Acta metall, mater. Vol. 42, No. 9, pp.

3035-3043,1994

Pergamon

0956-7151(94)E0084-T

Copyright 1994ElsevierScienceLtd Printed in Great Britain.All fights reserved 0956-7151/94$7.00+ 0.00

N U C L E A T I O N MECHANISM OF DISCONTINUOUS PRECIPITATION IN Mg-AI ALLOYS A N D RELATION WITH THE M O R P H O L O G Y

D. D U L Y I and Y. B R E C H E T z

tDepartment of Engineering, Cambridge University, Trumpington Street, Cambridge CB2 1PZ, England and 2Laboratoire de Thermodynamique et Physico-Chimie M~tallurgiques, ENSEEG, B.P. 75, 38402 Saint Martin d'H&es, France
(Received I June 1993; in revised form 2 February 1994)

Abstract--The nucleation rate of discontinuous precipitation in Mg-AI has been measured as a function of temperature, initial grain size and solute content. From these measurements, it appears that at high temperatures (T/> 220C) all precipitation nodules nucleate via Fournelle and Clark's mechanism, whereas at lower temperatures (T ~ 140C), at least one of the mechanisms identified by Tu and Turnbull or Purdy and Lange is also active. The proportion of double seam nodules determined by optical microscopy decreases from more than 1/2 to 0 when the temperature increases. In the low temperature domain, this behaviour is in agreement with that predicted by Baumann, Williams and Michael. Rtsumt---Le taux de germination de la prtcipitation discontinue dans les alliages Mg-A1 a 6t6 mesur6pour difftrentes temptratures, tailles de grains initiales et teneurs en solutt. A partir de ces mesures, il apparait qu'~ haute temptrature (T/> 220C), tousles nodules de prtcipitation se forment suivant le mtcanisme de Fournelle et Clark alors qu'fi de plus basses temptratures (T ~ 140C), l'un des mtcanismes identifits par Tu et Turnbull et Purdy et Lange est 6galementactif. La proportion de nodules prtsentant une double courbure, dtterminte par microscopie optique, dtcrolt d'une valeur suptrieure A 1/2 jusqu'~ 0 lorsque la temptrature augmente. Dans le domaine des basses temperatures, ce comportement est en accord avec celui prtdit par Baumann, Williams et Michael.

1. INTRODUCTION The relationship between discontinuous precipitation and heterogeneous grain boundary precipitation is still an open problem. In particular, the nucleation step of discontinuous precipitation in relation with grain boundary precipitation needs to be precised. The various possible nucleation mechanisms have been clearly identified in numerous systems but the question of their relative importance, for a given system, depending on temperature and solute concentration needs some more extensive studies. The scope of this paper is to investigate this problem for Mg-A1 alloys. The variation of the nucleation rate of discontinuous precipitation has been measured as a function of the temperature, the Ai content CO and the grain size diameter d. It is shown that it is possible to identify the dominant nucleation mechanism from this data and from a combined study of the morphology of precipitation nodules. Finally, the possibility to generalize the characteristics of Mg-AI to other systems where discontinuous precipitation takes place is also considered.

2. POSSIBLE MECHANISMS OF NUCLEATION Three main nucleation mechanisms have been identified for discontinuous precipitation: In the first mechanism proposed by Tu and Turnbull, a precipitate first nucleates at the grain boundary and then acts to pull it from its initial position; the movement is associated with a reduction of interfacial energy [1-3]. In the second mechanism, the initial displacement of the grain boundary is due to chemical forces (similar to the DIGM driving force) as for steady state growth, as proposed by Purdy and Lange [41. In the third mechanism, the forces responsible for the initial grain boundary motion are capillarity forces, identical to those that act during grain growth or recrystallisation, as proposed by Fournelle and Clark [5]. Direct observation of the initiation of discontinuous precipitation is difficult, Therefore, Baumann, Michael and Williams have attempted to correlate the morphology of discontinuous precipitation nodules with their nucleation mechanism [6]. They

