Provisional A1-Be(continued)

AI-Be
Al-Zn
2092-2094 (1971) in Russian; TR: Russ. J. Phys. Chem., 45(8), 81BAP: "Melting Points of the Elements (IPTS-68)", Bull. Alloy
1186-1187 (1971). (Thermo, Equi Diagram) Phase Diagrams, 2(1), 145-146 (1981).
76Mye: S. M. Myers and J. E. Smugeresky, "Phase Equilibria and *81Cer: S. Ceresara, "Determination of the Miscibility Gap in the
Diffusion in the Be-A1-Fe System Using High-Energy Ion A1-Be System by Resistivity Measurements and X-Ray Small-
Beams", Met. Trans., 7A, 795-802 (1976). (Equi Diagram) Angle Scattering", Philos. Mag., 43A, 1093-1101 (1981). (Equi
76Pet: J. Petersen, "Superconducting Transition Temperatures of Diagram, Meta Phases)
Amorphous Binary Alloy Systems Based on Bi, Pb, Ga and Be", 82G1o: R.E. Glover, III, private communication (1982). (Meta
Z. Phys., B24, 273-278 (1976). (Meta Phases) Phases)
80Ell: R.P. Elliott and F.A. Shunk, "Evaluation of the A1-Be
(Aluminum-Beryllium) System", Bull. Alloy Phase Diagrams, *Indicates key paper.
1(1), 49-50 (1980). (Equi Diagram; Review)
AI-Beevaluation contributed by J. L. Murray and D. J. Kahan, Center for Materials Science, National Bureau of Standards. This work was jointly funded
by the Defense AdvancedResearch Project Agency(DARPA)and the National Bureau of Standards through the Metallurgy Division and through the Office
of Standard Reference Data. Literature searched through 1981. Dr. J. L. Murray and Dr. A.J. McAlister are the ASM/NBS Data Program Category Editors
for binary aluminum alloys.

The Al-Zn (Aluminum-Zinc) System

26.98154 65.38

By J. L. Murray
National Bureau of Standards

Equilibrium Diagram region s h r a n k to a very n a r r o w r a n g e n e a r 50 at.%. In

The single-phase fcc (AI) solid solution h a s an extended
composition range, i n t e r r u p t e d by a miscibility gap. The
(A1) solid solution will s o m e t i m e s be denoted a or a ' to
d i s t i n g u i s h b e t w e e n A1- a n d Zn-rich compositions, re-
spectively. The (A1) liquidus and solidus descend to a eu-
tectic e q u i l i b r i u m with cph (Zn) at 381 ~ and at 277 ~ a
eutectoid (monotectoid) e q u i l i b r i u m of a, a', a n d (Zn) oc-
curs. N e a r equiatomic compositions, the (A1) solidus curve
has an inflection caused by the n e a r n e s s of t h e fcc mis-
cibility gap. The t h r e e - p h a s e e q u i l i b r i a and pure m e t a l
t r a n s f o r m a t i o n s t h a t define t h e topology of the d i a g r a m
are s u m m a r i z e d in Table 1.
The liquidus, solidus, a n d solvus curves a r e well estab-
lished. The most recent e v a l u a t i o n of the phase d i a g r a m
[Elliott] r e p r e s e n t s ( a ' A l ) as s e p a r a t e d into two distinct fcc
phases, separated by a narrow two-phase region at
50 at.%. This two-phase region intersects t h e solidus at
443 ~ and the (aAl) m i s c i b i l i t y gap at 340 ~ The p r e s e n t
assessed d i a g r a m does not include these r e a c t i o n s and dif-
fers only s l i g h t l y from t h e e a r l i e r version of [Hansen]. The
m e t a s t a b l e miscibility g a p for the s e p a r a t i o n of coherent
precipitates from s u p e r s a t u r a t e d (A1) is established.
E a r l y investigators (1897 to 1911) believed t h a t t h e r e ex-
isted an i n t e r m e t a l l i c compound A1Zn2, based on t h e r m a l
analysis work (proposed peritectic a r r e s t s at 443 ~ Lat-
er studies identified the second phase as an fcc solid solu-
tion. W i t h t i m e (1922 to 1935), the two-phase (a + a')
1938, t h e h i g h - t e m p e r a t u r e p a r t of the two-phase region
disappeared, l e a v i n g a monotectoid reaction. By m e a n s of
h i g h - t e m p e r a t u r e lattice p a r a m e t e r and r e s i s t i v i t y mea-
surements, a smooth m i s c i b i l i t y g a p was defined, with a
critical t e m p e r a t u r e of 351 ~ [Hansen].
In 1961 and 1963, the o b s e r v a t i o n of a n o m a l i e s in high-
t e m p e r a t u r e lattice p a r a m e t e r s led to the r e i n s t a t e m e n t of
a very n a r r o w two-phase region (a + a ' ) at 50 at.%, and a
d i a g r a m a l m o s t identical to t h a t of [24Tan]. A c c u r a t e defi-
nition of the two-phase region was not p u r s u e d further.
Such a r e c a n t a t i o n leaves one w i t h several difficulties.
The intersection of the two-phase region with the solidus
was p u t b a c k at 443 ~ and the evidence a g a i n s t such a
t h r e e - p h a s e e q u i l i b r i u m is strong. The two-phase region
cannot be reconciled w i t h previous d e t e r m i n a t i o n s of the
miscibility gap. Finally, t h e proposed two-phase region
s e p a r a t e s two s t r u c t u r a l l y i d e n t i c a l fcc solid s o l u t i o n
phases of n e a r l y equal compositions, and this is t h e r m o -
d y n a m i c a l l y implausible.
The Liquidus. A l u m i n u m m e l t s a t 660.45 ~ and Zn at
419.6 ~ [81BAP]. The p h a s e d i a g r a m is of the eutectic
type; t h e e u t e c t i c t e m p e r a t u r e a n d c o m p o s i t i o n a r e
381 -+ 1 ~ and 88.7 + 0.2 at.% Zn. Reported eutectic tem-
p e r a t u r e s r a n g e f r o m 380.5 ~ [ 1 8 9 7 H e y ] to 382 ~
[39Mor]; r e p o r t e d eutectic compositions r a n g e from 88.5 to
89.5 at.% Zn. Tables 2, 3, a n d 4 s u m m a r i z e e x p e r i m e n t a l
d e t e r m i n a t i o n s of the eutectic point and liquidus.

Table I Special Points in the Al-Zn Phase Diagram

Compositions,
Phases at.~ Zn Temperature, ~ Type
L ~ (a'A1) + (Zn) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88.7 67.0 97.2 381 Eutectic
(a'A1) ~ (aA1) + (Zn) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59 16.5 98.4 277 Eutectoid
(A1) ~ (aA1) + (a'A1) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39.5 351.5 Critical
L ~ (A1) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0 660.452 Congruent
L ~ (Zn) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100 419.58 Congruent

B u l l e t i n of Alloy P h a s e D i a g r a m s Vol. 4 No. 1 1983 55

Al-Zn Provisional

Table 2 Experimental Determinations Table 3 (continued)

of the Eutectic Temperature Composition, Temperature,
Reference at.% Zn ~ Method
Temperature, Composition,
Reference ~ at.% Zn Method [1897Hey] . . . . . 0 654.5 Thermal analysis,
[1897Hey] . . . . . 380.5 89.5 Thermal analysis 1.44 648.7 cooling, Zn added
(cooling) 2.5 644.9 to A1
[llRosl, 5.33 634.4
llRos2] . . . . . 375 88.7 Thermal analysis 8.44 623.2
(cooling) 12.24 613
[24Isi, 26Isi]... 380 88.7 Electrical resistivity 15.73 598.7
[24Tan] . . . . . . . 380 88.7 Electrical resistivity, 28.54 560.2
thermal analysis 32.46 548.5
[37Bro] . . . . . . . . 382.5 ... Mean, heating and 34.84 542.2
cooling 39.27 530.8
[38Gay] . . . . . . . 381 ". Cooling curves 44.31 518.2 A1 added to Zn
[39Mor] . . . . . . . 382 -90 Heating and cooling 48.66 508.4
[43Pel] . . . . . . . . 380 88.7 Thermal analysis, 55.29 492.6
specific volume 64 466.1
70.86 447.3
79.36 418.4
83.33 380.9
87.72 380.6
Table 3 Experimental Data on the AI-Zn Liquidus [24Tan] . . . . . . 15.2 609 Electrical resistivity,
21.6 585 heating and
Composition, Temperature,
Reference at.% Zn ~ Method 29.2 564 cooling
33.5 549
[38Gay] . . . . . . 29.2 565 Thermal analysis, 38.2 533
46.7 516 cooling 43.5 525
49.1 511 47.9 513
51.5 504 50.6 508
59.4 483 55.3{b) 504
62.3 474 59.0 481
68.4 455 62.4 473
71.7 445 63.9 469
77.0(a) 433 65.0 462
82.6 409 70.1 445
86.6 390 78.8(b) 430
[43Pel] . . . . . . . 29.2 560 Specific volume [24Isi] . . . . . . . . . 4.4(b) 645 Electrical resistivity,
33.5 550 9.4 620 mean of heating
49.1 515 15.0(b) 595 and cooling curves
54 500 21.6{b) 580
62.3 475 29.2(b) 565
70 450 38.1 540
73.4 440 49.1(b) 515
79.4 420 55.3{b) 495
82.6 410 62.3(b) 475
84 400 70.1(b) 455
86.8 390 71.5 443
88.7 380 73.2(b) 440
[45But] . . . . . . . . 1.7 653.5 Thermal analysis, 75 432
3.5 646.7 cooling 78.8(b) 422
7.8 632 84.4 402
20.2 592 88.5 378
35.2 549.8
53.9 500.2 (a) Heating, not used. (b) Not used.
67.2 459.5
80.2 421.1
[49Pel] . . . . . . . 15 603 Thermal analysis,
21.6 583 cooling The A1 branch of t h e liquidus (Fig. 1) is based on a com-
29.2 561 posite of the data of [45But, 38Gay, 1897Hey, 24Isi, 24Tan,
38.2 535 49Pel, 49Sol]. All of t h e chosen data lie w i t h i n 5 ~ of the
49.1 504 liquidus curve of Fig. 1. For Al-rich alloys, [45But] data
[49Sol] . . . . . . . . 4.3 640 Thermal analysis, ar e p r ef er r ed o v e r lower liquidus t e m p e r a t u r e s . F r o m
9.6 622 cooling, various [38Gay], the cooling curves were chosen; differences of up
15.5 603 rates to 7 ~ occurred b e t w e e n h e a t i n g and cooling curves. F r o m
21.4 584
[24Isi], averages of h e a t i n g and cooling curves were chosen
29.2 560
38.2 534 because of the g r e a t e r discrepancy b e t w e e n h e a t i n g and
49.5 504 cooling, and several points were rejected because discrep-
62 473 ancies were too h i g h (10 ~ Two a n o m a l o u s l y high melt-
78.2 415 i n g points from [24Tan] were not used. D a t a of [1897Hey]
lie consistently below the liquidus b e t w e e n 0 and 50 at.%
(a) Heating, not used. (b) Not used.
Zn, and above it b e t w e e n 50 and 100 at.% Zn; this is attrib-

56 B u l l e t i n of Alloy P h a s e D i a g r a m s Vol. 4 No. 1 1983

 Provisional Al-Zn

Fig. 1 Evaluated Al-Zn Phase Diagram

Weight Percent Zinc
800.
~o
.......
eo 3o
~,.,.J,,,,~
40
......
5o
I
6o
..i ........
To ,~
Jj . . . . . . . . . . . . . . . . . . . . . . . . . . .
, ~,r ......... r .........
1~o
;pHns[mnpl

