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Scripta Materialia, Vol. 39, No. 2, pp. 197203, 1998 Elsevier Science Ltd Copyright 1998 Acta Metallurgica Inc. Printed in the USA. All rights reserved. 1359-6462/98 $19.00 .00

PRECIPITATION KINETICS OF AA4032 AND AA6082: A COMPARISON BASED ON DSC AND TEM
G. Biroli*, G. Cagliotia,b, L. Martinia and G. Riontinoc
b

Politecnico di Milano, Dipartimento Ingegneria Nucleare, via Ponzio 34/3, 20133 Milano, Italy INFM UR Milano Politecnico, Milano, Italy cUniversita ` di Torino, Dipartimento Chimica IFM and INFM UR Torino Universita ` , via Giuria 9, Torino, Italy (Received September 29, 1997) (Accepted in revised form February 11, 1998)

1. Introduction The kinetics of precipitates and, in general, the far from equilibrium dynamics of an alloy after quench, can be conceptually described in two ways: by a theory at atomic level, which is, essentially, a kinetic theory. However, although all necessary physical parameters are known (diffusion coefficients, surface energy, atomic masses, . . . ), the description of precipitate formation is technically difficult and the theory does not supply an intuitive view of the phenomenon. by a macroscopic theory, based on the competition between the surface and volume energy contributions to the Gibbs potential. The objective of this note is to utilize the macroscopic theory in order to obtain an additional criterion for the identification of the nature of the precipitates. To this aim the formulation of the activation energy for the growth of precipitates is used in conjunction with differential calorimetry performed at different scanning velocities. In the following section we critically examine the steps leading to the currently adopted kinetic expression da/dt K(T)f(a), a being the precipitating fraction at time t, K(T) the temperature dependent kinetic activation term and f(a) a function depending exclusively on the reaction mechanism. In section 3 experimental data on the AA4032 and AA6082 alloys are given, including those at several scanning velocities; the data are discussed, showing that the activation energy could be safely used as a parameter for the identification of the nature of the precipitates. For alloys of similar compositions, such as the pseudo-binary Al-Mg-Si alloys considered here, this criterion of identification could prove useful.

2. Dynamic Model for Precipitation Kinetics A system far from equilibrium is forced toward energy minima (minima of Gibbs potential for an alloy after quench), but at the same time it is subjected to a thermal noise, which allows the system to explore the energy landscape. The standard analysis of far from equilibrium dynamics is based on the Langevin approach. However this approach is not viable for an alloy after quench because of the lack of knowledge of the Gibbs potential for all the a priori possible configurations.
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In practice the system evolution can be approximated by confining the accessible configurations along a one dimensional trajectory of the metastable phases. The precipitation of each metastable phase occurs in two steps: nucleation, up to a critical size, followed by growth. The very early nucleation stage is controlled by surface energy, but its critical limit is determined also by a volume dependent energy determined by the strain energy density and the chemical potential: at equilibrium the critical state is characterized by a balance between the force driving toward the surface reduction and the cohesive force driving toward the bulk formation. The growth stage is controlled by diffusion toward the surface at the atomic level and by volume dependent terms at the macroscopic scale. For both alloys of the present study Mg2Si precipitates are the most relevant ones; due to the relations between the atomic volumes (Si and Mg slightly smaller and larger than Al respectively), the strain energy density contribution should be smaller than that due to the chemical potential. Incidentally this circumstance comparatively decreases in these alloys the size of the residual stresses induced by thermal treatments. The above model can be formulated by the following master equations, describing the rate of variation of the quantity of matter undergoing precipitation and dissolution, while the system moves along the trajectory described by a(i), its density at the time t, and a(i*), its critical density at the corresponding time t: da i E i 1 * 3 i c i 1 * 3 i exp a i 1 * dt kT c i * 3 i exp

Ei* 3 i ai* kT

c i 3 i 1 * exp c i 3 i * exp

Ei 3 i 1* ai kT

Ei 3 i* ai kT

da i 1 * Ei 1 3 i 1* c i 1 3 i 1 * exp ai 1 dt kT c i 3 i 1 * exp

Ei 3 i 1* ai kT

c i 1 * 3 i 1 exp c i 3 1 * 3 i exp

E i 1 * 3 i 1 a i 1 * kT

E i 1 * 3 i a i 1 * . kT

Here E[i 3 i*] is the activation energy for the dissolution process i 3 i*, and E[i* 3 i] is an energy barrier associated to diffusion, which can be envisaged as equivalent to an activation energy for the precipitation process i* 3 i; c[i 3 i*] and c[i* 3 i] are, accordingly, the frequencies of attempts to overcome the barriers E[i 3 i*] and E[i* 3 i](Fig 1).