3035

3036

DULY and BRECHET:

DISCONTINUOUS PRECIPITATION IN Mg-A1 show that when the whole sample is invaded by discontinuous precipitation, the macroscopic kinetics obey Johnson-Mehl-Avrami's equation and can then be interpreted to give a value of the nucleation rate. In [10], the Vickers measurements were shown to agree with the results of X-ray diffraction as the transformed volume fraction X and the hardness D are then related by X(t) = D(t) - D ( O ) D(tmax)--O(O) (1)

have observed that in Cu-Be, nodules may grow either on one side of the grain boundary (the so called "single seam" morphology) or develop alternately on both sides of the boundary. In the latter case, nodules first exhibit the "S" morphology [7], which then evolves towards the "double seam" morphology [8] while the growth proceeds. Based on these observations, Baumann et aL made the three following assumptions: (i) Double seam nodules are typical of Tu and Turnbulrs mechanism whereas nodules formed via Fournelle and Clark's mechanism should mainly result in a single seam morphology. (ii) The proportion of double seam nodules decreases as T increases. The temperature Tl/2, at which this proportion is 1/2, is related to the melting temperature Tm. (iii) As a consequence of (i) and (ii), it may be concluded that when T < Tt/2, Tu and Turnbull's mechanism is dominant, whereas when T > T~/:, most discontinuous precipitation nodules initiate via Fournelle and Clark's mechanism. Recently, Gust, Chuang and Predel have confirmed for different systems that the fraction of double seam nodules decreases when T increases but have found that Tl/2 is proportional to Ts, the solvus temperature, rather than to Tm [9]. They have proposed that Baumann et al.'s assumption (i) may be too simplistic, since double seam nodules might also form via Fournelle et aL's mechanism.
3. MATERIALS AND EXPERIMENTAL PROCEDURES

Four binary Mg-A1 alloys with a solute content ranging from 3.6 to 10at.% A1 were provided by Pechiney as bars whose diameter was approx. 16 mm. The alloys, previously melted using conventional alloying techniques, had been extruded at 250C under a pressure of 250 bars. The alloys were 99.91% pure, and the impurities were mainly Mn (480 ppm), Si (350 ppm) and Fe (30 ppm). For each alloy, two solution annealing heat treatments were carried out. Some specimens were solution treated for 128 h at 420C: after this treatment, their average grain diameter was approx. 95 #m. Other samples were annealed at 420C for 8 h, which resulted in an average grain size of approx. 35 tim. Heat treatments were then carried out at temperatures ranging from 140 to 340C. The Vickers hardness was measured after different annealing times. The use of Vickers hardness to investigate discontinuous precipitation is always a subject of concern. In order to feel confident about this technique, we rely on a previous work on the same alloy [10] in which we have characterized the macroscopic kinetics by optical metallography, Vickers hardness and in situ X-ray experiments. The X-ray experiments are difficult to perform but are very precise. They

in which D (0) is the initial hardness value and D (tmax) is the hardness when the precipitation process is completed. The 95% confidence interval for D is generally about 0.7 hV [cf. Fig. l(a)]. From equation (1), it is possible to determine an upper and a lower nucleation rate for which a calculated curve D(t) passes through most of the 95% confidence intervals of the experimentally measured hardness points. It was found that when no continuous precipitation occurs, there is never more than a ratio of 2 between these two limit nucleation rates [Fig. l(b)], and it has been found that the nucleation rate value determined from X-ray experiments always lies within the range given by these two values. In the Mg-A1 system, the macroscopic kinetics of discontinuous precipitation can thus be reliably followed by Vickers hardness. The statistical analysis of the morphology of discontinuous precipitation nodules was performed by optical microscopy. Before observation, the samples were etched for one or two seconds with a solution containing 10 ml H F and 90 ml H20, and then rinsed with water and ethanol. N~ and N: being respectively the number of single seam and double seam nodules, the fraction of double seam nodules N2/(N ~+ N2) was determined from a consideration of at least 250 nodules for each sample.