701)-
$80.452~

c~
0 500-

400-
381oc 419"6~
~ ~ O C ' 3 5 L 5 ~ B8.7~972.
300-

16.5 59.0 98.4

ioo:
(zn)

...... i ......... i ......... i ......... r ......... i ......... i ......... i ......... i ......... i ......... 1
10 20 30 4-0 50 60 70 80 90 100
A1 Atomic Percent Zinc Zn
J.L. Murray, 1983.

uted to the use of two sets of alloys (Zn added to A1, and A1 Table 4 Experimental Data on the
to Zn). Data of [38Gay] and [43Pet] lie consistently above Al-Zn Liquidus L/((Zn) + L)
the others. Data of [49Pel] and [49Sol] lie consistently
below the others, but agree remarkably with each other Composition, Temperature,
Reference at.% Zn ~ Method
( - 1 ~ [49Sol] took particular care in the chemical analy-
sis of alloys, temperature measurements, and choice of an [1897Hey] . . . . . . 92.59 392.2 Thermal analysis,
optimal cooling rate. 95.24 401.4 cooling, A1 added to
97.09 407.7 Zn
98.04 410.4
[05She, 10Ewe, l l R o s l , 11Ros2, 22San] are considered 99.01 414.5
obsolete or do not present tabulated data. [22Han] and 100 418.6
[43ButJ were superseded by later work by the same au- [24Isi] . . . . . . . . . . 92.8 395 Electrical resistivity
thors. [39Mor] and [49Gebl, 49Geb2] appear to be careful 95.1 400
work, but data could not be read from the published graphs [38Gay] . . . . . . . . 90.8 386 Thermal analysis,
with sufficient accuracy for meaningful comparison with cooling
other data. [37Bro, 50Lya, 73Nay] have large errors be- [43Pel] . . . . . . . . . 96.4 410 Specific volume
cause less attention was paid to cooling rate. 93.3 400
90.8 390
Data on the Zn-rich liquidus were reported by [1897Hey, 88.7 380
[24Tan] . . . . . . . . 97.2 415 Electrical resistivity,
24Isi, 24Tan, 43Pel]. [24Tan] showed liquidus tempera- 93.6 410 heating and cooling
tures that are high and thermodynamically ruled out by 88.7 385 (not used)
the known heat of fusion of Zn. The liquidus is based on a
composite of the other work. Data of [43Pel] lie about 3 ~
above the evaluated curve; other data lie 1 to 3 ~ below given by [llRosl, llRos2, 24Tan, 34Owe, 35Owe, 37Bro,
the curve. 39Gue, 43Pe], 47Pet], and they are considered obsolete.
Large composition changes ( - 3 5 at.%) occur in the solid
The (AI) solidus is the least accurately known phase over a narrow temperature range during solidification.
boundary of the system. It intersects the eutectic horizon- [78Cial, 78Cia2, 80Duk] showed that alloys in the com-
tal (381 ~ at 67 - 1 at.% Zn. The solidus (Fig. 1) is based position range 30 to 50 at.% (especially 38.2 at.% Zn) are
on careful microscopic studies of [22Han, 38Gay, 45But, particularly resistant to homogenization treatments. Seg-
49Gebl, 49Geb2, 39Mor] and on high-temperature X-ray regation causes low incipient melting temperatures in
work of [51Ell]. The data of [24Isi] are also shown in Al-rich alloys and the nonequilibrium extension of the
Fig. 2 and tabulated (Table 5), but not used to determine eutectic arrests to Al-enriched compositions. For this rea-
the phase boundary. Even the most accurate data show son, early work showed very low solidus temperatures (up
considerable scatter, deviating from the assessed phase to 50 ~ too low in the earliest work, and 20 ~ discrepan-
boundary by up to 10 ~ Additional solidus data were cies among later determinations, e.g., [72Veil).

Bulletin of Alloy Phase Diagrams Vol. 4 No. 1 1983 57

Al-Zn Provisional

Fig. 2 Comparison of Evaluated Diagram to the Experimental Data

Wcight Pcrccht Zillc
zo ZO 70 4o 50 60 7o 8O 9O LOO
800 ,,,i ..... ~ .... + ,+' ........ Lr . . . . . . . . i r [ . . . . . : [ . . . . . . . i i ii . . . . . . . I ....... :'J . . . . . . . . J ......

p~n3Kmnn

700

600-

500

400-

O~ 300
E-,

200 "

100 -

0
10 20 30 40 50 60 70 80 90 100

A1 Atomic Percent Zinc Zn

J.L. Murray, ~983.

Between 440 and 447 ~ [11Ros1, 11Ros2, 22Han, 24Isi, were determined by high-temperature resistivity mea-
24Tan] found a series of thermal arrests, which they at- surements; the third, an average of two determinations
tributed to a peritectic reaction, L + (A1) --* compound by TEM and DTA methods.
(a'). [38Gay, 39Mor, 40Mor] demonstrated that the ther-
Early observations of two-phase (a + a') alloys above the
mal effect is the result of segregation. Even when the effect
critical point include [22Han] (metallography), [24Tan]
of segregation was recognized, a peritectic reaction was
(resistivity, t h e r m a l expansion), and [35Owe] (high-
considered to be a likely explanation of the inflection in
temperature X-ray). [22Han] and [24Tan] published dia-
the solidus between 40 and 50 at.% Zn. (The inflection,
grams r e m a r k a b l y similar to [Elliott's], with inverted
however, can be understood as an effect of the miscibility
funnel-shaped two-phase regions meeting the solidus at
gap in the solid.) The peritectic reaction still enjoys a
50 at.% Zn. [38Gay] found metallographic indications in a
following [60Pre, 61Pre, 63Gol, 73Nay]; in this evaluation,
49 at.% Zn alloy that it had been two-phase immediately
the narrow two-phase field extending to the solidus is
not accepted. prior to melting, but rejected this as an indication of the
equilibrium relations because of the careful work on the
The fcc Miscibility Gap. The miscibility gap is based on solidus, indicating that apparent peritectic arrests were
data of[74Sim] and [56Mue, 60Mue]; other data that agree due to segregation.
within 1 to 2 at.% are [36Fin, 40Ell, 51Ell, 48Bor, 67Lar]. [38Gay] and [39Mor] examined quenched specimens:
The critical point lies at 351.4 ~ and 39.5 -+ 0.2 at.% Zn [38 Gay] by etching at high temperature, [39Mor] by using
[56Mue, 60Mue]. The eutectoid temperature [74Sire] is small additions of Mg to prevent decomposition. The ob-
277 -+ 0.5 ~ The compositions of a and a ' at the eutectoid served critical points were 370 ~ [39Mor] and 360 ~
are 16.5 -+ 0.5 and 59 -+ 1 at.% Zn (based on composites of [38GayS. More accurate work is based o n X-ray or elec-
the data). The equilibrium of three fcc phases at 340 ~ trical resistivity measurements [48Bor, 56Mue, 36Fin,
proposed by [61Pre, 63Gol] is not accepted. 35Owe, 67Lar, 74Sim, 67Ger] (see Table 7). Measured crit-
ical points range between 350 ~ [36Fin] and 358 ~
First estimates of the eutectoid temperature were aver-
[67Lar]. Except in the range 45 to 52 at.% Zn, the various
ages of thermal or resistivity arrests on heating and cool-
measurements form a smooth curve with a scatter of
ing [24Tan, 24Nis, 34Sch, 35Ful, 24Isi, 35Owe, 36Aue]
+-1 at.%. The observed compositions at the eutectoid
and ranged between 270 -+ 5 and 278 ~ (see Table 6).
temperature range between 15 and 16.6 at.% Zn on the A1
Undercooling is common, and in work based only on cool-
side and between 59.4 and 60 at.% Zn on the Zn side.
ing curves the eutectoid is reported as n e a r 256 ~
[llRosl, llRos2, 26Tiel, 26Tie2; 73Nay, 236 ~ (sic)]. [36Fin] and [56Mue] did the most careful resistivity work
[35Ful] observed t h a t because the transformation on and found the miscibility gap to be a smooth curve without
heating is independent of heating rate, the transforma- any effect corresponding to a two-phase (a' + a") region
tion temperature on heating (277.7 ~ should be used. near 50 at.% Zn and above 351 ~ [56Mue] used 29 alloys
Other reported values are 275 ~ [36Fin], 278 ~ [48Bor, with 3 compositions near 50 at.%. [56Mue] found anoma-
51Bor, 67Lar], and 277 -+ 0.5 ~ [74Sim]: the first two lies in the resistivity/temperature curves of several alloys

58 Bulletin Of Alloy Phase Diagrams Vol. 4 No. 1 1983

 Provisional AI-Zn

Table 5 Experimental Data on the AI-Zn Solidus Table 6 Experimental Determinations

Composition, Temperature, of the Eutectoid Point
Re~rence at.% Zn ~ Method Eutectoid
[49Geb] . . . . . . . 62.3 410 Microscopic Reference temperature, ~ Method
55.3 438 [llRosl, 11Ros2],
49.1 445 [22Hem] . . . . . . . . . . . 256 Microscopic methods
43.4 452 [22Han], [24Tan]. . . . . 270
38.2 460 [24Nis] . . . . . . . . . . . . . . 256 . , ,