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Figure 1. Average trajectory in the energy landscape, G is the Gibbs potential and is the current coordinate along the average trajectory. While temperature increases, the trajectory visits successively the Gibbs energy minima, overcoming the critical states (labelled by *) of growth of the metastable phases. The increase of thermal energy discloses the access of the system to deeper and deeper Gibbs energy minima.

DSC Measurements Referring again to fig. 1, immediately after quench at low temperature, there is only phase 1(metastable solution); a temperature increase enables the system to overcome the energy activation barrier E[1 3 2*] (subcritical growth of metastable phase 2); a further temperature increase activates the diffusion processes leading to the growth 2* 3 2, assisted by the chemical potential. Step 1 3 2* requires a comparative small thermal energy absorption, while step 2* 3 2 is accompanied by a comparatively large thermal energy release. Under the hypotheses that the minima of the metastable phases, though accessible via diffusion, are located far apart one from the other in the Gibbs potential space, and that the overall trajectory followed in this space while performing the DSC measure is preferably covered in the sense of lower and lower Gibbs potential, the master equations becomes: da i Ei* 3 i c i * 3 i exp ai* dt kT da i * Ei 1 3 i* c i 1 3 i * exp ai 1. dt kT In fact, under the above hypotheses, the transformations i 3 (i 1)* ((i 1)* 3 i 1)(third addenda at the right hand side of the full master equation) start only when the transformations i* 3 i (i 3 (i 1)*) (second addenda) are completed, since in practice the system evolution is not affected by distant configurations due to the limited number of phases. Furthermore the contributions to the master equation of the terms which represents a flow in the direction opposite to the drift direction should be negligeable, so that the probabilities of transformations (i 1)* 3 i and i 1 3 (i 1)* (first addenda) are small with respect to the probabilities of transformations i 3 (i 1)* and (i 1)* 3 i 1 (fourth addenda). During the process i 1 3i* due to conservation of matter a(i1) a(i*) 1; during the process i* 3 i, similarly, a(i) a(i*) 1. Therefore: da i * Ei 1 3 i* c i 1 3 i * exp 1 a i * dt kT da i Ei* 3 i c i * 3 i exp 1 a i dt kT

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TABLE 1 Composition (wt%) of the Alloys

Si AA4032 AA6082 11.04 0.89 Fe 0.36 0.37 Cu 1.30 0.07 Mn 0.05 0.57 Mg 1.13 0.78 Cr 48 (ppm) 0.16 Zn 0.07 0.20 Ti 0.02 0.02 Ni 0.97 -----Al rem rem

The above energy landscape analysis justifies and helps to set the limits of validity of the phenomenological form da/dt K(T)f(a) currently used for homogeneus nucleation. In particular this formula applies when the metastable phases dont approach too closely along the trajectory. 3. Comparative Analysis Between Precipitates Kinetics of AA4032 and AA6082 Alloys In a series of measurements, reported here only partially, whose objective was to optimize the thermal treatment so as to realize low residual stresses and, at the same time, good mechanical performance, among the investigated samples we focus here on two groups of samples of AA4032 and AA6082 alloys, each extracted from two cylinders 10 cm dia., 5 cm high of the above alloys, whose composition is reported in Table 1. Both the alloys, in form of nearly 1.5 mm-thick plates extracted from the core of the cylinders, have been solution treated at 520C for one hour and quenched in cold water, and maintained in freezer immediately before cutting the samples for the DSC measurements. Three runs have been performed for each alloy, at several scanning velocities in the range 570 K/min. Because of scarse information on AA4032 alloy, more extensive experimental analysis has been done on it than on AA6082. It will be shown that, as indicated in the objective, a comparison of the DSC data for the two alloys allows in practice to identify the nature of the main exothermal peak in AA6082 without making recourse to the TEM measurements performed on AA4032 (1). 3.1 AA4032 By TEM analysis it has been confirmed that the hardening component of this alloy is -Mg2Si; by DSC measurements (fig. 2) and comparative TEM analysis the following precipitation sequence has been recognized: Guinier Preston zones (GP)3(metastable coherent phase)3(metastable semicoherent phase)3 (stable phase).