4. NUCLEATION RATE OF DISCONTINUOUS PRECIPITATION 4.1. Results The dependence of the macroscopic kinetics of discontinuous precipitation on the initial grain size varies with temperature: (i) at T = 220C, alloys containing between 5.4 and 10at.% A1 are fully or almost fully invaded by discontinuous precipitation. The alloys with the smallest grain size d are systematically softer than the other ones. The effect of d is simply a translation in hardness, and not a modification of the kinetics [Fig. l(a)]. The curve - l n ( 1 - X ) = g(t) is a straight line [Fig. l(b)] whose slope a represents the nucleation rate per grain, i.e. [10, 11] a = r~d2l~ (2)

where Is is the nucleation rate per unit area of grain boundary. For alloys with a solute content between

DULY and BRECHET: (a) r = 220C

100

DISCONTINUOUS PRECIPITATION IN Mg-A1 (b) r -- 220C / /

3037

90

?
~
I

4 I

. . / ' "

;> e~

80 [] d = 35 p_m 70

7
60 0

d = 95 ktm

,i
0 0.5 1.0 1.5 2.0

1
1

I
2

I
3

I
4

t (h)

t (h)

(C) T = 140C 100

(d) T = 140C 4

90

>.
80

_=

70

60

I
I0

I
20

I
30

I
40
10

20

30

40

t (h)

t (h)

Fig. 1. Evolution of the Vickers hardness D of the alloy Mg-10 at.% A1 with time at different annealing temperatures: (a) At 220C, the slope of the curve D =f(t) does not depend on d. The error bars give 95% confidence intervals. They are not shown when they are smaller than the symbol used for the points in the graph. (b) At this temperature, -In(1 - X ) = g(t) where X = [D -D(O)]/[D(t~x)- D(0)] can be fitted by a straight line. The plain line shows the best fit straight line whereas the two dashed lines indicate the limits of the domain of good fit (a good fit straight line is expected to cross at least all but one 95% confidence intervals of the experimental points). The ratio between the slopes of the upper and lower dashed lines is 1.95. (c) At 140C, the slope of D =f(t) varies with d. (d) - l n ( l - X ) = g(t) cannot be fitted by a straight line.

5.4 and 10 at.%, the nucleation rate of discontinuous precipitation per grain does not depend on d (Table 1). (ii) at T = 140C, discontinuous precipitation only invades about 20% of the alloys which contain 7.7 and 10 at.% A1. In contrast with the previous case,
Table 1. Variation of the nucleation rate of discontinuous precipitation with grain size at two different temperatures d(#m) T = 220'C T = 140'~C 35 95 35 95

nd21s (h t ) C0 = 7.7 at.%

0.18 0.18 1.9 10 +3 2.8 10 -3

7td21s(h- ~) Co= 10 at.%

2.2 2.2 1.5 10-2 2.1 10 2

there is no systematic influence of d on hardness: the kinetics of discontinuous precipitaiton is influenced by a change in grain size. The error bars on Fig. l(c) clearly demonstrate that the curves cannot be superimposed by a mere translation. In contrast to the previous temperature, the curves - l n ( 1 - X ) = g(t) are not straight lines [Fig. l(d)]. However, optical metallography has shown that during the first 15 h of the heat treatment, only discontinuous precipitation occurs and that further heating essentially produces continuous precipitation. It has also been shown in a previous work that the contributions to hardness due to discontinuous precipitation and coarse continuous precipitation are roughly equivalent [12]. Thus, we can have a rough estimate of the nucleation rate

3038

DULY and BRECHET:

DISCONTINUOUS PRECIPITATION IN Mg-AI

--i--~A-10----eB

C0= 9at.% from [12] CO= 9at.% C0= 9at.% CO= 9at.% C0= 9at.%

.i<>i.
1 -~" ~'O--

\ ....