29.2 484 [24Isi] . . . . . . . . . . . . . . . 280 Electrical resistivity

21.6 508 [34Owe] . . . . . . . . . . . . . 300-310 High-temperature X-ray
15.0 540 [34Sch] . . . . . . . . . . . . . . 270 High-temperature X-ray
9.4 572 [35Ful] . . . . . . . . . . . . . . 277.7 Thermal analysis,
4.4 632 heating, cooling
[49Pel] . . . . . . . . 14.7 537 '" [35Owe] . . . . . . . . . . . . . 272 High-temperature X-ray
20.2 508 [36Aue] . . . . . . . . . . . . . 270 Magnetic susceptibility
27.2 483 [36Fin] . . . . . . . . . . . . . . 275 Electrical resistivity
34.3 460 [37Bro] . . . . . . . . . . . . . . 255 Thermal analysis,
46.7 437 cooling
[38Gay] . . . . . . . 26.6 483 Metallography 285 Thermal analysis,
31.2 467 heating
36.0 459 [48Bor, 67Lar] . . . . . . . 278 Electrical resistivity
40.0 454 [73Nay] . . . . . . . . . . . . . 236 (sic) Quantitative thermal
40.6 452 analysis
43 448 [74Sim] . . . . . . . . . . . . . 276.5 -+ 0.5 TEM
53.0 436 277.5 -+ 0.5 DTA
55.1 431 [75Koj] . . . . . . . . . . . . . . 275 Positron annihilation
[39Mor] . . . . . . . 62.5 410 Microscopic, [75Ter] . . . . . . . . . . . . . . 270 SAXS, cooling,
55 440 data read ~omgraph 0.01 ~
52.5 440
[45But] . . . . . . . . 3.4 628 Metallography
8.2 590
13.6 550 In order to evaluate the claims of [61Pre] and [63Gol] t h a t
[51Ell] . . . . . . . . 16.5 520 High-temperature h i g h - t e m p e r a t u r e lattice p a r a m e t e r data showed t h a t a
20 500 X-ray very n a r r o w two-phase region exists at constant composi-
25.8 480 tion above To, h i g h - t e m p e r a t u r e lattice p a r a m e t e r s are
37.5 460 graphically compared (see ~'Crystal Structures and Lattice
51 440 Parameters"). At 360 ~ there is a n u n e x p l a i n e d a n o m a l y
60 420
in the l a t t i c e p a r a m e t e r s a t a b o u t 40 at.% Zn. N e a r
64.6 400
[24Isi] . . . . . . . . . 2.2 635 50 at.%, the slight deviations of the lattice p a r a m e t e r data
4.4 615 Electrical resistivity, of [63Gol] or [63Pre] from a s t r a i g h t line are smaller t h a n
6.7 590 dilatometry, the differences between lattice p a r a m e t e r s of the various
9.3 565 diverges 10-15 ~ studies. A l t h o u g h lattice p a r a m e t e r s can be m e a s u r e d
12 550 ~om highest values very accurately, errors i n composition and t e m p e r a t u r e
18.1 510 also contribute to the error in lattice parameters. Slight
21.5 490 anomalies i n the lattice p a r a m e t e r versus composition
22.9 480 curve at t e m p e r a t u r e s above the critical point do not ap-
25.2 475
50.2 440 pear to be sufficient evidence to establish a narrow two-
52.6 425 phase region in the fcc phase.
54 420
56.5 415 T h e S o l u b i l i t y o f Zn in (AI) increases from 2.2 at.% at 110 ~
47.9 410 to 16.5 at.% at the eutectoid t e m p e r a t u r e . Above 277 ~
59.4 405 the solvus curve lies on the Zn-rich side of the fcc mis-
61.5 400 c i b i l i t y g a p ; t h e s o l u b i l i t y i n c r e a s e s f r o m 59 -+
62.1 395 1 at.% Zn at 277 ~ to 67 -+ 1 at.% Zn at the eutectic
63.8 390 temperature.
65.3 385
[22Han] . . . . . . . 4.4 570 "'" On the Al-rich side, early d e t e r m i n a t i o n s significantly
21.6 496 overestimated the solubility of Zn i n (A1) a n d will not be
37.6 457 considered here [22San, 24Nis, 24Isi, 26Isi, 16Bau, 32Fin].
43 453 Data of [74Sim2, 67Lar, 32Sch, 34Sch, 36Fin] are given in
50 446 Table 8. The solvus is based p r i m a r i l y on [74Sim2], and the
54 432 data of [36Fin] and [67Lar] agree w i t h i n +0.5 at.%. The
60.8 407
63.8 395 solvus reported by [32Sch] is c o n s i s t e n t l y displaced to
66.1 382 lower Zn content over the entire t e m p e r a t u r e range.
Above 277 ~ u n c e r t a i n t i e s are greater because of the
same segregation problems t h a t lead to discrepancies i n
in the composition r a n g e 41 to 42 at.% Zn; they a t t r i b u t e d the solidus. Resistivity data for the a ' / ( a ' + (Zn)) bound-
these anomalies to improper sample p r e p a r a t i o n a n d used ary are consistent [24Tan, 36Fin, 48Bor, 51Bor, 67Lar].
smooth data to d e t e r m i n e the phase diagram. D a t a of [24Tan, 3 6 F i n , 48Bor] are c o n s i s t e n t w i t h a

Bulletin of Alloy Phase D i a g r a m s Vol. 4 No. 1 1983 59

 Al-Zn Provisional

s t r a i g h t l i n e f r o m 59 to 66.5 a t . % Zn. T h e d a t a o f [ 6 7 L a r ] p e r a t u r e , d e c r e a s i n g to 1.6 a t . % (98.4 a t . % Zn) a t 277 ~

show more scatter, but are not inconsistent with the s a m e a n d 0.07 (99.93 a t . % Zn) a t 20 ~ S e e T a b l e 9 for t h e ex-
p h a s e b o u n d a r y . F i g u r e 1 is b a s e d on t h e r e s i s t i v i t y d a t a perimental data [23Pie, 36Bur, 36Ful, 36Aue, 40Loe,
o f [ 3 6 F i n , 48Bor, 51Bor, 6 7 L a r ] . 50Hof, 52Pas]. T h e m a x i m u m d i s c r e p a n c y i n t h e s o l u b i l i t y
a t 370 ~ a m o n g t h e v a r i o u s d e t e r m i n a t i o n s is 0.7 at.%.
Solubility of At in (Zn). T h e m a x i m u m s o l u b i l i t y o f A1 i n T h e d a t a of [ 3 6 A u e , 40Loe, 50Hof] c a n b e u s e d to d e f i n e
(Zn) is 2.8 -+ 0.2 a t . % (97.2 a t . % Zn) a t t h e e u t e c t i c t e m - a n A r r h e n i u s p l o t o f ln(x) v s 1 / T o v e r t h e e n t i r e t e m p e r a -
t u r e r a n g e f r o m 150 to 370 ~ T h e a s s e s s e d s o l u b i l i t i e s
Table 7 Experimental Data on a r e e x t r a p o l a t i o n s b a s e d on t h e s t r a i g h t l i n e fit t h r o u g h
their data.
the a Miscibility Gap
Compositions, Temper- Metastable Phases
at.% Zn ature,
Reference a~Al.rich) a'(Zn-rich) ~ Method Decomposition of the Supersaturated (AI) Solid Solution.
T h e s u p e r s a t u r a t e d fcc (A1) solid s o l u t i o n c a n b e r e t a i n e d
[24Isi] . . . . . . . 18.1 9.. 28O Electrical
9.. 300 resistivity at t e m p e r a t u r e s below the e q u i l i b r i u m solvus. Decom-
20.8
21.5 3O5 p o s i t i o n o f t h e solid s o l u t i o n g i v e s r i s e t o a s e r i e s of m e t a -
22.3 310 stable structures: spherical and ellipsoidal Guinier-Preston
25.2 330 (GP) zones, p l a t e l e t s of c o h e r e n t fcc p r e c i p i t a t e s t h a t u n -
26.7 345 d e r g o a r h o m b o h e d r a l d i s t o r t i o n , a n d i n c o h e r e n t (a'A1).
[24Tan] . . . . . 15.2 . .
282 The sequence of s t r u c t u r e s observed d u r i n g aging d e p e n d s
21.6 . .
305 on the homogenization temperature, quenching rate
29.2 . .
329 [ 7 7 S i m l ] , Zn c o n t e n t [80Acu], a n d q u e n c h i n g p r o c e d u r e ;
33.5 . ~
334
s u c h e f f e c t s a r e b e y o n d t h e scope of t h i s r e v i e w . W e a r e
38.2 341
43.5 369 c o n c e r n e d w i t h t h e m e t a s t a b l e p h a s e e q u i l i b r i a : (a) t h e
47.9 ~
387 m e t a s t a b l e e x t e n s i o n s of the e q u i l i b r i u m (incoherent) mis-
50.6 390 c i b i l i t y gap, (b) t h e m e t a s t a b l e m i s c i b i l i t y g a p g o v e r n i n g
55.3 312
. . .
59 287 Table 8 Experimental Data on the (AI) Solvus,
[36Fin] . . . . . . 29.6 9-- 340 Electrical a in Equilibrium with (Zn)
34.1 9.. 35O resistivity
38.5 ~ 1 7 6
353 Compositions, Temper-
43.3 351 at.% Zn ature,
Reference a(Al-rich) a'(Zn-rich) ~ Method
. ~
46.7 346
47.8 342 [24Isi] . . . . . . . 10.9 ... 60 Electrical
, . ~
48.5 341 12 o.. 160 resistivity
[48Bor] . . . . . . 15.1 9" 275 Electrical 15 "" 260
20.0 9" 307 resistivity 16.8 ... 270
25.0 . ~ 1 7 6
331 [24Tan] . . . . . "" 62.4 315 ""
55.0 321 63.9 351
, ~ 1 7 6
56.6 304 [48Bor] . . . . . . ." 60.8 297 Electrical
[51Ell] . . . . . . 16.7 59 28O High-temperature 9" 62.3 321 resistivity
21.7 56.3 3OO X-ray 9" 65.0 357
25 53.3 32O 9-" 65.3 362
30.5 49 340 9" 66.0 374
[56Mue] . . . . . 27.2 9.- 329 Electrical 5.0 ... 195
32.1 9.. 342 resistivity 8.1 ... 240.5
43.3 347 12.0 ... 264
. , .
47.8 337 15.1 ... 275
. . .
52.3 317 [36Fin] . . . . . . .." 60.3 293 Electrical
[67Lar] . . . . . . 15.1 9.. 275 Electrical 9" 61.6 312 resistivity
2O 9" 316 resistivity 9" 62.9 330
27.5 353 9" 64.6 350
32.5 . ~
349 2.4 -.. 125
37.5 352 3.0 --- 150
4O ~
351 4.1 -.- 175
42 354 5.5 ... 200
43.4 ~ 1 7 6 1 7 6
355 7.3 ... 225
45 ~
358 10.6 ... 250
50 349 16.0 ... 275
~ 1 7 6
51 35O [51Ell] . . . . . . ... 60 280 High-temperature
54 323 9" 61.6 300 X-ray
, ~ 1 7 6
56.6 307 9" 62.7 320
59.4 28O 9" 64.0 340
[74Sim2] . . . . . 9.6 9" 210 TEM, X-ray 9" 65.3 360
12.3 9.. 242 diffraction [74Sim2] . . . . . 2.2 --. 110 TEM, X-ray
15.4 . . ~
268 4.4 ... 195
19.0 290 6.8 ... 227
22.4 . ~ 1 7 6
3O8 8.9 ... 246
29.8 . . .
333 12.3 ... 261
[75Ter] . . . . . . 39.2 9"" 352 SAXS, cooling 15.4 ... 273

