The Surface Tension of Molten Aluminum and Al-Si-Mg Alloy under Vacuum and Hydrogen Atmospheres

J.P. ANSON, R.A.L. DREW, and J.E. GRUZLESKI The surface tensions of pure molten aluminum, A356 alloy (Al-7 pct Si-0.3 pct Mg), and strontiummodified A356 alloy have been measured under vacuum and hydrogen atmospheres using the sessile drop technique. The values obtained for pure aluminum at 680 C and for A356 alloy and modified A356 alloy at 630 C are 1.007, 0.889, and 0.844 N/m, respectively, when measured under vacuum. The addition of hydrogen gas to the atmosphere of the liquid droplet has no significant effect on the surface tension of the unmodified A356 alloy, while it lowers the surface tension of the modified alloy to 0.801 N/m. This effect is possibly due to the formation of SrH2.

I. INTRODUCTION

ACCURATE information on the surface tension of aluminum and its alloys is necessary for many metallurgical and materials-related processes, such as casting, welding, brazing, sintering, and the fabrication of metal-matrix composites.[1,2] Small bubbles, known as microporosity, are a common defect found in aluminum castings. These pores arise primarily from the evolution of hydrogen gas during solidification due to a marked decrease in the solubility of hydrogen in liquid and solid aluminum.[3] Four forces act on a gas bubble that is present in a liquid metal. The internal gas pressure (Pg) acts to increase the bubble size, while the liquid head or metallostatic pressure (Pm), the atmospheric pressure (Pa), and the surface tension forces (Pst) tend to make the bubble shrink. Obviously, at equilibrium, the following relationship must hold:[4]
Pg Pm Pa Pst [1] In the majority of casting processes, the metallostatic pressure is quite small in comparison to the other pressures so that Pg Pa Pst [2]

surface tension of aluminum and its alloys have been carried out under vacuum or inert gas, typically argon, and do not necessarily represent the conditions that prevail when microporosity forms in a solidifying casting. This is particularly true for aluminum alloys where the gas contained in the pore is hydrogen, and certain alloying elements form metal hydrides[9] (Table I). As a general rule, surface contaminants, such as the hydrides, reduce the surface tension of the metal. It is possible that such hydrogen-metal interactions may be responsible for increased amounts of porosity found with the addition of small amounts of certain alloying elements. This holds particularly true for strontium, which is added to the alloy to modify the silicon structure. Strontium forms a stable hydride at temperatures up to 1000 K and is known to cause an increase in porosity[10,11] in cast aluminum alloys. The present article reports on measurements of the surface tension of a nonmodified and strontium modified aluminum casting alloy (A356) under vacuum and hydrogen gas atmosphere. One of the main objectives of this work was to determine whether the presence of hydrogen gas has an effect on the surface tension.

The surface-tension pressure is determined by the surface tension of the liquid metal ( ) and the bubble radius. For a nonspherical bubble, Pst (1/r1 1/r2) [3]

II. MEASUREMENT OF SURFACE TENSION The surface tension is an intrinsic property of all liquids and is due to an incomplete coordination of the atoms at the liquid-gas interface. Atoms in the bulk of the liquid are completely surrounded by other atoms, while those at the surface are only in contact on the side and below. Interatomic attractions cause an uneven pull on the surface atoms, drawing them into the body of the liquid and resulting in a curvature of the surface as the liquid tries to assume a shape that has a minimum surface area. The effect of surface tension is commonly observed in the form of capillary action, meniscuses, and beading of droplets. Thermodynamically, surface tension is defined as the surface free energy per unit area (J/m2). From a dynamic point of view, the surface tension represents the work required to create one unit of additional surface area at constant temperature (N/m). The units J/m2 are equivalent to N/m and the units dyn/cm are also frequently used (1000 dyn/ cm 1 N/m). The surface tension of a liquid can be measured by a variety of methods.[12,13,14] These are based on the change
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where r1 and r2 are the principle radii of curvature. If the bubble is spherical, this expression becomes Pst 2 /r [4]