Figure 2. DSC trace for the AA4032 sample at 20 K/min.

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Figure 3. DSC traces for the AA4032 sample at different scanning velocities (10, 20, 40, 60, 80 K/min).

GP zone formation (fig. 2) is seen to occur at about 120C, GP zone dissolution at 200C, formation of phase at 250C, dissolution of phase at 270C, formation of phase at 285C and its partial dissolution at 300C; the hump around 330C is interpreted in terms of a complete dissolution of delayed due to the presence of copper, whose role is believed to stabilize the Mg2Si precipitates, even if the reversion of more complex precipitates formed during the scanning cannot be excluded; it is uncertain whether the signal at 520C corresponds to formation of stable phase or to a step formed by the dissolution line meeting the eutectic fusion line. From the rates of the temperature peaks displacements vs the scanning velocity (fig. 3), on the basis Ozawas method (2), the activation energies have been obtained and reported in Table 2. 3.2 AA6082 For this alloy it is known (3, 4) that the precipitation sequence is: GP3(coherent metastable phase)3 (semicoherent metastable phase)3 (stable phase). Here also the hardening precipitate is Mg2Si. The DSC measures of fig. 4 for AA6082 confirm this pattern. Here we focus on the broad peak around 280C obtained at a scanning rate of 30 K/min. A numerical analysis of this peak has been performed by referring the peak itself to a simple, linear baseline, in order to minimize the number of free parameters in the handling of the numerical fit. The experimental data, so freed from the background, clearly exhibit the composite nature of the original peak which can be interpreted as a superposition of two bell-shaped functions whose centers, though strongly dependent on the scanning rate, occur at around 280C and 330C. The larger peak at 280C is interpreted as due to precipitation while the smaller one at 330C as due to . The peak at 450 C corresponds to
TABLE 2 Activation Energies (in kJ/mole)
AA4032 GP precipitation GP dissolution precipitation precipitation precipitation 61.9 2.1 106.1 4.7 94.2 5.0 114.8 4.5 -------AA6082 --------------89.3 6.5 -------170 9.1

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Figure 4. DSC trace for the AA6082 sample at 30 K/min.

precipitation of the stable phase and the peak at 120 C, more pronounced in the AA4032 (fig. 2), corresponds to a partial GP zone formation. Also for this alloy, from the temperature peaks displacements vs the scanning velocity (fig. 5), on the basis Ozawas method the activation energies have been obtained and reported in Table 2. Lets compare now the above results for the two alloys. The excess of silicon in AA4032 seems to be unimportant on the prepitation kinetics. The precipitation patterns are similar, the main difference being the peak at 470 C for AA6082 alloy and the hump after peak for AA6082 alloy. As indicated before this difference could be explained in terms of stabilization of the phase by copper; similar explanation could be held for the hump following the peak, indicating a slowing down of the dissolution of this phase. Coming back to the objective of this note, we draw attention on the close similarity of their kinetic patterns, suggesting similar kinetic histories. In particular, focusing on the activation energies measured for the precipitate in the two alloys, their values are equal within an experimental error of the order 6%; furthermore the peaks occur at close values of the temperature.

Figure 5. DSC traces for the AA6082 sample at different scanning velocities (5, 10, 30, 60, 70 K/min).

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Therefore it seems possible to conclude that even without additional TEM analysis, the identification of precipitate in one of the alloys implies the same identification in the other one, whenever the peak temperatures and the activation energies lie in the same ranges. Acknowledgments This work is part of a coordinated project involving, besides the authors institutions, Professor G. Albertini, Dr. M. Fiori and Professor F. Rustichelli, Universita ` di Ancona. Thanks are due to these colleagues and to Dr. P. Fiorini and Dr. E. Olzi for enlightning discussions. Thanks are also due to Mr E. Signorelli for his assistance with the TEM measurements. The work has been partially financed by Consiglio Nazionale delle Ricerche, Comitato Tecnologico (contract number 96.01803.CT11). References
1. 2. 3. 4. L. Martini, Undergraduate Thesis, Politecnico di Milano (1996). T. Ozawa, J. Thermal Anal. 2, 301 (1970). M. Takeda, F. Ohkubo, T. Shirai, and K. Fukui, Mater. Sci. Forum. 217222, 815 (1996). N. Maruyama, R. Uemori, N. Hashimoto, M. Saga, and M. Kikuchi, Scripta Mater. 36, 89 (1997).