10-1

z:---" .... y /'--, .,Y /

.....

\ ,,

\
X

:.l
%
10-2 _

f'/ io

/~'

I ' - . ~ . I'lb,

',,.,
. .

., (?)

i
I I

//

" "'t)

10-3

i
I I

I I I

..
| I
0.22
RT

10-4 _

ji
0.18

'1
0.20

/I
0.24 1000 (j-l)

I
0.26

I
0.28

x,

I
0.30

Fig. 2. Variation of the nucleation rate of discontinuous precipitation with temperature for different solute contents when d = 95/~m. The symbol (&) for Co = 10 at.% at 140C indicates that 95% confidence interval is more than two orders of magnitude large. The curve giving the variation of the nucleation rate for the Mg-9 at.% AI alloy studied by Clark [12] is also shown.

of discontinuous precipitation by fitting a JohnsonMehl expression to the first 15 h. It seems that for both the alloys Mg-7.7 and Mg-10 at.% A1, ~zd2Is tends to increase when d increases (Table 1). However, the nucleation rate values estimated at 140C are much less precise than that obtained at 220, 260 and 300C. Figure 2 shows the variation of the nucleation rate with temperature for different compositions when d = 95/~m (the curve obtained from the Vickers hardness measurements carried out by Clark [13] on a Mg-9 at.% A1 alloy is also shown for comparison). F o r a given value of Co, the curve I s vs T has the classical C shape. Note that I s decreases to 0 before the solvus temperature is reached and discontinuous precipitation is replaced by continuous precipitation at high T [14].

dependences are as follows: (i) F o r Tu and Turnbull's mechanism, we may postulate that the nucleation rate is given by

L,~r = IBP..o,rr

(3)

where IB is the heterogeneous nucleation rate of grain boundary precipitates and P..c,rr is the probability that this precipitate induces the first displacement of the boundary. I B is independent of d and is classically given by [15] IBocexp[

( as(vm)2 ~ , ,

/ ' ( 0 ,j )]

(4)

4.2. Interpretation
Depending on which nucleation mechanism is dominant, we expect different behaviours of the nucleation rate with the experimental parameters (grain size, initial supersaturation). Conversely, from our experimental observations of these dependences, we can attempt to identify the dominant nucleation mechanism for a given temperature For the nucleation mechanism classically proposed, the expected

where AGa is the energy of formation of one mole of the precipitate, Vm is the molar volume, tr is the precipitate matrix interface energy, f(O) is a function of the contact angle 0 between the precipitate and the grain boundary. We can assume that P~c,rr does not depend on d, as it is related to a local mechanism of absorption of the precipitate on one side of the grain boundary. For the same reason, AGp or AGo, the molar chemical energy stored in the supersaturated solution, should not enter P.~,rr. The nucleation rate per grain d2Is,rr is thus given by
d2/s'TT OCd2 exp[L

(aG~

0"3(Vm) 2 ]to . . . . n. 7

(5)

DULY and BRECHET:

DISCONTINUOUS PRECIPITATION IN Mg-AI

3039

(ii) For Purdy and Lange's mechanism, it has been proposed in a previous paper that [10]
l s , , ocv

exp'I_

E 7 [-AGo-] ~ - ~ J s h L - ~ J P.~,pL

(6)

of the two curves ln(nd2I~)=fl[-(AGo) -2] or ln(nd2Is) =f2[ln(AG0)] is a straight line [Fig. 3(a,b)]. The variation of the nucleation rate with Co and d when 3.4 at.% ~< Co ~< 10 at.% may be described by the empirical relationship d2/s ~ exp[A (AG0)1/4]. (9)

where v is the vibration frequency of the grain boundary considered as a membrane, E is the activation energy for the vibration of the membrane, AGo is responsible for the first displacement of the boundary, and Pnuc.PL is the probability that the displacement of the boundary induced by chemical forces will lead to discontinuous precipitation. v was estimated to be proportional to d - l (vibration modes of an elastic membrane) [10]; E is independent of d and only depends on the structure of the grain boundary (more precisely on its surface energy y). Though the details of Purdy and Lange's mechanism are not well understood, it is unlikely that Pnuc,PL is related to d and its dependence on AGo or AGa should be weak. Since AGo ,~ RT, it results that