60 Bulletin of Alloy P h a s e D i a g r a m s Vol. 4 No. 1 1983

Provisional Al-Zn

Table 9 Experimental Data on the (Zn) Solvus particle (or plate) is less than that for the sphere and
governs a distinct coherent miscibility gap.
Composition, (Zn) Temperature,
Reference at.% Zn (at.%AI) ~ Method
The first structure to form at low temperatures in super-
[23Pie] . . . . . . 98.6 (1.4) 230 Electrical saturated (A1) is the spherical GP zone. [66Bon] aged alloys
98 (2.0) 335 resistivity at - 4 5 ~ and measured the growth of spherical GP zones
[36Aue] . . . . . 99.5 (0.5) 140 Magnetic (SAXS) from 2 to 3.4 nm in radius. At 20 ~ the spherical
99.3 (0.7) 170 susceptibility particles grow to a critical radius, when the strain fields
98.8 (1.2) 230
98.4 (1.6) 270 change symmetry to rhombohedral and the particles are
98.1 (1.9) 305 distorted to oblate ellipsoids [66Mer, 77Fum]. [65Mer,
97.4 (2.6) 370 66Mer] measured a radius of 3.0 to 3.5 nm as the maxi-
[24Isi] . . . . . . . 99.3 (0.7) 25 Electrical mum size of undistorted spherical particles. Later work
resistivity [77Lasl, 78Aga, 78Loe, 79Fab, 82Hen] indicated that the
[36Bur] . . . . . 98.1 (1.9) 300 Lattice parameters transition to ellipsoidal zones occurs sooner, between 1.5
99.9 (0.1) 25 and 2.0 nm.
[36Ful] . . . . . . 99.8 (0.2) 95 Lattice parameters
99.6 (0.4) 150 (small Mg In the ellipsoidal zones, coherency is maintained with the
99.3 (0.7) 175 additions) matrix on the (111) planes, and the distortion consists of a
99.2 (0.8) 200 compression of close-packed planes in the (111) direction.
98.1 (1.9) 375 [67Sim] (X-ray diffraction) e x a m i n e d the growth of
[40Loe]. . . . . . 98.6 1.4 250 Lattice parameters
97.1 2.9 375 particles in a 15.05 at.% Zn alloy aged at 225 ~ The co-
[50Hof]. . . . . . 99.8 (0.2) 100 Lattice parameters herency on the (111) planes is maintained, but gradually
99.5 (0.5) 150 the coherency in other directions is lost. The effect of the
99.2 (0.8) 200 partial loss of coherency is that diffusion across these in-
98.8 (1.2) 250 terfaces can take place quickly, and the ellipsoidal GP
98.3 (1.7) 300 zones can grow to large sizes (70 to 200 nm). The result is
97.9 (2.1) 350 a plate, referred to in the literature as the "partially inco-
[51Pas] . . . . . . 99.16 (0.84) 232 Electrical herent rhombohedral transition (R) phase". The elastic
resistivity energy is primarily associated with maintaining the co-
[24Tan] . . . . . 97.6 (2.4) 385
98.8 (1.2) 270 herency on the (111) planes, and very little is required to
97.8 (2.2) 25 m a i n t a i n the coherency in other directions. Thermo-
dynamically, the R phase is still "fully coherent", and the
difference between R phase and ellipsoidal GP zones is one
the precipitation of fcc particles coherent with the matrix, of size only. Eventually the coherency on the (111) planes
and (c) the coherent spinodal. is lost, and this marks the coherent-to-incoherent transi-
Some recent reviews of m e t a s t a b l e p h a s e equilibria tion. [77Fum, 79Fum, 80Fum] analyzed the internal struc-
[69Ana, 73Ana, 77Sat, 81Satl, 81Sat2] argued that the ture of ellipsoidal GP zones aged at room temperature
metastable equilibria are governed by two metastable using diffuse X-ray scattering. They found that the rhom-
miscibility gaps, a "coherent solvus for the GP zones" and bohedral distortion of the lattice in the GP zones is the
a "miscibility gap for the transition R phase". That is, the same as that observed in the plates, direct structural
GP zones and the rhombohedrally distorted platelets were evidence that the transition phase R is identical to the
considered to be two distinct phases. In our opinion, both ellipsoidal GP zone.
experimental evidence and theoretical considerations fa- At temperatures above 150 ~ the coherent precipitate
vor the view that the formation of rhombohedral platelets grows quickly, to become a coherent plate with a rhom-
is governed by the coherent solvus, and that, independent bohedral crystal structure. The coherent critical point has
of p a r t i c l e size, t h e m e t a s t a b l e p h a s e is t h e r m o - been determined by measuring coherent composition fluc-
dynamically a single phase, the fcc Zn-rich solid solution.* t u a t i o n s by n e u t r o n s m a l l - a n g l e s c a t t e r i n g [78Sch,
The coherent miscibility gap is depressed below the inco- 77Sch]. The critical composition is 40.1 -+ 0.8 at.% Zn, the
herent equilibrium gap because of the additional elastic critical temperature, 324 ~ Other determinations of the
energy required to maintain coherence with the matrix, metastable coherent solvus in this regime were made by
and this elastic energy depends upon the shape of the [64Las, 69Ard, 74Siml,74Sim3, 79Sat]. [74Siml, 74Sim3]
coherent particle. A spherical particle is undistorted by examined the formation of the coherent phase by means of
the matrix and maintains the fcc structure even in the slow cooling and aging treatments and showed that super-
stressed environment [66Mer, 68Eli]. The spherical shape cooling and superheating occur. The DTA (cooling) curves
is favored at small particle size. At a critical size, a cross- agreed with the resistivity (cooling) measurements of
over occurs to a preferred shape of oblate ellipsoid, with [64Las]. The X-ray data of [74Siml] represent the meta-
the short axis in the O l D directions. For an ellipsoidal stable equilibrium.
particle, the stress applied by the matrix distorts the fcc The determination of the coherent solvus by aging at low
lattice to a rhombohedral structure. Thermodynamically, temperatures and reheating to find the reversion tem-
the structure of the phase is that to which it relaxes in a perature of the GP zones is hindered by the complex pre-
stress-free environment, namely fcc. The designation "R cipitation kinetics in the temperature range 80 to 160 ~
phase" refers to the structure that the coherent particle Thermal, resistivity, or h a r d n e s s anomalies at tem-
assumes in the matrix, rather than the equilibrium struc- peratures much below the coherent solvus [48Bor, 51Bor,
ture. The elastic energy associated with the ellipsoidal 69Wah, 67Str, 65Ric, 66Joh, 71Wah, 80Pra] are probably
*Wealsoidentifytwo distinct miscibilitygaps, but they are associatedwith not connected with the metastable phase equilibria. Use of
spherical vs ellipsoidal precipitates. resistivity and hardness m e a s u r e m e n t s without veri-

Bulletin of Alloy Phase Diagrams Vol. 4 No. 1 1983 61

AI-Zn Provisional

Table 10 Data on the Metastable Table 10 (continued)

Coherent Miscibility Gap Composition, Temperature,
Reference at.% Zn ~ Method
Composition, Temperature,
Reference at.% Zn ~ Method [74Siml] .... 6.8 160 X-ray (metastable
[60Pan] . . . . . 4.4 94 Electrical resistivity 12.3 224 equilibrium)
(isothermal aging) 18.5 250
[64Las]. . . . . 12.2 190 Electrical resistivity 22.0 284
18.3 255 (cooling) 30.4 318
25.2 295 6.7 150 DTA
38.5 328 9.5 189
50 317 12.1 214
55 382 15.1 241
[66Bon] . . . . . 1.2 -+ 0.2 -45 SAXS 16.5 251
95.9 -+ 2 -45 18.1 264
[66Carl. . . . . . 4.5 104 Hardness reversion 19.9 272
7.9 170 [74Sim3] ...9.5 156 DTA (undercooled)
10.7 210 12.0 196
[61Ger, 14.7 223
67Ger] .... 1.7 20 SAXS, integrated 16.5 239
70.7 20 intensity 18.1 249
[68Oht] . . . . . 1.7 7 Electrical resistivity, 19.9 264
2.1 26 SAXS, formation 21.0 272
2.6 40 of zones 24.8 295
3.5 67 28.5 310
[69Ard] .... 28.4 315 -+ 2 TEM 32.7 319
39.2 337 -+ 2(a) 37.1 328
50.3 315 -+ 5 [76Jun] ... 5.3 135 Magnetic susceptibility
[69Nik] . . . . . 6.8 160 Diffuse X-ray 6.77 155
scattering 9.35 2O5
[71Mur] . . . . . 6.8 155 SAXS, electrical [7SPell . . . . . . 1.1 0 Thermoelectric power
resistivity, TEM 1.9 45
[72Ray] . . . . . 1.0 20 SAXS, integrated 3.7 100
64.1 20 intensity 4.2 120
[72Riv] . . . . . . 2.6 40 Electrical resistivity, [78Sch]..... 40.1 324 Neutron scattering,
3.5 67 isothermal aging critical point
6.8 134 (direct quench)
9.4 164 -+ 2
15.0 216 higher aging temperatures, (Zn) precipitates continuously
[72Jac] . . . . . . 4.4 97 -+ 4 TEM, reversion of from the R plates, and the incoherent a' does not appear.
8.1 164 -+ 2 ellipsoidalzones The sequences of intermediate structures in various
12.7 213 -+ 2 temperature ranges were delineated by [68Eli, 75Sim,
77Siml, 77Sim2, 78Sim].
(a) Critical point.
Additional work has been done on the decomposition pro-
cesses and their effects on physical and mechanical proper-
flcation of the structures present leads to contradictory ties. For further review and theory, see [62Fed] and
results: critical t e m p e r a t u r e s r a n g i n g from 225 ~ [73Mue]. For the effect of impurities on decomposition ki-
[73Ana, 66Joh, 80Pra] to almost 400 ~ [72Hir, 77Sat]. netics, see [70Sat, 75Bar2, 77Fla]. For further discussion
Direct methods such as X-ray diffraction or TEM [74Siml, of continuous and discontinuous decomposition processes,
74Sim3] are therefore preferred. Direct quenching from see [60Gra, 62Gra, 63Mur, 70Cia, 70Dut, 71Dob, 74Cia,
the homogenization temperature to the aging temperature 76Bar, 78Tol, 80Lui, 82Paw]. Cellular precipitation of (Zn)
also gives more consistent results than quenching and re- is discussed by [73But, 74Anal; the kinetics of the eu-
heating: [72Jac] (TEM), [71Mur, 72Riv] (resistivity). Physi- tectoid transformation are discussed by [73Smi, 74Che,
cal properties that depend only on the composition of the 77Bos]. [72Jac] reported an octahedral-shaped precipitate
matrix are also used to measure the solvus: [76Jun] (mag- (Y phase), with an fcc structure in supersaturated (A1)
netic susceptibility), [78Pel] (thermoelectric power). SAXS solutions, which had been rapidly quenched before aging.
provides compositions of both the GP zones and the matrix [79Zahl, 79Zah2] made a calorimetric study of the for-
[61Gerl, 61Ger2, 66Bon, 67Ger, 71Ray]; measurements of mation and dissolution of GP zones.
the composition of the precipitate by integrated intensity
or lattice parameter data show considerably more scatter T h e C o h e r e n t S p i n o d a l . The spinodal is the locus of com-
than Al-rich phase boundary measurements. Selected
positions and temperatures where the second composition
data are given in Table 10 and Fig. 3.
derivative of the free energy (including elastic coherency
The simple picture of continuous precipitation used to elu- contributions) changes sign. Within the spinodal, the
cidate the coherent equilibria does not fully describe the early stage of decomposition of the supersaturated solid
complex precipitation processes observed in Al-Zn. From solution is governed by growth of composition fluctua-
the early stages, (Zn) also precipitates discontinuously at tions, rather than by nucleation. [68Cah, 75Def, 81Def]
the grain boundaries [66Rao3, 70Jon]. At aging tem- reviewed the theory of spinodal decomposition with par-
peratures below 85 ~ R plates do not grow and (Zn) pre- ticular reference to Al-Zn; [81Loe] reviewed experimental
cipitates continuously from the GP zones. At somewhat data on the spinodal in A1-Zn.

62 Bulletin of Alloy Phase Diagrams Vol. 4 No. 1 1983

Provisional AI-Zn

Fig. 3 Coherent fcc Miscibility Gap and the Spinodal

Weight Percent Zinc
0 10 20 30 40 50 60 70 80 100
3 5 0 { . . . . I. . . . . I e
i polllslnlnpJ
Coherent M i s c i b i l i t y Gap

%% 64Las
"- o 72Rtv

v/ 9%
'%
z~ 78Pel
+ 89Nlk
• ~Siml (xray)

!
'~o ~sim.t(DT.A)
O
v ~.Sim3 (DTA)
OJ
200" q B 76Jun

/ 72Jac
/ 9 880hi
7 / 9 67Ger
/ z 71Mur
[--, 78Sch
B 6BArd
100-

Sp~od~
50-
/ o 73Tru
! o 77Kro

!
/ A 79C/a

0 10 2O 30 40 5O 6O 70 80 90 100
A1 Atomic Percent Zinc Zn
J.L. Murray, 1983.