There is considerable current interest in the development of mathematical models to describe microporosity formation in cast parts.[48] Realistic models require that the surface tension of the liquid alloy be known. The majority of the experimental measurements of the

J.P. ANSON, Postdoctoral Student, Department of Metallurgy Engineering, R.A.L. DREW, Professor and Chair, Department of Mining and Metallurgical Engineering, and J.E. GRUZLESKI, Professor and Dean, Faculty of Engineering, are with McGill University, Montreal, PQ, Canada H3A 2B2. Manuscript submitted November 18, 1998.
METALLURGICAL AND MATERIALS TRANSACTIONS B

Table I. Temperature Stability Range for the Hydrides of Some Elements Commonly Found in Aluminum Foundry Alloys (Solid Phase)[9]
Hydride Phase
AlH3 B10H14 CaH2 LiH MgH2 NaH Si2H6 SrH2

Range (K)
298 295 298 298 298 298 298 298 to to to to to to to to 400 300 1053 962 560 700 1300 1000

in profile of a drop as it deforms under gravity (sessile drop, pendant drop), capillary action (capillary height method), the maximum force to pull an object from the liquid (Wilhelmy plate method, Du Nouy ring), or the pressure required to form a bubble in the liquid (maximum bubble pressure method). The sessile-drop method was chosen for the current experimentation. This technique is commonly used for the evaluation of the surface tension of liquid metals as it allows an accurate determination at high temperatures, is relatively easy to perform, and the mathematical treatment of the results is simple. The sessile-drop method is based on the measurement of the profile of a stationary drop placed on a flat, nonwetting, substrate. In the absence of gravity, the drop shape will be determined solely by the surface tension and will thus be perfectly spherical (minimum surface area). In the presence of gravity, the drop will deform under its own weight and its final shape will depend on the surface tension and the drop size. A drop of low surface tension will tend to flatten while a drop of high surface tension will tend to remain spherical. The shape of a small droplet will be dominated by the surface tension, and the droplet will remain spherical (large surface-to-mass ratio) no matter what the magnitude of its surface tension. On the other hand, a large droplet will have a greater tendency to deform under its own weight (small surface-to-mass ratio), but the degree to which it deforms will be determined by the surface tension. By observing a drop of known size deform under its own weight, the surface tension can be calculated. There are several equations to determine the surface tension from the profile of a sessile drop. One of the oldest and most commonly used is the Bashforth and Adams equation:[15] g b2/ [5] where is the surface tension, g is the gravitational acceleration, the liquid density, b a measure of the droplet size, and a shape factor. From the drop dimensions R, X, ZR , and Z90 (Figure 1), the values of b and can be calculated by means of successive approximations using values provided in tables. The most complete tables are those provided by White.[16] Alternatively, the Bashforth and Adams tables can be used to draw profiles, which, when superimposed on the drop image, can be used to determine the value of the surface tension. Paday[12] provides an explanation and tables for this method.
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Fig. 1The dimensions of a droplet for the calculation of the surface tension.

Occasionally, the difference between R and X becomes too small to allow accurate of use the Bashforth and Adams method. In this case, it is possible to use the Dorsey equation,[17] which is a simplification of the Bashforth and Adams calculations. The Dorsey equation gives the surface tension as g A2 where A2 and f Y/X 0.4142 [8] Here 2X is the width of the droplet and Y is the distance from the top of the drop to the 45-deg intercept, as shown in Figure 1. Note that the Dorsey equation is a simplification and thus entails some error, although this error is limited and can be corrected using a table supplied by Dorsey. In general, if X lies between 1.5A and 3.2A, the correction is less than 0.06 pct. In the current work, the Bashforth and Adams equation and Whites list of tables were used to determine the surface tension values. If the difference between R and X was too small to accurately apply this method, the Dorsey equation was used. It should be noted that the liquid density, , is not accurately known for many common alloys and is sometimes a major source of error. For silicon concentrations between 0 and 15 wt pct, the density ( , g/cm3) of liquid aluminumsilicon alloys is given by[18] (0.3970 4.0924 10
5