It may thus be concluded that at this temperature, all the discontinuous precipitation nodules nucleate via Fournelle and Clark's mechanism, as had previously been proposed [10]. Note that equation (9) is certainly invalid for very low supersaturations for it would give a finite nucleation rate for AGO= 0. (ii) At T = 140C, d2ls increases slightly when d increases by a factor of 2.7 (Table 1). The experimental uncertainty of this result prevents any precise statement about the nature of the dependence on d. However, this slight increase suggests that a non negligible proportion of nucleation events is d dependent, i.e. of the Tu and Turnbull or of the Purdy and Lange's type.

d2I~PLOC d AGo.
' /~1

(7) 5. MORPHOLOGY OF DISCONTINUOUS PRECIPITATION NODULES According to Baumann et al., Tu and Turnbull and Fournelle and Clark's mechanisms are preferentially related to single seam and double seam morphologies respectively. We have therefore performed a quantitative study of the respective proportions of both morphologies by optical metallography.

(iii) For Fournelle and Clark's mechanism, it has also been proposed in [10] that

:s,,co v exp[-

E-]TVm

7 eoc,Fc

<S)

where v and E have the same values as in equation (6), YVmd-l is the capillarity energy responsible for the first displacement of the boundary and P~o.FC is the probability that the displacement of the grain boundary induced by capillarity forces will allow a discontinuous precipitation nodule to nucleate. As in (ii), v is proportional to d - j , and assuming that the dependence of P~.ec on d and AGo is very small, it follows that the dependency of d2I~.FCon d and AGo (or AGo) should be negligible. Table 2 summarizes the expected dependence of the nucleation rate per grain on the grain size and the driving energy available for the three initiation modes. From our experimental results, it appears that in the Mg-AI system, the mechanism of discontinuous precipitation depends on the temperature: (i) At T = 2 2 0 C , d2I~ does not depend on d (within experimental accuracy) and exhibits only a very small dependence on the initial solute content. Neither equation (5) nor equation (7) are fulfilled for the whole concentration range since none

5. I. Results
Optical microscopy of the Mg-7.7 at.% A1 alloy shows that single and double seam nodules can form at all temperatures between 140 and 300C. The single seam morphology corresponds to the motion of the grain boundary on one side only [Fig. 4(e, f)]. The direction of the reaction front does not seem to depend solely on the initial curvature direction, as would be the case for grain growth. The double seam and S shaped morphologies are more complex: Fig. 4(a~l) show different stages of the growth of double seam nodules at T = 220C. Two distinct domains nucleate on a grain boundary and begin to grow in opposite directions [Fig. 4(a)]. This growth is accompanied by a lateral expansion, so that the two domains finally come into contact [Fig. 4(b)], which results in the S morphology described by Fournelle [7]. The width of the two domains continue to increase, leading to the

Table 2. Expected dependence of the nucleation rate per grain on the grain size and the initial supersaturation for each initiationmechanism Dependence of d21s Initiation Mechanism Dependence of d2I~on d on the initial supersaturation Tu and Turnbull [1-3] ~d 2 ocexp[-aa(vm)2f(O)/(AG~)2RT] Purdy and Lange [4] ocdj ocAG 0 Fournelle and Clark [5] ocd Weak dependence

3040 15
(a)

DULY and BRECHET:

DISCONTINUOUS PRECIPITATION IN Mg-A1 140C ~< T ~< 300C, N2/(N 1+ N2) is a linear, decreasing function of T [Fig. 4(g)]