[77Sch, 78Sch] (neutron scattering) probed coherent com- Table 11 Experimental Data on
position fluctuations in alloys of near-critical composition the Coherent Spinodal
(39.4 to 40.1 at.% Zn); the coherent critical temperature
was determined to be 324 ~ Away from the critical com- Composition, Temperature,
Reference at.% Zn ~ Method
position, determinations of the spinodal temperature are
made primarily by small-angle X-ray scattering (SAXS). [51Bor] . . . . . . 8 52 Electrical resistivity
The spinodal temperature is determined [68Mur, 77Kro, 15 145 (lower limit of
79Cia, 8lUng] by the relation between the critical wave- 24 290 retardation of
length of the fluctuations and the aging t e m p e r a t u r e 51 280 precipitation)
56 195
[68Cah]. [74Jun, 76Jun, 51Bor] used qualitative changes 59 110
in the kinetics of decomposition to locate the spinodal us- 65 8O
ing resistivity, magnetic susceptibility, or SAXS. The data 8(a) 37
(Table 11, Fig. 3) lie in two groups: [76Jun, 69Mur] placed 14(a) 145
the spinodal temperature for a 6.8 at.% Zn alloy within 5 [69Mur] . . . . . 6.8 125 SAXS
to 10 ~ of the coherent miscibility gap; [77Kro, 73Tru, [73Tru] . . . . . 21 -200 TEM
79Cia] placed it about 10 at.% farther within the coherent [74Jun,
miscibility gap. 76Jun] .... 2.5 32• Magnetic susceptibility
4.43 92
The kinetics of spinodal decomposition were investigated 6.8 128
by SAXS experiments [67Run, 73Aga, 78Aga, 75Barl, 9.35 166
75Lew]. [67Run] claimed that the early stage of spinodal 15 186
decomposition was observed; [67Ger] argued that models [77Kro] . . . 15 86• 5 SAXS, dilatometry,
of the early stages of decomposition were inapplicable be- 16 95_+5 microhardness
18 116 • 5
cause phase separation took place during quenching. [78Aga] . . . . 7 -50 SAXS
[73Aga, 74Acu, 75Barl, 75Lew] used liquid quenching or [78Sch] . . . . 40.1 _+ 0.8 324 Neutron small angle
additions of Mg and Sn to retard the precipitation of equi- scattering, critical
librium (Zn) and make earlier stages of decomposition ex- point
perimentally accessible. [75Barl, 75Lew] concluded that [79Cia] . . . . . 22 230 • 10 SAXS
spinodal decomposition was nearly completed during (a) Calorimetry.
quenching and that [67Ger] had been correct in attribut-
ing the [67Run] observations to the coarsening stage. appearance of the characteristic modulated *'spinodal"
The "microstructural sequence method" has not been suc- microstructure and X-ray sidebands [68Wah, 70Sat,
cessfully applied to determination of the spinodal in Al-Zn 69Doul, 69Dou2, 71Mel, 72Mel], are incomplete evidence
[82Ala, 82Vij]. Indirect probes of incubation times for pre- of spinodal decomposition [77Lasl, 81Loe]. [77Las2]
cipitation [51Bor, 76Jun, 74All, 74Nau, 75Del], or the pointed out that the famous "scattering ring" also appears

Bulletin of Alloy Phase Diagrams Vol. 4 No. 1 1983 63

AI-Zn Provisional

Table 12 Al-Zn Crystal Structure Data Table 13 (continued)

Composition Struktur- Composition, Lattice parameter a, nm
range, Pearson bericht Space Reference at.% Zn (360 ~ (340 ~ (25 ~
Phase at.% Zn symbol designation group Prototype
[63Gol] . . . . . . . . . 23.2 0.40697 . . . . . .
(A1) . . . . . 0-67 cF4 A1 Fm3m Cu 40.3 0.40537 0.40425 ...
(a'AI)R . . 6 0 -- 70 . . . . . . R 3m "" 45.5 0.40494 0.40431 -..
CR") .... (a) . . . . . . . . . . . . 46.5 0.40471 0.40430 ...
(Zn) . . . . . 97.2-100 hP2 A3 P6Jmmc Mg 48.8 0.40459 0.40433 -..
Metastable phase 49.7 0.40455 0.40429 ...
52.0 0.40419 0.40397 ...
Y ....... --. (b) (b) ... (b)
53.1 0.40408 0.40382 ...
(a) Coherent precipitate. (b) Unknown. [81Satl] ........ 4.5 . . . . . . 0.40460
8 . . . . . . 0.40432
10 . . . . . . 0.40420
12 . . . . . . 0.40398
16 . . . . . . 0.40358
20 . . . . . . 0.40320
Table 13 Lattice Parameters of (AI) 30 . . . . . . 0.40290
Composition, Lattice parameter a, nm [48Axo] . . . . . . . . 0 . . . . . . 0.404950
Reference at.% Zn (360 ~ (340 ~ (25 ~ 0.44 . . . . . . 0.40494
1.7 . . . . . . 0.40486
[35Owe] ........ 0 0.40852
2.76 . . . . . . 0.40479
4.4 0.40817
2.91 . . . . . . 0.40476
7.2 0.40812
5.44 . . . . . . 0.40454
9.4 0.40790
5.96 . . . . . . 0.40452
15 0.40760
6.72 . . . . . . 0.40442
20.7 0.40722
[50Dor] . . . . . . . . . 0 . . . . . . 0.404942
26 0.40684
0.211 . . . . . . 0.404929
30.8 0.40656
0.402 . . . . . . 0.404914
34.4 0.40622
0.755 . . . . . . 0.404887
37.5 0.40602 0.40401 ""
1.616 . . . . . . 0.404836
41.2 0.40577
[34Sch] . . . . . . . . . 2.1 . . . . . . 0.40474
48.5 0.40530 0.40403 "'"
3.1 . . . . . . 0.40465
48.5 0.40442
3.7 . . . . . . 0.40460
50.4 0.40437
4.6 . . . . . . 0.40452
53.1 0.40416 0.40390 ""
5.3 . . . . . . 0.40446
57.2 0.40395 0.40361 "'"
6.6 . . . . . . 0.40436
63.0 0.40352 0.40310 "'"
8.6 . . . . . . 0.40418
64.8 0.40329 0.40286 "'"
11.5 . . . . . . 0.40394
70.1 0.40314 0.40284 "'"
12.2 . . . . . . 0.40388
78.8 0.40314
15.1 . . . . . . 0.40364
[51Ell] ......... 0 0.40852 0.40832 "'"
19.1 . . . . . . 0.40331
5 0.40839 0.40813 "'"
27.7 . . . . . . 0.40258
9.6 0.40818 0.40795 ""
[62Hell ......... 2.24 . . . . . . 0.40480
11.75 0.40805 0.40785 "'"
4.45 . . . . . . 0.40458
13.9 0.40790 0.40770 ""
6.07 . . . . . . 0.40442
16.5 0.40769 0.40742 "'"
6.87 . . . . . . 0.40432
21.7 0.40739 0.40713 "'"
9.46 . . . . . . 0.40410
25.2 0.40716 0.40693 "'"
11.9 . . . . . . 0.40383
31.5 0.40665 0.40654 "'"
25.3 . . . . . . 0.40278
40.7 0.40563 0.40651 "'"
30.0 . . . . . . 0.40258
48.8 0.40655 ""
55.2 0.40409
59.8 0.40371
[51Ell] ......... 2.24 -,,,
9" 0.40484 in the late stages of decomposition because of the spatial
4.45 9" 0.40464
ordering of GP zones (see also [64Syn, 68Kha]), and it is an
6.07 ,,
9"" 0.40452
indication of spinodal decomposition only if it appears
6.87 9" 0.40444
9.46 9" 0.40419 from the early stages.
11.9 ~176
9"" 0.40392 [69Ard] attributed one modulated microstructure to the
25.3 9" 0.40291
selective coarsening of precipitates; however, they identi-
30.0 o,
9" 0.40241
fied a microstructure similar to that which appears in the
[63Pre] ......... 38.2 0.40544 0.40409 "'"
42.4 0.40496 0.40409 "" spinodal decomposition of glasses as a spinodal structure.
44.6 0.40480 0.40410 "'" [70Jon, 73Rob] attributed the latter structure, which ap-
47.9 0.40444 0.40412 "" pears in alloys near 60 at.% Zn, to the rapid precipitation
48.6 0.40435 0.40414 "" and coarsening of (Zn). (See also [69Mim, 69Doul, 69Dou2,
49.1 0.40447 0.40413 "" 71Uma] for interpretation of microstructures.)
49.7 0.40448 0.40412 ""
50.4 0.40434 0.40406 "'" Rapid Solidification. During rapid quenchingfrom the liq-
50.9 0.40429 O.40398 "" uid s t a t e ,
AI-Zn alloys, unlike other Al-based alloys, do not
52.3 0.40407 0.40379 "'"
form single-phase fcc solid solutions beyond the equi-
56.7 0.40358 0.40325 ""
librium maximum s o l u b i l i t y o f Z n i n (A1). T h e s o l u b i l i t y o f

64 Bulletin of Alloy Phase Diagrams Vol. 4 No. 1 1983

Provisional AI-Zn

A1 in (Zn), however, c a n be e x t e n d e d b y r a p i d solidi- Thermodynamics

fication. [79Bos] quoted u n p u b l i s h e d d a t a on t h e To curve*
of the liquid and (Zn), based on m e t a l l o g r a p h i c evidence. Model Free Energy Functions. The free energies of the
To descends from t h e m e l t i n g point of Zn to 280 ~ at solution p h a s e s a r e r e p r e s e n t e d by:
84 at.% Zn. O t h e r r a p i d solidification work is reported by
Gi=Fkl(1-x) + F zi, x + R T ( x In x + (1 - x) ln(1 - x))
[80Cha].
+ B ' x ( 1 - x) + C i x ( 1 - x)(1 - 2x)
Crystal Structures and Lattice Parameters where i d e s i g n a t e s the phase; x, t h e atom fraction ofZn; F +,
The crystal s t r u c t u r e s of the e q u i l i b r i u m and m e t a s t a b l e the lattice s t a b i l i t y p a r a m e t e r s of t h e pure metals, and B ~
phases are s u m m a r i z e d in Table 12. Lattice p a r a m e t e r s of and C', t h e interaction p a r a m e t e r s .
the fcc solid solution at various t e m p e r a t u r e s are given in
Table 13 and compared g r a p h i c a l l y in Fig. 4, 5, and 6. The Experimental Thermodynamic Data. [Hultgren] evalu-
fcc lattice p a r a m e t e r s a t room t e m p e r a t u r e a r e for solution ated t h e r m o d y n a m i c d a t a on Al-Zn alloys; more recent
t r e a t e d and quenched alloys. Work of [35Kos] is obsolete. work can be found in [71Pta], [72Seb], and [75Vel]. [54Hill
The fcc lattice p a r a m e t e r d a t a h a v e been given special
a t t e n t i o n in order to e v a l u a t e claims t h a t a two-phase Table 14 Lattice Parameters of the Rhombohedral
region exists above t h e miscibility gap b e t w e e n 49 and Transition Phase
50 at.% Zn [61Pre, 63Gol]. D a t a of [51Ell, 61Pre, 63Gol] Lattice
have been t r a n s c r i b e d from the published g r a p h s by com- parameters Temperature, Composition,
p u t e r digitizer; other d a t a have been t a k e n from published Reference a(nm) T ~ at.% Zn
tables. The accuracy of the d a t a t r a n s c r i p t i o n is e s t i m a t e d [64Gra] . . . . . . . . 0.2776 60.57 ~ 275 21.5
as -+0.2 at.%. [65Syn] . . . . . . . . 0.2783 61.53 . . . . ...
The lattice p a r a m e t e r s of the r h o m b o h e d r a l t r a n s i t i o n [66Mer] . . . . . . . . 0.3985 61.54 ~ 130 9
phase, a'R are compared in Table 14, t o g e t h e r w i t h the [66Raol,
66Rao2] . . . . . . 0.2798 61.29 ~ (a) 29
alloy studied and h e a t t r e a t m e n t . [68Cia] discussed the [67Carl . . . . . . . . .
0.2805 60.27 ~ 200 11
effect of the Zn c o n t e n t on t h e a m o u n t of d i s t o r t i o n . [67Sim] . . . . . . . . 0.2789 62.1 ~ 175 15
[73Anal s i m i l a r l y c o m p a r e d r e s u l t s of v a r i o u s experi- 0.2780 61.84 ~ 225 ""
m e n t s to deduce t h e Zn-rich side of the coherent mis- [68Wahl . . . . . . . . 0.2796 61.50 ~ 260 30
c i b i l i t y gap; t h i s d e p e n d s on e x t r a p o l a t i n g t h e l a t t i c e 0.2805 61.01 ~ 290 30
p a r a m e t e r / c o m p o s i t i o n curve to h i g h Zn c o n t e n t s and, (a) Cooledfrom 400 ~
based on Fig. 4, the r e s u l t s are p r o b a b l y not accurate.

