four decades ago and the results are available mainly in internal reports.[2,3,4] The data processing performed in those studies was composition specic, resulting in a group of equations that used different parameters for different alloy compositions. Consequently, the prediction of properties of alloys with compositions not covered by the experiments was unreliable, if feasible at all. Advanced models, taking advantage of better descriptions of thermodynamic properties available after the widespread use of computers in thermodynamic assessY.H. LIU, Senior Scientist, is with the Product Technology Centre, Teck Cominco Metals Ltd., Mississauga, ON, Canada, L5K 1B4. Contact e-mail: daniel.liu@teckcominco.com Manuscript submitted January 30, 2006.
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ments, are able to predict viscosity at any composition in the system. A reassessment of the experimental data using the advanced models is therefore justied. The density of a molten alloy is normally a linear function of temperature. Its modeling is a relatively easy task, as the density of a binary alloy does not usually deviate signicantly from the simple weighted average of the densities of two constituent elements. The modeling of density is discussed in the current study largely because its result is needed in the modeling of viscosity. The modeling of viscosity, on the other hand, is more challenging. To start with, data collected from different sources may not agree very well, probably due to the difculties in accomplishing the experiments. Data for Zn-based alloys are typically needed and available in a temperature range lower than the melting point of Al. Extrapolating the viscosity of Al to temperatures lower than the melting point becomes necessary for modeling this property of Zn-Al alloys. As the viscosity is a relatively complex function of temperature, such an extrapolation can induce signicant errors. Various thermodynamic models were examined in the current study, and the one that provided the best t to the experimental measurements is introduced. II. THERMODYNAMIC MODELING OF LIQUID DENSITY

The modeling of density is essentially the modeling of molar volume. Once the molar volume is obtained, the density is calculated by dividing the molar weight by the molar volume. The molar volume of liquid metal Vi can be described as a linear function of temperature T. The molar volume of an alloy can be represented by the values of the constituent elements and the excess Gibbs energy DGex of the liquid solution. For the molten Zn-Al alloys, V 5 X Al V Al 1 X Zn V Zn 1 CDGex [1]

where C is an adjustable coefcient for curve tting. A negative DGex signies afnity between two constituent elements that normally leads to a negative deviation of the molar volume from the weighted average. A positive DGex, on the other hand, indicates repulsion between dissimilar atoms and, hence, a positive deviation in volume. The excess Gibbs energy DGex of the liquid Zn-Al solution has been evaluated by many researchers in their critical
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assessments of the Zn-Al system. The values suggested by the latest assessments[5,6] were adopted in this study. In those latest assessments, DGex was expressed in the RedlichKister polynomial: DGex 5 XAl X Zn L0 1 L1 XAl XZn [2]

where L0 5 10,288 3.035 T and L1 5 810 1 0.471 T. The density of molten Al was measured by Magnusson and Arnberg[7] using an indirect Archimedean method. The measured densities of Al at different temperatures were used in the current study to derive the molar volume of Al, VAl. The linear regression of data points, as shown in Figure 1, yielded VAl 5 10.058 1 0.001397 T. The density of molten Zn and 13 Zn-Al alloys with Al contents ranging between 0.15 and 15 pct were measured by Thresh et al.[24] using a pycnometric method, which was considered most suitable for Zn-based alloys due to their high vapor pressures. The measured densities of Zn at different temperatures were used to derive the molar volume of Zn, VZn. The linear regression of data points, as shown in Figure 2, yielded VZn 5 8.982 1 0.001400 T. The values of Zn-Al alloys were used in the determination of the constant C in Eq. [1]. A value of C 5 7.7 3 105 yielded the best overall t to experimental data. The difference between the measured density rm and the predicted density rp fell within a narrow range between 0.26 and 10.25 pct, as shown in Figure 3. The group of data located in the lower-left corner in Figure 3 was for Zn-Al alloys containing 15 pct Al. The spread within the group was due to the difference in temperature. The next group with the second lowest viscosity was for those alloys containing 8 pct Al. The rest of the data points in the chart formed a continuous band because of the proximity of alloy compositions. The standard deviation of the prediction, s +rp rm 2 s5 [3] n1

was 0.0084 g/cm3 for a total of 214 data points for Zn-Al alloys. The standard deviation decreased to 0.0075 g/cm3 when the 50 data points for pure Zn and Al were also included, as the model t the pure element data even more precisely. The advantage of a model such as Eq. [1] is the ability to predict the property at compositions not covered by experiments. Figure 4 demonstrates an example of its application. The density of Zn-Al alloys at 460 C (733 K) was calculated as a function of alloy compositions and was plotted as a solid line. The line stopped at a composition whose liquidus temperature was 460 C. Alloys with Al contents higher than this composition would be in semisolid or solid

Fig. 2The molar volume of Zn determined from the density measurements carried out by Thresh et al.[2,3]

Fig. 1The molar volume of Al determined from the density values measured by Magnusson and Arnberg.[7]
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Fig. 3The predicted densities of Zn-Al alloys t well with the experimental measurements.[2-4]
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Fig. 4The density of Zn-Al alloys at a bath temperature of 460 C (733 K). Data points shown as closed circles represent experimental measurements. The density predicted by using Eq. [1] is shown as a solid line, whereas that calculated from the simple weighted average of Al and Zn is shown as a dashed line.