[6] 0.0481f ) [7]

X 2(0.05200/f

0.12268

1.04

10

CL)

[9]

where T is the temperature in degrees Celsius and CL is the weight percent silicon. The experimental difficulties associated with accurate measurement of the surface tension of molten aluminum cannot be overemphasized. Only the absence of any source of contamination (from the bulk, substrate, or atmosphere) enables the correct measurement of the surface tension. Contamination is almost always the major source of error. In particular, molten aluminum reacts readily with oxygen and water vapor present in the atmosphere to form a fine film, or sometimes islands, of oxide that seriously affect the
METALLURGICAL AND MATERIALS TRANSACTIONS B

III. THE SESSILE DROP APPARATUS The apparatus was based on the design proposed by Kingery and Humenik[22] (Figure 3). A sample, placed on a substrate in the center of a furnace, is heated under vacuum until it melts. A photograph of the profile of the molten drop is taken, and all calculations to determine the surface tension are performed on a magnified version of this photograph. The apparatus itself consisted of a vacuum chamber made of a quartz tube sealed at one end by a window and attached at the other to a diffusion pump and a rotary pump. One end of the vacuum chamber passed through a tube furnace, effectively creating two zones, a hot zone, found within the furnace, and a cold zone, found outside the furnace. The two zones were used to limit the oxidation of the sample, which is particularly prevalent at high temperatures. The sample was placed initially in the cold zone, while the furnace heated and the system was evacuated to 10 6 torr. Once the required temperature and vacuum were reached, the sample was slid into the hot zone by using a magnet to attract a steel tube, which in turn was attached to the sample holder by means of a rigid wire. All tests were performed at a temperature of 680 C for pure aluminum and at 630 C for the A356 alloys. If desired, once the sample was melted, the vacuum chamber could be isolated from the pumps and ultra-high-purity hydrogen gas (99.999 pct H2 minimum, sum of N2, O2, Ar, CO2, CO, CH4, and H2O 10 ppm) could be backfilled into it. The gas was first passed through a manganese-aluminumsodium-silicate active metal purifier at room temperature in order to lower the oxygen and water vapor concentrations down to less than 20 parts-per-billion (ppb). In order to maintain the vacuum seal, a negative pressure had to be present at all times, and the pressure inside the apparatus after the addition of hydrogen was 0.85 atmospheres. Four different aluminum alloys were used in addition to pure aluminum (Table IV). Pure aluminum was used to test and calibrate the apparatus, while the four alloys, similar in composition to A356, were of interest because of their commercial importance. Magnesium levels in excess of those normally found in A356 alloy were required since there was vaporization of magnesium under the vacuum used in the apparatus. Sample preparation consisted of cleaning the sample in order to remove the aluminum oxide found on the surface. Samples, usually between 4.5 and 6.0 g, were ground on 120-grit paper, dipped in 5 pct hydrofluoric acid solution for 3 minutes, and rinsed in acetone. The sample preparation was performed just before putting the sample in the furnace. Electronic-grade alumina plates were used as the substrate, and it was not necessary to prepare the plates in any way since they were of excellent quality and superior surface