Fig. 4 Lattice Parameters at Room Temperature

o 81,~t2
o r

50Dot
+ O~ '" 34Scb
0.40~5
• ~0Ell

+o[9 o 02He]

4- Xn
0
~D 0.4040

O)
0

+
[9
0.4035.
.o
+
s

0,4030-
X [9

+ o
0,4025 ........ i i ] ......... i ........
5 I0 15 20 35 40
A t o m i c Percent Zinc

J.L. Murray, 1983.

*The To curve of two phases is the locus of compositionsand temperatures at which the two phases have equal free energy. The To curve is a thermodynamic
limit above which single-phase supersaturated solid solutions cannot be formed from the liquid at a given composition.

Bulletin of Alloy P h a s e D i a g r a m s Vol. 4 No. 1 1983 65

AI-Zn Provisional

Fig. 5 Lattice Parameters at 340 ~

0.4~085 . . . . . . . . . , . . . . . . . . . , . . . . . . . . . , ......... , . . . . . . . . . , ......... , . . . . . . . . . , . . . . . . . . .

i
0
0.4080i
0 0
0
0.40"/5 0

0
0.40'70-

0,4065 0 0 0
v

0.4060-

0,4055 ~
f~
rl, 0.4050-

0.40~5i
+ ++ +§
,-]
0.4040-

D
0.4835-
A
0.4030 ~
O []

0.4025 . . . . . . . . . i . . . . . . . . . i . . . . . . . i . . . . . . . . . i . . . . . . . . . [ . . . . . . . . . i ......... i . . . . . . . . .

O lO 20 30 40 50 60 70 8(3
A t o m i c Percent Zinc

J.L. Murray, 1983.

Fig. 6 Lattice Parameters at 360 ~

0.4090

0.4085

y: :: o c
0.4080

2 ~
0,40/5
c
2 0
0.4070 L

.=
0.4065 i

0.4060 c:

D., 0.4055 + .L
[]
o
0.405,0 + +~+

0.4045

~c
0.4040 cJ
o
0.4035 § o

0.4030
10 20 30 4-0 50 60 70 80 90 100
A t o m i c Percent Zinc

J.L. Murray, 1983.

66 B u l l e t i n of Alloy Phase D i a g r a m s Vol. 4 No. 1 1983

 Provisional AI-Zn

made emf m e a s u r e m e n t s of the partial free energies FAI in In addition to the phase d i a g r a m data, we used the follow-
solid (A1) at 300 and 380 ~ (see also [59Cor]). Over most ing information:
of the composition r a n g e studied, the composition de-
9 The liquid phase is n e a r l y a r e g u l a r solution
pendence of the derived excess q u a n t i t i e s is well described
9 The p a r t i a l free e n e r g y of A1 i n the fcc p h a s e was
by a polynomial expansion. However, at 380 ~ the data
described by [54Hil]
at 55 to 65 at.% Zn show a significant deviation from the
9 (Zn) can be described as a r e g u l a r solution because of the
model. The data at 300 ~ are fit well over the entire
restricted solubility of A1 i n (Zn).
composition range. I n Table 15, the original p a r t i a l free
energy data are shown together with the calculated excess The lattice stability terms are referred to the e q u i l i b r i u m
function F " S / x ( 1 - x ) . To derive the excess function, cor- solid phases, fcc (A1) and cph (Zn). The lattice stability
rections were made for the reference states (fcc A1 and cph p a r a m e t e r s of the liquid are thus e x p e r i m e n t a l l y k n o w n
Zn) u s i n g t h e l a t t i c e s t a b i l i t y p a r a m e t e r s g i v e n by quantities. A simplified model (linear in temperature) is
[70Kau]. To fit the excess functions u s i n g a n expansion in used; corrections for heat capacity differences [75Gay] do
Legendre polynomials, one m u s t ignore the anomalous not have a n y significant effect on the optimizations. The
data; the derived p a r a m e t e r s are given in Table 16. B fee is p a r a m e t e r F(A1)cph was t a k e n from [70Kau] and not varied
a t e m p e r a t u r e - d e p e n d e n t parameter, and C fcc, tempera- in the course of the calculations. The p a r a m e t e r F(Zn)fcr is
ture independent. This free energy function gives a good i m p o r t a n t for the calculation of the phase diagram: it
approximation to the miscibility gap. d e t e r m i n e s both the m e t a s t a b l e t r a n s f o r m a t i o n points
Data on t h e r m o d y n a m i c properties of the liquid phase
were given by: [75Vel], q u a n t i t a t i v e t h e r m a l analysis; Table 15 Excess Free Energies [54Hil]
[60Ere] and [69Pre], emf method; [63Lut], dew point mea-
Composition, E x c e s s free energy, J / m o l
s u r e m e n t of Zn vapor pressure; [60Wit, 63Wit], high- at.% Zn FA! FX~/x(1 - x)
temperature calorimetry; and [69Bol], isopiestic method.
Additional data are found in [71Pta] (emf), [72Seb] (carrier A t 300 ~
gas method), and [75Vel]. For the purpose of phase dia- 5 ............................... -209 11230
gram calculations, the q u a n t i t y of most i n t e r e s t is the 10 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . -356 11016
excess entropy. [Hultgren] gives a m a x i m u m S xs of +0.96 15 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . -431 10 749
18 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . -460 10 606
-+ 0.5 J / m o l . K at 50 at.% Zn at 1000 K. [69Bol] compared 8 799
52 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . -460
t h e i r r e s u l t s ( - 2 -+ 2.6 J / m o l . K ) to [ 6 3 L u t ] ( - 7 . 1 55 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . -628 8 665
-+ 2 J / m o l . K) a n d [60Ere] (+16.4 J / m o l . K at 1120 K). 57.5 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 845 8 468
Thus, the m e a s u r e d q u a n t i t i e s do not lend guidance to
At 380 ~
phase d i a g r a m calculations. The best derived v a l u e from
phase d i a g r a m calculations is - 6 J / m o l . K; the phase dia- 5 ............................... -247 11226
10 ............................... -423 11062
gram is not a very sensitive test of this function, however. 10 841
15 ............................... -552
20 ............................... -644 10 644
Thermodynamic Calculations, This Evaluation. The re- 25 ............................... -720 10 426
sults of the calculations are compared to the assessed dia- 30 ............................... -757 10221
gram in Fig. 7. The goal of the calculations was to find free 35 ............................... -770 10 0O8
energy functions t h a t s i m u l t a n e o u s l y give the best overall 40 ............................... -782 9 778
fit to the phase d i a g r a m data and to the t h e r m o d y n a m i c 45 ............................... -795 9 552
observations. Several calculations were performed, u s i n g 50 ............................... -895 9 322
successively more p a r a m e t e r s in order to find a n o p t i m u m 55 ............................... -1180 9146
60 ............................... -1799 9109
model and to test the s e n s i t i v i t y of the phase d i a g r a m to 65 ............................... -2151 9167
the choice of model.

Table 16 Interaction Parameters of the fcc Phase

Interaction parameters, J/tool, J / m o l . K
Reference B fcc C fcc Experimental basis
[75Gay] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11401 - 2.850 T 1778 - 0.445 T Phase diagram
[75Loe, 76Loe] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (24.11 - 0.0141 T ) T (10.808 - 0.0120 T)T [Hansen] 275-340 ~
(13 212 - 7.699 T) (5 923 - 6.609 T) (evaluated at 275 ~
This work . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 845 + 5.806 T 2 226 [56Mue, 74Sim2]
This work . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 833 + 5.387 T 2 360 [54Hil], emf
[62Hil] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6360 + 4.739 T 2 369 Eutectoid, Tc
This work . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3 183 + 10.607 T 7 251 - 9.085 T [56Mue, 74Sim2]
[65Las] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4057 + 9.31 T 6 285 - 7.48 T [36Fin, 56Mue]
Coherent miscibility gap
This work . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . [9384 + 0.8766 T + 909 (1 - 2x)] x(1 - x) S e e Fig. 3
[76Loe] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . [(13.72 - 0.0374 7~T
+ (28.35 - 0.0445 T)T(1 - 2x)]x(1 - x)
[65Las] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . R[124.3(1 - 0.000677 T + 0.204 x) Elastic energy,
- 0.308 T x ( 1 - x)](x - xo)2 Xo = brutto
concentration
[68Karl . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . R[80(1 - 0 . 0 0 0 5 8 8 T + 0.607x) Elastic energy,
-.00154 T x ) ] ( x - Xo) 2 Xo = brutto
concentration

Bulletin of Alloy Phase D i a g r a m s Vol. 4 No. 1 1983 67

 Al-Zn Provisional

Fig. 7 Comparison of Calculations to the Assessed Diagram

Weight Percent Zinc

10 20 3o 40 5o 60 ~i0 80 9o i00
800 . . . . t . . . . . r . . . . J . . . . . .u. .". . i u. . . . . . . . I . .i. .. . . . . . .. . . . . ... . . . n . ' n. . . . . . . . ~u . . . . .'.' . , .........
[PHnSEmMPJ Solvus Miscibility Gap Solidus Liquidus

o ~tSin~_2 n 48Bor o 45But [] 9 7 H e y

700- 0 51Eli 0 56Mue O 4OPel 0 45But
t~ 3 6 F i n A ~Sim2 z~ 3 8 G a y z~ 38C,a y
+ 50Hof 9 36Fin + 51Eli + 49Pel
)< 5~Ell x 49Geb x 493o1
o 07La/" o 39Mot 0 43Pel
v 24,Isi v ?..4Tan
~ 241si
O 500-

"~ 400 -

c~

~ 300-

200-

100 - f . . . . . . . . r . . . . . . . . . r . . . . . . . . . , ......... i ......... f ......... , ......... F ......... I ......... i .........