Fig. 5Different models provide the same good t to experimental measurements[10] but lead to different predictions when extrapolated to lower temperatures.

states at this temperature. Also presented in Figure 4 are data points at 14 different compositions (closed circles) where experimental measurements were carried out. The actual measurements were performed not exactly at 460 C but in a temperature range that encompassed 460 C. The data for 460 C were then calculated using the linear regression of data points for each composition. The standard deviation s for each composition was very small. If the 3s had been plotted as error bars in Figure 4 along with the data points, they would have been too short to be clearly visible. In other words, those data points shown in Figure 4 could be viewed as a good representation of experimental measurements. The dashed line plotted in Figure 4 shows the density values calculated using the weighted average of Al and Zn, without considering the interaction between Al and Zn atoms. Although the difference between the averaged value and the values predicted by the model was relatively small, it is apparent that the model provided a much better t to experimental points.

it was performed in the same period of time (1961) using the same type of viscometer (oscillating sphere). The results of Rothwell were plotted in Figure 5 together with tting curves using the Arrhenius equation and the KTH model. The Arrhenius equation is commonly used to depict the viscosity dependence on temperature:   E h 5 h0 exp [4] RT where h0 is a pre-exponential constant and E is the activation energy. The value of h0 and E are constants determined by the regression of experimental measurements. The KTH model[9] has a similar formula except that the pre-exponential constant is determined using the absolute reaction rate theory as hN0/Vm. The activation energy becomes the only term to be determined using the experimental data. It acquires a new name, the Gibbs energy of activation, and is denoted as DG*. It can usually be described as a function of temperature: DG 5 a 1 bT 1 cT ln T [5]

III.

THERMODYNAMIC MODELING OF VISCOSITY

The modeling of viscosity is a rather challenging task. A thorough overview of various models was given by Brooks et al.[8] Different models were evaluated in the current study. It was found that the model developed by Du et al.[9] at the Royal Institute of Technology, Sweden (hereafter referred to as the KTH model), provided the best t to the experimental results of Zn-Al alloys. The viscosity measurements of Zn-Al alloys are scarce. The most systematic studies available to the undersigned were those carried out by Thresh et al.[3,4] in the mid-1960s using the oscillating cylinder method. Unfortunately, Thresh did not measure the viscosity of pure Al. Because viscosity data from different sources may not agree well, caution must be exercised when looking for the replacement set of data for pure Al. The experimental work carried out by Rothwell[10] was found to be a satisfactory choice because
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where a, b, and c are constants that can be optimized from experimental data. The optimal values for a, b, and c were found to be 1328.04, 101.290, and 10.5558 for pure Al, as shown in Figure 5. The optimal values for pure Zn were determined in the same way as 9586.77, 63.6023, and 6.00523. It is apparent in Figure 5 that the Arrhenius equation and the KTH model both offered an adequate t to the experimental data, with standard deviations of 0.0053 and 0.0052 mPas, respectively. However, the extrapolations of these two models to lower temperatures differed signicantly. Although there was no means to judge which model provided better extrapolation to temperatures lower than the melting point of pure Al, this difference was carried over into the nal modeling of viscosity where the KTH model provided more accurate predictions, at least for Zn-Al alloys.
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The Gibbs energy of activation for the Zn-Al alloys, according to the KTH model, should be described as DG 5 XAl DG 1 XZn DG 1 RTXAl ln X Al 1 XZn ln X Zn Al Zn 1 DGex [6]

The prediction made by this model compared favorably to other models. The predicted viscosity using the KTH model was plotted against the experimental measurements, as shown in Figure 6. It is evident in Figure 6 that the KTH model has a tendency to underestimate the viscosity of Zn-Al alloys. It is, therefore, reasonable to believe that there is room for further improvement. Close examination of the model raised questions about the role that DGex plays in Eq. [6]. Further to the discussion in Section II, a negative excess Gibbs energy signies the afnity between dissimilar atoms, which tend to agglomerate, leading to an increase in viscosity and a decrease in diffusivity. In that sense, the sign preceding the excess Gibbs energy term in Eq. [6] should be negative rather than positive. In accordance with the change in the enthalpy term, introduction of an adjustable coefcient A to the entropy term becomes necessary in order to achieve a good t to the experimental data. The modied equation thus becomes DG 5 XAl DG 1X Zn DG 1 ARTXAl ln XAl 1 X Zn ln X Zn Al Zn [7] DGex Note that Eq. [7] did not follow the strict Gibbs energy expression of the original KTH model and, in this sense, represents a semiempirical modication. Nevertheless, using the modied model (Eq. [7]) resulted in a signicant improvement in accuracy, as shown in Figure 7. All predictions were within 63.1 pct of the measurements, and the standard devia-