Fig. 2Aluminum surface tension vs oxide coverage (X ).[19]

measured values. An oxygen pressure of less than 10 50 atmospheres is needed to avoid oxidation, thus making it virtually impossible not to have, at best, a partially oxidized surface. Using Auger electron microscopy, Goumiri and Joud[19] measured simultaneously the surface tension and oxide thickness of pure aluminum. Their meticulous experimentation showed that even a single monolayer of oxide can decrease the surface tension by more than 10 pct (Figure 2). They concluded that the value of the surface tension commonly reported by investigators, usually about 0.865 N/ m, corresponds to saturation coverage by a homogeneous oxide layer. Since contamination decreases the surface tension, it is advisable, as a general rule, to consider the highest reported values as the most correct. In an excellent review of existing data, Keene[20] concludes that the most accurate results to date indicate that the surface tension of pure aluminum is approximately 1.05 to 1.10 N/m (Table II). The surface tension of aluminum alloys has received only limited study, with wide variations in reported results. In general, the surface tension is observed to decrease with increasing levels of silicon, magnesium, and strontium.[21] It should be noted that the rather steep decrease in surface tension reported with increase in magnesium content may be due to the increased oxidation tendency of magnesiumcontaining aluminum alloys. The few results available for the A356 foundry alloy are given in Table III.

Table II. Surface Tension Values of Pure Liquid Aluminum as Reported by a Variety of Authors*
Investigators
Goumiri and Joud Garcia-Cordovilla et al.

Reference
19 25

Method
SD MBP

Atmosphere
vacuum argon

(N/m)
1.050 1.091

Temperature (K)
973 973

*SDsessile drop, and MBPmaximum bubble pressure.

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Table III. Surface Tension Values of Modified and Nonmodified A356 Foundry Alloy as Reported by a Variety of Authors
Investigators
Goicoechea et al. Emadi et al. Emadi et al.

Reference
21 24 24

Modifier
Sr

Method
MBP SD SD

Atmosphere
argon argon argon

(N/m)
0.845 0.790 0.640

Temperature (K)
973 958 958

Table IV. Chemical Compositions of the Pure Aluminum and A356 Type Alloys (Weight Percent)
Alloy
Al (99.9999 pct) A356 A356 Mg A356 Mg A356 Mg Sr

Pct Si
0.0001 7.2 7.0 7.0 7.5

Pct Mg
0.0001 0.38 0.87 1.74 0.79

Pct Fe
0.120 0.106 0.104 0.104

Pct Cu
0.0001 0.015 0.002 0.003 0.011

Pct Ti
0.032 0.032 0.031 0.090

Pct B
0.0029

Pct Sr
0.0150

Table V. Results for Pure Aluminum at 680 C

Test Surface Tension Number (N/m)
Fig. 3The apparatus used for the measurement of the surface tension using the sessile drop method.

Comments
no visible oxide islands of oxide slightly cloudy slightly cloudy, some islands of oxide

42a 43a 62c 74b

1.009 1.004 0.907 0.845

increased accuracy. This is an important consideration since differences of fractions of a millimeter can markedly alter the results. IV. SURFACE TENSION VALUES A. Pure Aluminum Pure aluminum was used to verify the accuracy of the apparatus and the procedure. Significant difficulties were encountered due to oxidation of the samples. Visually, oxidation was observed as either small islands of oxide floating on the sample surface or, occasionally, as a slight grayish skin. The presence of oxide islands did not generally decrease the surface tension, but the grayish film decreased the surface tension by about 10 pct. If the sample was not visibly oxidized, the sample surface was mirrorlike, and the droplet behaved in a wobbly manner when subject to the smallest vibrations. It should be noted that the lack of visible oxidation does not imply that no oxidation was present. It was impossible under the experimental conditions to completely avoid oxidation and even a visibly perfect surface most probably corresponds to at least a monolayer of oxide. Results and observations for pure aluminum are given in Table V, where it can be seen that visible oxidation of the sample surface decreases the measured value by about 15 pct. The surface tension measured under conditions of no visible oxidation is 1.009 N/m. This is close to the value reported by Goumiri and Joud[19] of 1.05 N/m. The addition of hydrogen to the atmosphere above the sample caused a grayish skin to form on the liquid. Since aluminum hydride is not stable in this temperature range (Table I), it must be assumed that the hydrogen gas contained trace amounts of oxygen and/or water vapor that caused the
METALLURGICAL AND MATERIALS TRANSACTIONS B

