QUENCHING FUNDAMENTALS QUENCHING OF ALUMINUM: IMPORTANCE OF UNIFORM SURFACE REWETTING

By H.M. Tensi1, P. Stitzelberger-Jakob1 and G.E. Totten2 1. Technical University of Munich, Munich, Germany 2. Union Carbide Corporation, Tarrytown, NY USA INTRODUCTION The cooling process of age-hardenable aluminum alloys are affected by material properties such as: strength, ductility, and thermal stresses. Thermal stresses are minimized by reducing the cooling rate from the solution heat treatment temperature. However, if the cooling rate is too slow, undesirable alloy segregation at the grain boundaries will result. Conversely, if the cooling rate is too fast an increased tendency for distortion may result. [1,2]

When water or water-soluble polymers are used to quench age-hardenable aluminum alloys, heat transfer from the workpiece to the quenchant is determined by three boiling phases: film boiling, nucleate boiling and convective heat transfer. Film boiling occurs upon initial immersion. This is a slow cooling process because the hot surface is

surrounded by a vapor blanket. As the part cools, the vapor blanket collapses and nucleate boiling results. The transition temperature between film boiling and nucleate boiling is called the Leidenfrost temperature. Heat transfer is fastest during nucleate boiling. The heat transfer coefficient, , for nucleate boiling is about 100 times the value

of for film boiling. [8,9] When the part has cooled below the boiling point of the quenchant, slow cooling occurs by a convective heat transfer process.

Since aluminum solution heat treatment temperatures are significantly higher than the Leidenfrost temperature, film boiling is to be expected initially when quenching into water or aqueous polymers. [3,4] If the surface temperature at any given point on the workpiece is less than the Leidenfrost temperature, stable wetting and nucleate boiling will occur at that point. [5,6,7]

Figure 1a illustrates a typical wetting sequence during cooling of a cylindrical specimen quenched in distilled water at 40C. The simultaneous presence of different boiling phases with the heat transfer coefficient of one surface region greater than 100 times the other causes extremely uneven cooling of the workpiece.

Figure 1b illustrates the rewetting sequence of a cylindrical aluminum (AlMg 5, 15 mm dia x 45 mm) quenched into distilled water at 80C with the percentage of the wetted surface ( A = A(t) ) and with the change in temperature at the geometric center of the cylindrical workpiece ( T = T(t) ) during cooling.

The consequences of uneven cooling include: Regions where the film boiling persists longer experience greater separation of the super-saturated mixed crystal structure than regions of faster cooling (low tS). During age-hardening, these regions (high tS) experience a smaller increase in hardness and

also exhibit greater potential for intergranular corrosion than neighboring regions with faster fooling. Volume regions where film boiling persists exhibit a much lower higher-temperature yield point during the cooling process than regions with shorter film-boiling phases. The non-uniformity of this process results in significant plastic deformation due to increased thermal stresses and increased distortion.

Therefore, determination and characterization of the cooling processes involved in quenching is critically important, especially with water quenching. To satisfy this need, a process to quantitatively measure the rewetting process of standard quenched aluminum probes was developed. [10,11]

DISCUSSION A. Surface Rewetting Measurements Temperature variation with time during the cooling process was measured by a thermocouple inserted to the geometric center of a cylindrical probe. Rewetting kinematics was determined by measuring the change in conductance between the probe and a counterelectrode during the transition from film boiling to nucleate boiling as shown in Figure 2.

If the heated probe is completely surrounded by a vapor blanket, the electrical resistance between the probe surface and the counterelectrode is high because of the insulating effect of the vapor blanket. As the vapor blanket collapses, the quenching fluid wets the

probe causing the electrical resistance between the probe surface and the counterelectrode to decrease and the conductance to increase. Using calibration curves, the percentage of the surface (A) from the conductance (G) and the wetting kinematics ( dA/dt) may be determined from the change in conductance with respect to time (dG/dt).