tion was reduced almost by half, from 0.070 mPas (Figure 6) to 0.039 mPas (Figure 7). The viscosity of molten Zn-Al alloys at 460 C (733 K) is shown in Figure 8. Each data point in the gure represents a set of experimental measurements[3,4] carried out in a temperature range that encompassed 460 C. Each set of experimental data had the same composition and, therefore, could be readily modeled using the Arrhenius equation. The standard deviation s between the experimental measurements and the Arrhenius model was evaluated. The error bar associated with each data point plotted in Figure 8 represents 63s. The data shown in Figure 8 demonstrate a signicant deviation from the simple weighted average of Al and Zn (dashed line). The original KTH model (Eq. [6]) captures the general trend, but the predictions fell outside 3s for most data points. The modied model (Eq. [7])

Fig. 7Viscosity modeling using the modied KTH model (Eq. [7]).

Fig. 6Viscosity modeling using the KTH model (Eq. [6]).

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Fig. 8Viscosity of Zn-Al alloys at 460 C (733 K) demonstrates a signicant deviation from the weighted average of Al and Zn properties. The modied model (Eq. [7]) shows a notable improvement over the original KTH model (Eq. [6]).
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provided much more accurate predictions, as shown in the solid line in Figure 8. It is interesting to note that data for 4.5 pct Al alloy (XAl 5 0.103) showed a much larger error band than others, attributable mainly to four scattering measurements carried out at temperatures only about 10 C above the eutectic temperature. Data for 5.0 pct Al alloy (XAl 5 0.113, the eutectic composition) did not show any anomaly at lower temperatures. It is, therefore, believed that the unusually large error at 4.5 pct Al was probably an isolated incident and should not be regarded as indirect evidence for the existence of some sort of eutectic structure in the melt. IV. SUMMARY Thermodynamic models using the excess Gibbs energy of mixing were successfully used to calculate the density and viscosity of molten Zn-Al alloys. The models offered reliable and accurate predictions of these two important material properties at compositions and temperatures not covered by experiments. ACKNOWLEDGMENT The author thanks Dr. X.G. Lu, Thermo-Calc Software AB, Sweden, and Dr. N.-Y. Tang, Teck Cominco Metals Ltd., Canada, for constructive discussions, and acknowledges the assistance of Mrs. Angeline M. Prskalo in the preparation of the manuscript. NOMENCLATURE DGex DG* excess Gibbs energy of mixing (J/mol) Gibbs energy of activation (J/mol)

L 0 , L1 N0 R T Vm XAl XZn h n h r

thermodynamic interaction parameters (J/mol) Avogadros number, equals 6.022142 3 1023 mol1 gas constant, equals 8.31447 J/mol/K absolute temperature (K) molar volume, in cm3/mol (106 m3/mol) molar fraction of Al in molten Zn-Al alloy molar fraction of Zn in molten Zn-Al alloy Plancks constant, equals 6.626068 3 1034 kgm2/s number of experimental data points used in modeling or regression viscosity, in mPas (103 Pas) density, in g/cm3 (103 kg/m3) REFERENCES

1. M. Dubois: R&D Center of Arcelor Cockerill, Liege, Belgium, private communication, 2005. 2. H.R. Thresh, D.W.G. White, J.O. Edwards, and J.W. Meier: Internal Report No. PM-R-64-26, Mines Branch, Canada Department of Mines and Technical Surveys, Ottawa, Canada, 1964, pp. 1-47. 3. H.R. Thresh: Internal Report No. R-133, Mines Branch, Canada Department of Mines and Technical Surveys, Ottawa, Canada, 1964. 4. H.R. Thresh, D.W.G. White, J.O. Edwards, and J.W. Meier: Internal Report No. PM-R-64-27, Mines Branch, Canada Department of Mines and Technical Surveys, Ottawa, Canada, 1965, pp. 1-64. 5. S.L. Chen and Y.A. Chang: CALPHAD, 1993, vol. 17, pp. 113-24. 6. H. Liang and Y.A. Chang: J. Phase Equilibria, 1998, vol. 19, pp. 25-37. 7. T. Magnusson and L. Arnberg: Metall. Mater. Trans. A, 2001, vol. 32A, pp. 2605-13. 8. R.F. Brooks, A.T. Dinsdale, and P.N. Quested: Meas. Sci. Technol., 2005, vol. 16, pp. 354-62. 9. S.C. Du, J. Bygden, and S. Seetharaman: Metall. Mater. Trans. B, 1994, vol. 25B, pp. 519-25. 10. E. Rothwell: JIM, 19611962, vol. 90, pp. 389-94.

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