N2
~ 1o

T2--T

NI + N2

T2- T~"

(lO)

0 -400

I -300
_

I -200
AGI 3 ,~-2

I -100

I 0

15

T2 and T~ are the extrapolated temperatures at which N2 and NI respectively cancel. Table 3 gives the values of /'2, T~, TI/2 = (T2+ 7"1)/2; the melting temperature Tm and the solvus temperature Ts of the two alloys are also shown for comparison. There is no simple relationship of proportionality between Ta, T2, TI/2 and Tm. But the ratio T~/2/T~ is equal to 0.63 for both alloys. Note finally that optical microscopy observations have revealed that in Mg-A1, T2 is the temperature above which no discontinuous precipitation takes place.

5.2. Interpretation of the evolution of the proportion of single and double seam nodules with temperature
,~ 10

In order to understand the decrease of the fraction of double seam nodules when T increases, it is necessary to consider separately the low temperature domain, in which more than one initiation mechanism is active and the high temperature domain, in which only Fournelle and Clark's mechanism operates:
i 2 I 4

(i) Low temperature domain: following Baumann

et al. [6], we may assume that Tu and Turnbull's

In (104 AG0).-~--), mechanism should result mainly in the formation of double seam nodules. But with Fournelle and Clark's mechanism we expect a majority of nodules to exhibit a single seam morphology. When T increases, the proportion of nodules that form via Fournelle and Clark's mechanism increases, and as a result, N2/(NI + N2) decreases, in agreement with our experimental results. (ii) In the high temperature domain (T i> 220C) where only Fournelle and Clark's mechanism is effective, the preceding explanation can no longer hold. We have to study within this mechanism itself which parameters favour one of the two morphologies.
I 1.5

15-

(C)

/~

(
...~ 10
--

I 0.5

I 1.0

(100 TM.--~), AG0~ Fig. 3. (a) At T=220C, the curve ln(Trd21~)= fI[-(AG#) -2] is not a straight line; (b) the curve ln(nd21s) =f2[ln(AG0)] is not well fitted by a straight line; (c) the curve ln0td21s)=f3[(AG0) TM]is a straight line.

double seam morphology identified by Frebel and Schenk [8] [Fig. 4(c,d)]. The S and double seam morphologies correspond to two different stages of the same phenomenon [6]. We have measured the evolution of the fraction N2/(N 1 + N2) of double seam nodules with T when C O= 7.7 at.% and CO= 10 at.%. It appears that for

The formation of single seam nodules via Fournelle and Clark's mechanism corresponds to the vibration of the boundary in its fundamental eigenmode (vibration frequency v~, activation energy El and probability of initiation of discontinuous precipitation Pnuc,FCA),whereas the formation of double seam nodules is possible through the excitation of a superior (excited) vibration mode for the membrane (vibration frequency Vz, activation energy E 2 > E l and probability of initiation of discontinuous precipitation Pnu~,Fc,2). From equation (8), it follows that

NI+N 2

Nz

FC1e xrE2 -- 1-1 YI Pnuc ......... p -- EI~-]-' . (11)

V2Pnuc,FC,2

~ RT

)J

There comes an apparent paradox: if E E - E~ and Pnu,~C,I/Pnu,FC,2 were independent of T, one would

DULY and BRECHET: DISCONTINUOUS PRECIPITATION IN Mg-A1

3041

N2 N2 + N 1 3.7 ~ ~ 3.6 C).5 D.4-o% 0.3-0.2-0.1

0 --

(g)

Co= 10% C0= 7.7 %

100

150

200

250 T (C)

300

350

400

Fig. 4. Different morphologies of discontinuous precipitation nodules as observed from optical microscopy: (a~l) different stages of growth of double seam nodules; (e, f) examples of single seam nodules; (g) variation of the fraction of double seam nodules N2/(NL+ N2) with temperature.