B. Rewetting Kinematics from Quenched Aluminum Bodies Cooling behavior of aluminum during quenching is affected by: quenchant composition (type and concentration of a polymer quenchant), bath temperature, temperature of the aluminum being quenched, and surface condition of the aluminum.

Aluminum rewetting behavior when quenched into distilled water is strongly affected by bath temperatures above 40C. Figure 3 shows that the temperatures for the beginning of the rewetting process (TS) and for the end of the process (Tf) and the elapsed time between tf and tS within which the two boiling phases, film boiling and nucleate boiling, appear simultaneously, as a function of bath temperature. Up to bath temperatures of 40C, the probe surface wets very quickly (< 1 s ) and the rewetting process always began at the lower surface. At temperatures above 60C, the rewetting time, the time when the entire probe surface is wetted with the quenchant (tf tS) increases sharply with increasing bath temperature and the temperature distribution in the probe becomes extremely uneven. This means that with increasing bath temperature, the precipitation kinetics become increasingly non-uniform in the longitudinal direction. For example, if aluminum castings are quenched in water at 60C to reduce distortion and residual stresses, the opposite results will be achieved. [13,14]

These difficulties can be avoided by using water-soluble polymers as aluminum quenchants. [15 - 18] These polymers are usually used at bath temperatures of 20-35C. The quenching characteristics of these polymers in this temperature range are practically independent of bath temperature. [18] Aqueous polymer quenchants provide a less severe quench than cold water and the quench severity can be varied by varying quenchant concentration. [17-20]

Figure 4 shows the effect of polymer concentration on the wetting behavior of a cylindrical ALMgSiCu probe quenched in a commercial polymer quenchant. The time until unitial wetting of the probe surface increases with polymer concentration which means that film boiling persists for longer periods of time with increasing polymer quenchant concentration. This behavior appears in Figure 4 as a decline of the starting temperature for wetting (TS) measured at the geometric center of the probe. The rewetting time increases only about 2 seconds with increasing quenchant concentration.

The cooling time from the solution treating temperature where the mixed crystal phase begins is very important for age-hardened Al alloys. [2] Therefore, the effect of water temperature and the effect of polymer quenchant concentration on cooling time was compared. Figure 5 shows that the cooling time varies between 2 s and 16 s in both cases; however, the effect achieved by varying the polymer quenchant concentration was more favorable. [Note: The temperature was measured in the center of the probe which reveals nothing about rewetting behavior or about the temperature distribution within the probe.]

In addition to bath temperature and polymer concentration, agitation is also an important variable which will be reported in a subsequent report. [20-21].

The aluminum surface condition effect on

during the quenching process also exhibits a large

quenching performance. Surface characteristics can be greatly altered by

various factors such as variations in the duration of solution treatment. [22] Figure 6 shows the cooling and rewetting behavior of ALMgSiCu cylindrical probes that were solution-treated for variable lengths of time then quenched in distilled water (TB = 25C). With increasing duration of the solution treatment time from 1 minute to 180 minutes

which results in corresponding increases in the depth of the surface oxide layer, the conductance-time curves and temperature-time curves clearly show the retardation of cooling, i.e., the prolongation of wetting time with increasing duration of heat treatment (Figure 6a). The cooling rate decreases with increasing duration of solution heat treatment (Figure 6b).

C. Comparison of Quenching Characteristics of Silver and Aluminum Probes Silver probes are often used to evaluate quench severity exhibited by different quenchants. [23,24] Because of the similarity of the thermal characteristics of silver and aluminum and because of the significantly lower oxidation tendency for silver relative to aluminum, the cooling behavior of AlMgSiCu compared. and a silver (99.5 %) probe was

Thermal conductivity (a) and specific heat capacity of various materials are provided in Table 1. Thermal conductivity, a, is a measure of the rate of propagation of

temperature change in a body and is related to the specific heat capacity:

Cp

Where: Cp is the specific heat capacity, is the thermal conductivity and is the density. Table 1 Thermal Conductivity and Specific Heat Capacity for Different Materials Material Aluminum 99.5 Silver 99.5 Nickel Cr Ni Steel* INCONEL 600** Thermal Conductivity (m s ) -6 95 x 10 174 x 10 -6 14 x 10 4 x 10 -6 4 x 10
-6 -6 2 -1

Specific Heat capacity (kJ kg K ) 0.896 0.235 0.448 0.477 0.465

-1 -1

* Austentic stainless steel SAE 30304 ** Ni-based alloy Figure 7 shows the cooling curves recorded during quenching of an aluminum (AlMgSiCu) and a silver specimen (Ag 99.5) in a water-soluble polymer. The aqueous polymer quenchant concentration was 10% by volume and the bath temperature was 25C. The temperature of both materials when quenched was 520C. Both probes were cleaned with 600 grit abrasive paper before each test.

The polymer film surrounding the probe surface ruptured simultaneously around the entire surface, also called explosive rewetting, for both probes and the rewetting times

(tf tS) were extremely short. However, a stable film-boiling range lasting about 4 s was observed for the silver probe which was not observed for the aluminum probe. The centerline probe temperature was about 440C for silver and 500C for aluminum. The reason that the rewetting of the silver occurs about 4 s later for the silver probe is the greater oxidation resistance of silver. (The ratio of heats of formation of Ag2O2 and Al3O is 0.05.) When the quenching temperature of the silver probe is increased to 800C, considerable stabilization of the film-boiling occurs as observed in Figure 8a. Wetting now starts at about 260C after 24 s compared to the start of wetting of the AlMgSiCu probe after 1 s at about 500C.

The main reason for this stabilization of the film-boiling phase of the entire surface of the silver probe is the reduction of the silver oxide at the higher temperature. The hightemperature annealing of the silver probe removes the oxide and leaves a bare metal surface, resulting in stabilization of film boiling during quenching, especially in watersoluble polymers. Accordingly, the maximum cooling rate of the silver probe is not reached until a centerline probe temperature of 200C as shown in Figure 8b.

If distilled water at room temperature is used as the quenchant instead of an aqueous polymer, the silver and the AlMgSiCu probes show almost identical cooling behavior with coinciding rewetting kinematics as shown in Figure 9. This means that the quenching behavior determined in water with silver probes can be safely compared with those obtained for aluminum probes. However, when polymer solutions are used, there are clear differences, especially with respect to initial wetting.

SUMMARY Cooling rate and wetting behavior have very strong effects on the properties of quenched aluminum alloys. Age-hardening and quench distortion are determined, to a large extent, by the variations in the duration of the film boiling to nucleate boiling transition. The rewetting process can be determined exactly by measuring conductance and temperature during the quenching process. The duration of the film boiling and rewetting kinetics during quenching of aluminum alloys can be systematically influenced by varying the bath temperature when water is used as the quenchant or by varying the aqueous polymer quenchant concentration when a polymer quenchant is used. Surface oxidation of

aluminum alloys and the behavior of silver oxide at high temperature also affect the rewetting process. Therefore, the cooling behavior of silver and aluminum probes is comparable only when both metals have comparable states of surface oxidation.

REFERENCES 1. W. Kster and G. Hofmann, The Effect of Quenching Rate on the Kinetics of Cold Age Hardening of an Aluminum-Zinc Alloy with 10% Zinc, Z. Metallknd., 1963, Vol. 54, p. 570-575. 2. C.E. Bates, Selecting Quenchants to Maximize Tensile Properties and Minimize Distortion in Aluminum Parts, J. Heat Treating, 1987, Vol. 5, p. 27-40. 3. O. Zach, Experimental Investigation of the Cause of the Variation of the Leidenfrost Point, Institute of Nuclear Energetics, IKE 2-34, Stuttgart, 1976, 78 pages. 4. Y. Kikuchi, T. Hori, and J. Michiyoshi, Minimium Film Boiling Temperature for Cooldown of Insulated Metals in a Saturated Liquid, Int. J. Heat Mass Transfer, 1985, Vol. 28, No. 6, p. 1105-1114.