Fig. 4A typical example of the digitized photograph of a drop after magnification. The measured values are for a magnification of 8.064 times.

finish (99.8 pct alumina, scratches 0.0005 cm depth, and camber 0.002 cm/cm). Once the sample had melted, a photograph of its profile was taken using a camera placed at a fixed distance to give a constant magnification. The resulting photograph was scanned and imported into CorelDraw where it was magnified, and all necessary dimensions were measured to the hundredth of a millimeter (Figure 4). The exact magnification was determined by initially applying the procedure on samples of known dimensions. The advantage of digitizing the image was that the measurements could be made with
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Fig. 5The surface tension of A356 and A356 Mg alloys at 630 C. The dotted lines represent the compositional limits for A356 alloy (0.25 to 0.45 pct Mg).

surface tension with magnesium content. The surface tension of strontium-containing alloys is, however, significantly lower than that of nonstrontium-containing alloys. Measurements made under vacuum indicate a decrease in the surface tension of 5 pct, while under hydrogen atmosphere, a decrease of 8 pct is evident. This is expected since strontium itself has a low surface tension (approximately 0.290 N/m at 850 C).[20] The addition of hydrogen does not significantly affect the results for a nonstrontium-containing alloy. A hydrogen atmosphere does lead to a somewhat lower average surface tension in the presence of strontium, but the decrease falls within the standard deviation of the measurements. It is apparent that strontium does not cause a marked decrease in surface tension, and that the surface changes alone cannot account for the significant increase in microporosity found in strontium-modified castings. The value of the surface tension of A356 alloy found in the current study is significantly higher than that previously reported in the literature (Table III). It is quite possible that the previous results, in particular those of Emadi et al.[24] pertain to a relatively heavily oxidized surface, which would act to lower measured values. V. CONCLUSIONS
1. All measured values of surface tension, even if not visibly oxidized, probably correspond to at least a monolayer of oxide. 2. The measured surface tension of pure aluminum at 680 C is 1.009 N/m. 3. Preferential oxidation of magnesium vapor from aluminum alloys can be used to protect the sample from heavy oxidation. 4. The surface tension of A356 alloy under vacuum at 630 C is 0.889 N/m. 5. The addition of hydrogen does not significantly decrease the surface tension of A356 alloy. 6. The addition of strontium does decrease the surface tension of A356 alloy at 630 C by about 5 pct to 0.844 N/m. 7. The addition of hydrogen to a strontium-bearing alloy apparently causes a slight decrease in the surface tension, perhaps by forming SrH2, but the results are not conclusive. 8. Changes in surface tension alone cannot account for the significant increase in microporosity found in strontiummodified castings

Table VI. Average Surface Tension Values of A356 Alloys at 630 C

Atmosphere
Vacuum Hydrogen Vacuum Hydrogen

Sr
no no yes yes

Surface Tension (N/m)

0.889 0.874 0.844 0.801

Standard Deviation (N/m)

0.025 0.027 0.032 0.007

sample surface to oxidize. The addition of hydrogen was consistently accompanied by a decrease in the surface tension, a further indication of oxidation of the surface. B. Aluminum-Silicon-Magnesium Alloys In order to measure the surface tension of the common Al-Si-Mg casting alloy, A356, it was necessary to increase the magnesium level to compensate for magnesium evaporation under vacuum. This evaporation resulted in a coating of the walls of the quartz tube at the limits of the hot zone. Although this at first appeared to be an obstacle to the experimentation, it was quickly observed that samples containing magnesium generally had a visually perfect, mirrorlike finish upon melting. This was the case even after addition of hydrogen gas, which, from the pure aluminum tests, was known to contain a trace amount of oxygen and/ or water vapor. Apparently, the magnesium vapor, as well as magnesium deposited on the walls of the quartz tube, acted as an oxygen getter, thus protecting the sample surface from heavy oxidation. This conclusion is supported by the work of Silva and Talbo,[23] who showed that, in liquid aluminum-magnesium alloys, magnesium oxidizes preferentially to form MgO, and that this is the only oxide found during initial stages of oxidization. The surface-tension values measured under vacuum and hydrogen gas atmosphere for the unmodified and modified alloys are shown in Figure 5, and the average results are listed in Table VI. Overall, there is no apparent variation in
METALLURGICAL AND MATERIALS TRANSACTIONS B