10 20 30 40 50 60 70 80 9O 100
A1 Atomic Percent Zinc Zn

Solid lines represent the evaluated data, dotted lines are calculated using temperature-independent excess free energies, and dashed lines
are from the three-parameter model using excess entropies. J.L. Murray, 1983.

fcc --~ L and fcc ~ cph in pure Zn. Both the eutectic and In the second calculation, excess entropies were attributed
eutectoid are sensitive to F(Zn)rcc. Its initial value was to both fcc and liquid phases. The miscibility gap now lies
taken from [70Kau] and it was optimized with respect to within the experimental data, and the critical point is
the phase diagram data. raised to 347 ~ The liquidus and (Zn) curves are imper-
ceptibly changed. The solidus curve and high-temperature
In the optimization calculations, the fcc phase was consid- branch of the (A1) solvus are shifted toward the evaluated
ered first because the miscibility gap data allow the excess curves. The low-temperature branch of the solvus, how-
functions to be determined without reference to the other ever, shifts away from the experimental data. That is, the
phases. Miscibility gap data from the temperature region slopes of the solvi as they intersect the eutectoid horizontal
near the eutectoid were used in preference to the critical are strongly correlated. If the large curvature on the A1-
point. The phase equilibria of cph (Zn) were considered rich side is reproduced, a strong curvature on the Zn-rich
next; the cph regular solution parameter and the lattice side leads to error in the eutectic temperature. Fixing the
s t a b i l i t y F(Zn)rcc were s i m u l t a n e o u s l y fitted to the (A1) compositions at the eutectoid temperature, the opti-
(Zn)/(A1) solvus curves. The liquid equilibria with the fcc mization calculation represents a competition between the
and cph phases were used to determine the liquid excess two branches of the solvus. Thermodynamic calculations
free energy. In several calculations, the cph and liquid will favor one branch of the curve over another, but will
free energies were optimized simultaneously using the probably not succeed in matching both branches simulta-
liquidus, solidus, and solvus data. This was not found to neously. This points to either the intrinsic limitations of
work as well as the two-step calculation in matching the the free energy representations we are using or the possi-
eutectoid equilibrium. bility of errors in the experimental data in the high-
temperature high-Zn portion of the solvus (where the
Although [54Hil] showed that an excess entropy term experimental solidus also is uncertain).
should be used to describe the fcc phase, the first calcu-
In the third calculation, using four parameters to describe
lation does not use excess entropies, in order to test the
the fcc phase, the miscibility gap could be calculated essen-
sensitivity of the phase diagram to the excess entropy. The
tially exactly. However, by minimizing the error in the
calculated critical point of the miscibility gap is low by
miscibility gap, the errors in all the other phase bound-
about 10 ~ The calculated liquidus, (Zn) solvus, and low-
aries are enhanced. Large errors appear even in the liq-
temperature portion of the (A1) solvus lie within the ex-
uidus curve. It was concluded that no further improvement
perimental error. The solidus curve lies within the bounds
in the model was possible and the series of calculations
of the experimental data, down to 400 ~ below which it
was ended.
lies to Al-rich compositions. The high-temperature branch
of the A1 solvus extends from 60 at.% Zn at the eutectoid Independently, the coherent miscibility gap was calcu-
to 74 at.% Zn (cf. 67 at.% Zn) at the eutectic temperature. lated, based on the phase equilibrium data. The calcu-

68 Bulletin of Alloy Phase Diagrams Vol. 4 No. 1 1983

 Provisional AI-Zn

Table 17 Free Energy Functions for the Cited References

Calculated Diagrams, J/mol, J/mol K 9
*1897Hey: C.T. Heycock and F. H. Neville, "The Freezing Points
Lattice stability parameters of AI and Zn [70Kau] of Alloys Containing Zinc and Another Metal", J. Chem. Soc.,
FL(A1) = 10711 - 11.506 T 71,389 (1897). (Equi Diagram)
05She: E.S. Shepard, "Aluminum-Zinc Alloys", J. Chem. Phys.,
FfCC(A1) = 0
Fcph(A1) = 5481 - 1.799 T 9, 504-512 (1905). (Equi Diagram)
10Ewe: D. Ewen and T. Turner, "The Aluminium-Zinc Alloys", J.
FL(Zn) = 7 3 8 5 - 10.669 T
Inst. Met., 4,140-156 (1910). (Equi Diagram)
Ffr162 = 2281- 1.6928 T(a)
F~ph(Zn) = 0 l l R o s l : W. Rosenhain and S. L. Archbutt, "The Constitution of
the Alloys of Aluminium and Zinc", Phil. Trans. Roy. Soc.
Interaction parameters (calculation 1) (London), A211,315-343 (1911). (Equi Diagram)
BL = 7 894 l l R o s 2 : W. Rosenhain and S.L. Archbutt, "The Alloys of
CL = -68 Aluminium and Zinc", J. Inst. Met., 6, 236-250 (1911). (Equi
B fr162 = 9105 Diagram)
Cf~c = 2 282 *22Han: D. Hanson and M.L. Gayler, "A Further Study of the
B Cph = 14494 Alloys of Aluminium and Zinc", J. Inst. Met., 27, 267-294
(1922). (Equi Diagram)
Interaction parameters (calculation 2) 22Hem: T. Hemmi, "Alloys of Aluminium and Zinc",'Kogyo-
BL = - 9 0 3 9 + 24.1213 T Kwaghaku-Zasshi, 25, 511-524 (1922) in Japanese; abstract:
CL = - 2 440 J. Inst. Met., 28-644 (1922). (Equi Diagram)
B fee = 5845 + 5.8062T 22San: W. Sander and K. L. Meisser, "On the Constitution of the
Cf~c = 2 226 Alumindm-Zinc System", Z. MetaUkd., 14,385-387 (1922) in
B Cph = 14 494 German. (Equi Diagram)
(a) Optimized, see text. 23Pie: W.M. Pierce, and M. S. Palmerton, "Studies on the Consti-
tution of Binary Zinc-Base Alloys", Trans. AIME, 68, 767
(1923). (Equi Diagram)
*24Isi: T. I s i h a r a , "On the E q u i l i b r i u m Diagram of the
lation was used to d r a w Fig. 3. The Zn-rich side of the
Aluminium-Zinc System", Sci. Rep. Tohoku Univ., 13, 18-21
miscibility gap should not be considered to be accurate, (1924). (Equi Diagram)
because no information on the q u a n t i t i e s d e t e r m i n i n g t h a t 24Nis: H. Nishimura, "On the Age-Hardening of Aluminium-
portion of the gap e n t e r e d the calculation. Rich A1-Zn Alloys", Mere. Coll. Eng. Kyoto Imp. Univ., 3(6),
133-163 (1924). (Equi Diagram)
Discussion and Comparison with Other Calculations. *26Isi: T. Isihara, "A Further Investigation on the Equilibrium
The p a r a m e t e r s used in calculations 1 and 2 a r e compared Diagram of the Aluminium-Zinc System", Sci. Rep. Tohoku
in Table 17 and phase d i a g r a m s a r e d r a w n t o g e t h e r with Univ., 15,209-224 (1926). (Equi Diagram)
the assessed d i a g r a m (Fig. 7). The calculation u s i n g excess 26Tiel: O. Tiedemann, "Investigations of the A1-Zn System", Z.
entropies for both l i q u i d u s and solidus is preferred. The Metallkd., 18,221-223 (1926). (Equi Diagram)
26Tie2: O. Tiedemann, "Investigations of the A1-Zn System", Z.
a p p r o x i m a t i o n of ~asymmetric r e g u l a r solution" m a y be Metallkd., 18, 18-21 (1926). (Equi Diagram)
useful in a context w h e r e a simpler model is desirable. 32Fin: W.L. Fink and H.R. Freche, "Equilibrium Relations in
W i t h i n the f r a m e w o r k of the p r e s e n t model free energies, Aluminum-Zinc Alloys of High Purity", Trans. AIME, 99,
the use of f u r t h e r p a r a m e t e r i z a t i o n has been shown not 132-140 (1932). (Equi Diagram)
to lead to i m p r o v e m e n t of the phase d i a g r a m . The only 32Sch: M.V. Schwarz and O. Summa, "Does the Compound
phase d i a g r a m f e a t u r e t h a t distinctively c h a n g e s when Al~Zn3 Exist?", MetaUwirtsch., 11,369-371 (1932) in German.
one passes from the three- to the f o u r - p a r a m e t e r calcula- (Equi Diagram)
tion is the position of t h e m e t a s t a b l e a ' (Zn-rich) side of the 34Owe: E.A. Owen and J. Iball, "X-Ray Study of Aluminium-
miscibility gap. A t h r e e - p a r a m e t e r description places the Zinc Alloys", Philos. Mag., 17,433-457 (1934). (Equi Diagram,
Crys Structure)
a ' branch of the gap b e t w e e n 90 and 100 at.% Zn a t 273 K. 34Sch: E. Schmid and G. Wassermann, "On the Aluminum-Zinc
The f o u r - p a r a m e t e r model gives a concentration of 77 at.% System", Z. Metallkd., 26, 145-150 (1934) in German. (Equi
Zn at 273 K. Diagram, Crys Structure)
Because of i n t e r e s t in t h e spinodal, m a n y calculations 35Ful: M.L. Fuller and R.L. Wilcox, "Phase Changes During
Aging of Zinc-Alloy Die Castings, I- Eutectoidal Decomposition
have been m a d e of the excess free e n e r g y of (A1), and the of Beta Aluminum-Zinc Phase and Its Relation to Dimensional
results are compared in Table 16. The v a r i o u s free energy Changes in Die Casting", Trans. AIME, 117, 338-354 (1935).
r e p r e s e n t a t i o n s i l l u s t r a t e the r a t i o n a l e for r e s t r i c t i n g the (Equi Diagram)
description of the free e n e r g y to t h r e e p a r a m e t e r s . In four- 35Kos: G.F. Kossolapow and A. K. Trapesnikow, "X-Ray Analy-
p a r a m e t e r models, serious discrepancies in p a r a m e t e r s sis of the Beta Phase in Cu-Be and A1-Zn Alloys at High
arise from small discrepancies in the chosen i n p u t phase Temperature", Metallwirtsch, 14, 45-46 (1935) in German.
d i a g r a m d a t a . M o s t c a l c u l a t i o n s c o n s t r a i n t h e com- (Crys Structure)
positions at the eutectoid to be correct, a n d use for addi- 35Owe: E.A. Owen and L. Pickup, "X-Ray Study of Aluminium-
tional input d a t a e i t h e r t h e shape of t h e phase b o u n d a r i e s Zinc Alloys at Elevated Temperatures", Philos. Mag., 20,
761-777 (1935). (Equi Diagram)
n e a r the eutectoid t e m p e r a t u r e [75Loe] or t h e critical tem- *36Aue: H. Auer and K. E. Mann, '~Magnetic Investigation of the
p e r a t u r e [62Hil]. F o r our calculations t h e c a l c u l a t e d criti- Aluminum-Zinc System", Z. MetaUkd., 28, 323-326 (1936) in
cal t e m p e r a t u r e was not expected to be accurate, and a German. (Equi Diagram)
b e t t e r fit of the d a t a overall was o b t a i n e d by optimizing 36Bur: A. Burkhardt, "Zinc Alloys as a Substitute Material", Z.
with respect to d a t a at t e m p e r a t u r e s n e a r t h e eutectoid. Metallkd., 28(10), 299-308 (1936) in German. (Equi Diagram)
*36Fin: W.L. Fink, "Equilibrium Relations in Aluminum-Zinc
F o r additional calculations, see [61Fri, 67Kru]. [74Mue] Alloys of High Purity, II", Trans. AIME, 12, 244-260 (1936).
gives an extensive discussion of the calculation of t h e mis- (Equi Diagram)
cibility gap u s i n g more sophisticated s t a t i s t i c a l m e c h a n i - 36Ful: M.L. Fuller and R.L. Wilcox, "Phase Changes During
cal models for the excess entropy. Aging of Zinc-Alloy Die Castings, II-Changes in the Solid Solu-