5. Th. Knzel, Effect of Rewetting on Allotropic Modification of Quenched Metal Bodies, Ph.D. Thesis, Technical University of Munich, Munich, Germany, 138 pages. 6. K.J. Baumeister and F.F. Simon, Leidenfrost Temperature Its Correlation for Liquid Metals , Cryogens, Hydrocarbons and Water, J. Heat Transfer, 1973, p. 166173. 7. R.E. Henry, A Generalized Correlation for the Minimum Point in Film Boiling, 14th National Heat Transfer Conference, AlCHE-ASME, August, 1973, Atlanta, Georgia. 8. D. Hein, Model Concepts on Rewetting by Flooding, Ph.D. Thesis, Technical University of Hanover, Hanover, Germany, 1980, 182 pages. 9. R. Jeschar and R. Maass, Determination of Heat Transfer During Quench Hardening of Metals in Water, Gas Wrme Intern., 1985, Vol. 34, No. 9, p. 348-354. 10. W. German Patent No. 3,538,807.2, 1987. 11. H.M. Tensi, Th. Knzel, and P. Stitzelberger, Wetting Kinetics as an Important Hardening Characteristic in Quenching:, Hterei-Tech. Mitt., 1987, Vol. 42, No. 3, p. 125-132. 12. Th. Knzel, H.M. Tensi and G. Welzel, Rewetting Rate The Decisive Characteristic of a Quenchant, Tagungsband 5th Intern. Congress on Heat Treatment of Materials, Budapest, 20-24 October 1986, p. 1806-1813. 13. H. Bomas, Quenching Rate of AlMgSi Alloys Affects the Strength Values, Maschinemarkt, 1982, Vol. 88, p. 1220-1222. 14. T. Croucher, Water Quenching Procedure for Aluminum Alloys, Heat Treating, 1982, Vol. 14, No. 9, p. 18-19. 15. E.H. Burgdorf, Properties and Uses of Synthetic Quenching Solutions, Z. Wirtsch. Fertig., 1979, Vol. 74, p. 431-436. 16. H. Beitz, Uses and Limitations of Synthetic Aqueous Quenching Liquids in Hardening Technology, Hrterei-Tech. Mitt., 1979, Vol. 34, No. 4, p. 180-188. 17. Totten, G.E., C.E. Bates and L.M. Jarvis, "Type I Quenchants for Aluminum Heat Treating", Heat Treat., 1991, December, p 16-19. 18. Bates, C.E. and Totten, G.E., "Procedure for Quenching Media Selection to Maximize Tensile Properties and Minimize Distortion in Aluminum - Alloy Parts", Heat Treat. of Metals, 1988, 4, p. 89-98.

19. H.M. Tensi and E. Steffen, Measuring the Quenching Effect of Liquid Hardening Agents on the Basis of Synthetics, Steel Research, 1985, Vol. 56, No. 9, p. 489-495. 20. H.M. Tensi and P. Stitzelberger-Jacob, Convection in Quenching Baths Different Ways of Determining the Effects of Convection, Eingereicht bei Materials Science and Technology, October, 1987. 21. H.M. Tensi, P. Stitzelberger-Jacob and Th. Knzel, Laboratory Test for Assessing the Cooling Characteristics of Polymer Quenchants, Draft International Standard, Technical University of Munich, Munich, Germany, Inst. Of Material and Processing Sciences, 1987, 28 pages. 22. K. Wefers, Properties and Characteristics of Surface Oxides on Aluminum Alloys, Aluminum, 1987, Vol. 57, p. 722-726. 23. J. Wnning and D. Leidtke, Tests for Determining Heat Flux Density During Steel Quenching in Liquid Quenchants by the QTA Method, Hrterei-Tech. Mitt., 1983, Vol. 38, No. 4, p. 149-155. 24. M. Tagaya and I. Tamura, Studies on Quenchants. Part 8: Effects of the Dimensions of the SilverSample on the Quenching Process, Hrterei-Tech. Mitt., 1963, Vol. 18, No. 4, p. 63-76.