expect N2/(N1 + N2) to increase when T increases. That is experimentally not the case. Therefore, one needs to assume a T dependence in the parameters of equation (11). This can be justified as follows: E 2 - E l is likely to be proportional to the grain boundary energy ~,, as the higher this energy is, the more difficult it is for the boundary to vibrate.
Table 3. Characteristic temperatures of the morphology of discontinuous precipitation nodules in the alloys Mg-7.7at.% AI and Mg-10 at.% AI CO(at.%) 7.7 10 T I (K) 183 222 T2 (K) 613 625

Ti/2 (K)
398 424

Ts (K) 633 675

Tm(K) 784 738

7"1 and T2 are the extrapolated temperatures at which the proportion of single and double seam nodules respectively cancel; TI/2 is defined by Tt/2 = (T I + /'2)/2; Ts and Tm are respectively the solvus and melting temperatures of the alloy.

STEM annular dark field images have shown that the solute A! tends to segregate at the boundary [16]. (This result has been confirmed by calculation of the segregation energy of Al in Mg via Miedema's model [17].) The absorption of solute by the boundary thus reduces y. When Co is fixed, an increase in the temperature leads to an increase in the A1 content in the matrix at equilibrium, therefore reducing the amount of solute likely to segregate in the boundary. This leads to an increase in y, which reduces the proportion of double seam nodules. (Note also that at constant T, the increase in Co leads to an increase in the solute content in the boundary, and thus to a reduction of T and of g 2 -- E l , which tends to favour the formation of double seam nodules, in agreement with the experimental results.)

3042

DULY and BRECHET:

DISCONTINUOUS PRECIPITATION IN Mg-Al d2Ij/M

Therefore, we can understand why, even in the high temperature regime, N2/(N~ + N2) is a decreasing function of T.

5.3. Interpretation of the disappearance of discontinuous precipitation at high temperature

The disappearance of discontinuous precipitation at high temperature is experimentally observed to be correlated with the cancellation of N2/(Nt + N2). In order to understand this observation, it is necessary to take the variation of Pnuc,FC,l/Pnuc,Vc,2 into account. P..c,FC is the probability that the first displacement of the grain boundary allows the formation of a discontinuous precipitation nodule, i.e. that the aUotriomorphs that precipitate in the boundary are efficient to pin it during its migration. When Co and T are fixed, the smaller the migration speed (i.e. the smaller the vibration frequency) of the boundary, the higher this pinning probability is. It is therefore expected that P..c,FC,2 will cancel whereas P..,FC,] still has a finite value. This is why N2/(N 1+ N : ) goes asymptotically to 0 for a finite temperature T2. The coincidence between T2 and the temperature above which discontinuous precipitation is no longer present suggests that P~.c,FC,l has become so small (impossibility of pinning by allotriomorphs) that nucleation of discontinuous precipitation becomes virtually impossible. The disappearance of discontinuous precipitation at high temperatures could thus result from its inability to initiate rather than from its inability to propagate, as had been previously proposed [18]. 6. EXTENSION OF THE FEATURES ENCOUNTERED IN Mg-AI TO OTHER SYSTEMS WHERE DISCONTINUOUS PRECIPITATION OCCURS The variation of the discontinuous precipitation nucleation rate with the initial grain size and solute content in Mg-A1 shows that in this system, Fournelle and Clark's mechanism is the only operating system at high temperatures whereas at low temperatures, another mechanism is also active. According to Baumann et al., this result should apply in every system that exhibits discontinuous precipitation [6]. The calculations carried out in Section 4.2 are expected to be valid in any such system, and provide a theoretical justification to Baumann et al.'s assumption. Table 2 gives for each initiation mechanism the dependence of the nucleation rate on the initial driving energy when T is fixed: as the mobility of the boundary is the same for each mechanism, we just have to compare the activation energies in equations (5), (7) and (9). Tu and Turnbull's mechanism has the highest dependence on T, since it is related to a precipitation event. Then comes Purdy and Lange's mechanism (chemical driving force without precipitation) and then Fournelle and Clark's one (capillarity forces). The expected variation with T of the

ITT i"PL", i
1

I1 2

\\

"-.