ACKNOWLEDGMENTS The authors are grateful to the Centre Quebecois de Recherche et de Developpement de lAluminium (CQRDA) and Centre Technique Des Industries de la Fonderie (CTIF) for their financial assistance and to Montupet Ltd. for its valuable support. REFERENCES
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3. Metals Handbook, 9th ed., vol. 15, Casting, ASM INTERNATIONAL, Metals Park, OH, 1988, pp. 85-87. 4. K. Kubo and R.D. Pehlke: Metall. Trans. B, 1985, vol. 16B, pp. 359-66. 5. G.K. Sigworth and C.Wang: Trans. Am. Foundrymens Assoc., 1992, vol. 100, pp. 989-1004. 6. S. Shivkumar, D. Apelian, and J. Zou: Trans. Am. Foundrymens Assoc., 1990, vol. 98, pp. 897-904. 7. D.R. Poirier, K. Yeum, and A.L. Maples: Metall. Trans. A, 1987, vol. 18A, pp. 1979-87. 8. Q.T. Fang and D.A. Granger: Trans. Am. Foundrymens Assoc., 1989, vol. 97, pp. 989-1000. 9. C. Dupuis, Z. Wang, J.-P. Martin, and C. Allard: Light Met., 1992, pp. 1055-67. 10. K. Tynelius, J.F. Major, and D. Apelian: Trans. Am. Foundrymens Assoc., 1993, vol. 101, pp. 401-09. 11. D. Argo and J.E. Gruzleski: Trans. Am. Foundrymens Assoc., 1988, vol. 96, pp. 65-74. 12. Surface and Colloid Science, J.F. Padday and E. Matijevic, eds., WileyInterscience, Toronto, 1969, pp. 101-52. 13. T. IIda and R.I.L. Guthrie: The Physical Properties of Liquid Metals,

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Oxford University Press, Cambridge, United Kingdom, 1993, pp. 109-24. W.D. Kingery: Property Measurements at High Temperatures, John Wiley & Sons, New York, NY, 1959, pp. 362-84. F. Bashforth and J.C. Adams: An Attempt to Test the Theory of Capillary Action, Cambridge University Press, London, 1883. D.W.G. White: A Supplement to the Tables of Bashforth and Adams, Queens Printer, Ottawa, 1967. N.E. Dorsey: J. Wash. Acad. Sci., 1928, vol. 18(19), pp. 505-09. D.R. Poirier and K. Yeum: Light Met., 1988, pp. 469-76. L.Goumiri and J.C. Joud: Acta Metall., 1982, vol. 30, pp. 1397-1405. B.J. Keene: Int. Mater. Rev., 1993, vol. 38(4), pp. 157-92. J. Goicoechea, C. Garcia-Cordovilla, E. Louis, and A. Pamies: J. Mater. Sci., 1992, vol. 27, pp. 5247-52. W.D. Kingery and M. Humenik, Jr: J. Phys. Chem., 1953, vol. 57, pp. 359-63. M.P. Silva and D.E.J. Talbot: Light Met., 1989, pp. 1035-40. D. Emadi, J.E. Gruzleski, and J.M. Toguri: Metall. Trans. B, 1993, vol. 24B, pp. 1055-63. C. Garcia-Cordovilla, E. Louis, and A. Pamies: J. Mater. Sci., 1986, vol. 21, pp. 2787-92.

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