LIST OF FIGURES Figure 1: a. Wetting sequence for a cylindrical specimen quenched in distilled water at 40C; b. Temperature TZ (measured in the center of the specimen) and wetted specimen surface as a function of time during cooling of an AlMg5 sample in distilled water at 80C. TZ and tZ: Temperature in the in the center of the specimen when it is immersed into the quenchant and the time of immersion. TS and tS: Temperature in the specimen center and time when wetting starts. Tf and tf: Temperature in the specimen center and time when the wetting process is concluded. Figure 2: Schematic illustrating the measuring principle for determining the percentage of wetted sample surface of rewetted immersion-cooled specimens.

Figure 3: Dependence of temperatures TS and Tf (measured at the geometric center of the probe) and wetting time ( tf tS ) on bath temperature during immersion cooling of a cylindrical AlMgSiCu probe ( dia. 15 x 45 mm) in distilled water. Figure 4 - Dependence of temperatures TS and Tf (measured at the geometric center of the probe) and wetting time ( tf tS ) on polymer quenchant concentration during immersion cooling of a cylindrical AlMgSiCu probe ( dia. 15 x 45 mm) in a watersoluble polymer at 25C. Figure 5 Time required for cooling a cylindrical AlMgSiCu probe ( dia. 15 x 45 mm) from solution treating temperature (temperature at which the probe was immersed) to 180C.; a. Cooling in distilled water at varying bath temperatures and b. Cooling in a water-soluble polymer quenchant at varying quenchant concentrations and 25C. Figure 6: Cooling process of a cylindrical AlMgSiCu probe ( dia. 15 x 45 mm) annealed in air for different periods of time: quenchant = distilled water, 25C, a. changes in temperatures and conductivity as a function of time; b. cooling rate as a function of the temperature at the geometric center of the probe. Figure 7: Comparison of the cooling processes of a cylindrical AlMgSiCu probe ( dia. 15 x 45 mm) with a silver probe of the same dimensions: probes quenched into a 10% solution of a water-soluble polymer at 25C (temperatures at the geometric center of the probe); solution treating temperature: 520C (AlMgSiCu probe); annealing temperature 520C for the Ag probe. Figure 8: Comparison of the cooling processes of a cylindrical AlMgSiCu probe ( dia. 15 x 45 mm) with those of a silver probe; cooled into a 10% solution of a water-soluble polymer at 25C (temperatures recorded at the geometric center of the probe); solution treating temperature is 520C for the AlMgSiCu probe; annealing temperature is 800C for the silver probe; a. changes in temperature and conductivity as a function of time and b. cooling rate as a function of temperature. Figure 9: Comparison of cooling processes of a cylindrical AlMgSiCu probe ( dia. 15 x 45 mm) with those of a silver probe; probes quenched into distilled water at 25 (probe temperatures recorded at the geometric center); solution treating temperature is 520C for the AlMgSiCu probe; annealing temperature is 520C for the silver probe; a. changes in temperature and conductivity as a function of time and b. cooling rate as a function of temperature.

Definition of Symbols
Symbol A G TB Tf Ts Tz
T

Unit mm S
o

Meaning Specimen surface area Electrical conductance Bath temperature Temperature in the center of the specimen at the conclusion of the wetting process (final temperature of the wetting) Temperature in the center of the specimen at the beginning of the wetting process (starting temperature of the wetting) Temperature in the center of the specimen Cooling rate Temperature conductivity Specific heat capacity Time at the conclusion of the wetting process (final time of wetting) Time at the beginning of the wetting process (starting time of wetting with respect to immersion of the specimen into the fluid)

C C C C

k/s m/s J/kg s s w/m /K w/m/K kg/m

3 2

a Cp tf ts

Heat-transfer coefficient Thermal conductivity Density

Figure 1

Figure 2

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Figure 5

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Figure 7

Figure 8

Figure 9