Fig. 5. Variation of l~/M--where M is the grain boundary mobility--with temperature for the different initiation mechanisms of discontinuous precipitation. Tu and Turnbull's, Purdy and Lange's, and Fournelle and Clark's mechanisms dominate in zones 1, 2 and 3 respectively. corresponding three nucleation rates normalized by the mobility is shown in Fig. 5. At high temperature, Fournelle and Clark's mechanism dominates whereas, at low temperatures, Tu and Turnbull's mechanism dominates. Purdy and Lange's mechanism may have a significant contribution in an intermediate range of temperatures. It has also been proposed that the decrease in the relative amount of double seam nodules as T increases is a general feature. Our present results in Mg-Al, together with Gust et al.'s investigations on several systems tend to confirm this assumption. At low temperatures, this result can probably be interpreted in all systems as the result of the transition from Tu and Turnhull to Fournelle and Clark's mechanism [6]. However, in order to understand why N2/NI still decreases as Tincreases when only the latter mechanism operates, other arguments have to be taken into account. The analysis performed for the Mg-AI system relies on two characteristics: positive solute segregation and necessity of pinning by allotriomorphs. The necessity of pinning by allotriomorphs is general when nucleation is dominated by Fournelle and Clark's mechanism. Therefore, at high temperatures, N 2 / N t should ultimately decrease towards 0 in all systems. This assumption is supported by Gust et al.'s results on Cu-In, Cu-Sb, Ni-In and Ni-Sn [9]. At the opposite, the solute segregation depends on the system. The four systems studied by Gust et al. are expected to exhibit a negative solute segregation (from Miedema's model), and for all of them, the curve N:/NI vs T always exhibits a more or less well defined plateau (note too that the ratio T~/2/T~ is equal to 0.77 in all these systems, whereas it is only equal to 0.63 in Mg-A1). The analysis carried out in Section 5.2 would even predict the possibility of a non monotonous behaviour due to this counter effect of segregation. 7. CONCLUSION From the measurement of the nucleation rate of discontinuous precipitation as a function of initial

DULY and BRECHET:

DISCONTINUOUS PRECIPITATION IN Mg-A1

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grain size, solute content and temperature and from optical microscope observations, we have been able to underline important features of the nucleation of discontinuous precipitation in Mg-AI alloys: (i) Relative importance of the various nucleation mechanisms: Tu and Turnbull's, and Fournelle and Clark's mechanisms respectively dominate at low and high temperatures. Purdy and Lange's mechanism may be important at intermediate temperatures. (ii) Morphological features associated with the nucleation mechanism: with increasing temperature, the relative frequency of double seam nodules is declining, even when Fournelle and Clark's mechanism is the d o m i n a n t one. (iii) Disappearance of discontinuous precipitation at high temperatures: it coincides with the asymptotic cancelling of the fraction of double seam nodules. F r o m the existing data in the literature on other systems, it seems that those conclusions may be quite general. However, depending on the nature of solute segregation at the grain boundaries, the decrease in frequency of the double seam morphology may be more or less pronounced. The method that we have used (determination of the influence of the grain size and initial solute content on the macroscopic kinetics and morphology analysis) allows us to identify the d o m i n a n t nucleation mechanism for a given concentration and a given temperature. It also gives a simple way to determine the temperature above which discontinuous precipitation does not occur and would therefore help to draw maps for continuous versus discontinuous precipitation in an initial solute content vs temperature plane.

Acknowledgements--D. Duly wishes to thank Pechiney, Centre de Recherches de Voreppe for providing financial support. The authors also want to thank Dr J. P. Simon and Pr. G. Purdy for enlightening discussion, and M. Gharghouri for careful reading of the paper.
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