Bulletin of Alloy P h a s e D i a g r a m s Vol. 4 No. 1 1983 69

 Al-Zn
tion of Aluminum in Zinc and Their Relation to Dimensional
Changes", Trans. AIME, 122,231-246 (1936). (Equi Diagram)
37Bro: W. Broniewski, J. Kucharski, and W. Winawer, "On the
Structure of Al-Zn Alloys", Rev. MetaU., 34(8), 449-461 (1937) in
French. (Equi Diagram)
*38Gay: M.L.V. Gayler, M. Haughton, and E.G. Sutherland,
"The Constitution of Aluminium-Zinc Alloys of High Purity:
The Nature of the Thermal Change of 443 ~ J. Inst. Met., 63,
123-147 (1938). (Equi Diagram)
39Gue: W. Guertler, H. Krause, and F. Voltz, "Experiments on
the Al-Zn System", Metallwirtsch., 18, 97:100 (1939) in Ger-
man. (Equi Diagram)
*39Mor: T. Morinaga, "On the Equilibrium Diagram of the
Aluminium-Zinc System", Nippon Kinzoku Gakkaishi, 3,
216-221 (1939). (Equi Diagram)
40Ell: E.C. Ellwood, "An X-Ray Study of the Constitution of
Aluminium-Zinc Alloys of High Purity above 275 ~ with
a Description of a New High-Temperature X-Ray Camera",
J. Inst. Met., 66, 87-97 (1940). (Equi Diagram)
*40Loe: K. Loehberg, "X-Ray Determination of the Solubility of
Aluminum and Copper in Zinc", Z. Metallkd., 32, 86-90 (1940)
in German; abstract: Chem. Abstr., 35, 1745 (1945); Met. Abstr.,
10,139 (1943). (Equi Diagram)
40Mor: T. Morinaga, "On the Peritectic Reaction of the
Aluminium-Zinc System", Nippon Kinzoku Gakkaishi, 4,
216-220 (1940) in Japanese. (Equi Diagram)
43But: E. Butchers, G.V. Raynor, and W. Hume-Rothery, "The
Constitution of Magnesium-Manganese-Zinc-AluminumAlloys
in the Range 0-5 percent Manganese, 0-8 percent Zinc. I. The
Liquidus", J. Inst. Met., 69, 209-228 (1943). (Equi Diagram)
*43Peh E. Pelzel and H. Schneider, "Contribution to the Under-
standing of Zn Alloys", Z. Metallkd., 35,124-127 (1943) in Ger-
man. (Equi Diagram)
*45But: E. Butchers and W. Hume-Rothery, "On the Constitution
of Aluminium-Magnesium-Manganese-ZincAlloys: The
Solidus", J. Inst. Met., 71,291-311 (1945). (Equi Diagram)
47Pet: D.A. Petrov and T.A. Badaeva, "Structures of A1-Zn
Alloys and Structural Analogues in Other Systems", Zh.
Fiz. Khim., 21,785-797 (1947) in Russian. (Equi Diagram)
48Axo: H.J. Axon and W. Hume-Rothery, "The Lattice Spacings
of Solid Solutions of Different Elements in Aluminium", Proc.
Roy. Soc. (London), A193, 1-24 (1948). (Crys Structure)
*48Bor: G. Borelius and L. E. Larsson, "Kinetics of Precipitation
in A1-Zn Alloys", Ark. Mat. Astr. Fys., 35A(13), 1-14 (1948).
(Equi Diagram, Meta Phases)
*49Gebl: E. Gebhardt, "Equilibrium Experiments on the Sys-
tems Z i n c - A l u m i n u m and Zinc-Aluminum-Copper", Z.
Metallkd., 40,136-140 (1949) in German. (Equi Diagram)
49Geb2: E. Gebhardt, "Zinc-Aluminum Phase Diagram",
Z. Metallkd., 40,463-464 (1949) in German. (Equi Diagram;
Review)
*49Pel: E. Pelzel, "The Positions of the Liquidus and Solidus
Curves in the A1-Zn System from 30 to 70 wt.% AI", Z.
Metallkd., 40,134-136 (1949). (Equi Diagram)
"498o1: I.S. Solet and H.W. St. Clair, "Liquidus Temperatures
and Liquid Densities of Zinc-Aluminum Alloys", Bureau of
Mines Report of Investigations 4553 (1949). (Equi Diagram)
*50Dor: J.E. Dorn, P. Pietrokowsky, and T. E. Tietz, "The Effect
of Alloying Elements on the Plastic Properties of Aluminum
Alloys", Trans. AIME, 188,933-943 (1950).
*50Hofi W. Hofmann and G.Fahrenhorst, "Precipitation Rates
in High Purity Zinc-Aluminum and Zinc-Copper Alloys",
Z. Metallkd., 42,460-463 (1950) in German. (Equi Diagram)
51Bor: G. Borelius, "Kinetics of Precipitation in Supercooled
Solid Solutions", Trans. AIME, 191,477-484 (1951). (Equi Dia-
gram, Meta Phases)
51Elh E.C. Ellwood, "The Solid Solutions of Zinc in Aluminium",
J. Inst. Met., 80,217-224 (1951). (Equi Diagram)
52Pas: A. Pasternak, "The Solid Solubility of Metals in Lead and
Zinc", Bull. Intern. Acad. Polon. Sci. Ser. A , 177-192 (1952);
abstract: Chem. Abstr., 48, 1097-1098 (1954). (Equi Diagram)
*54Hih J.E. Hilliard, B.L. Averbach, and M. Cohen, "Thermo-
dynamic Properties of Solid Aluminum-Zinc Alloys", Acta
Metall., 2,621-631 (1954). (Thermo)
70 B u l l e t i n of Alloy Phase D i a g r a m s Vol. 4 No. 1
Provisional
*56Mue: A. Muenster and K. Sagel, "Miscibility Gap and Critical
Point of the Aluminum-Zinc System", Z. Phys. Chem., 7,
296-316 (1956) in German. (Equi Diagram)
59Cor: H. Corsepius and A. Muenster, "On the Thermodynamic
Properties of Solid Aluminum-ZincAlloys", Z. Phys. Chem., 22,
1-19 (1959) in German. (Thermo)
60Ere: V.N..Eremenko, "Thermodynamics of Aluminium Zinc
Melts", Zh. Fiz. Khim., 34(7), 1495-1502 (1960) in Russian; TR:
Russ. J. Phys. Chem., 34(7), 714-718 (1960). (Thermo)
60Gra: R. Graf and B. Genty, "X-Ray and Electron Microscope
Study of Precipitation in an A1-40 wt.% Zn Alloy", C.R. Acad.
Sci. Paris, 251,2517-2519 (1960) in French. (Meta Phases)
60Mue: A. Muenster and K. Sagel, "Atomic Configurations in
the Solid State of the A1-Zn System", Z. Phys. Chem., 24,
217-239 (1960) in German. (Crys Structure)
60Pan: C. Panseri and T. Federighi, "A Resistometric Study of
Pre-Precipitation in Al-10 pct Zn", Acta Metall., 8, 217-238
(1960). (Meta Phases)
60Wit: R.E. Wittig and L. Schoeffi, "Heat of Formation in the
Aluminum-ZincSystem at 330, 370, and 430 ~ Z. Metallkd.,
51,700-707 (1960) in German. (Thermo)
61Fri: F. Frignet and R. Hagege, "The Consistency of Thermo-
dynamic Data and Certain Aspects of the A1-Zn Phase
Diagram", C.R. Acad. Sci. Paris, 253, 1938-1940 (1961) in
French. (Thermo; Theory)
61Gerl: V. Gerold and W. Schweizer, "Kinetics of Decomposition
of Supersaturated Aluminum-ZincAlloys", Z. Metallkd., 52(1),
76-85 (1961) in German. (Meta Phases)
61Ger2: V. Gerold, "Zone Formation in Aluminum-ZincAlloys",
Physica, 4, 37-49 (1961) in German. (Meta Phases)
*61Pre: A.A. Presnyakov, Y. A. Gorban, and V. V. Chervyakova,
"The Aluminium-Zinc Phase Diagram", Zh. Fiz. Khim., 35,
1289-1290 (1961) in Russian; TR: Russ. J. Phys. Chem., 35(6),
632-633 (1961). (Equi Diagram)
62Fed: T. Federighi, "The Concept of Ideal Pre-Precipitation in
Super-Saturated Solid Solutions", J. Phys. Rad., 23, 795-806
(1962). (Meta Phases; Theory)
62Gra: R. Graf, "Study of Pre-Precipitation in an A1-30 pct Zn
Alloy", J. Phys. Rad., 23,819-822 (1962). (Meta Phases)
*62Hel: W.J. Helfrich and R.A. Dodd, "Density Anomalies in
Binary Aluminum Solid Solutions", Trans. AIME, 224,757-762
(1962).
62Hih M. Hillert, "On the Nearest Neighbor Interaction Model
with a Concentration Dependent Interaction Energy", J. Phys.
Rad., 23,835-840 (1962). (Thermo; Theory)
*63Gol: G.R. Goldak and J.G. Parr, "A High-Temperature X-
Ray Diffractometer Study of the Zinc-AluminiumSystem in the
Region 40-75 wt.% Zinc", J. Inst. Met., 92,230-233 (1963). (Equi
Diagram)
63Lut: G.J. Lutz and A.F. Voigt, "A Radioactive Tracer Dew
Point Method for Measuring Vapor Pressures of Binary Alloys.
The Z i n c - A l u m i n u m System", J. Phys. Chem., 67(12),
2795-2799 (1963). (Thermo)
63Mur: Y. Murakami and O. Kawano, "Electron-Microscopic In-
vestigation on Precipitation Phenomena in Aluminium-Zinc
Alloys", Mem. Fac. Eng. Kyoto U., 25, 303-321 (1963). (Meta
Phases)
63Wit: F.E. Wittig and G. Keil, "Heats of Mixing of Binary Liq-
uid Aluminum-B-metal Alloys (Zinc, Cadmium, Indium, Thal-
lium, Tin, Lead and Bismuth)", Z. Metallkd., 54(10) 576-590
(1963) in German. (Thermo)
64Gra: R. Graf and M. Lenormand, "New Observations of the
Transition Phase in A1-40 wt.% Zn", C. R. Acad. Sci. Paris, 259,
3494 (1964) in French. (Meta Phases)
*64Las: J. Lasek, "Resistometric Experiments on the Coherent
Phase Boundary of the A1-Zn System", Phys. Stat. Solidi, 5,
Kl17-K120 (1964) in German. (Meta Phases)
64Ric: G.L. Richards and R.D. Garwood, "An Electron-
Microscope Study of the Isothermal Decomposition of an
Aluminium-25pct Zinc Alloy", J. Inst. Met., 93,393-397 (1964).
(Meta Phases)
648yn: V. Synecek and P. Sebo, "On the Configuration of
Guinier-Preston Zones in A1-Ag and Al-Zn Alloys", Czech. J.
Phys., 114,622-628 (1964). (Meta Phases)
1983
Provisional
65Las: J. Lasek, "On the Influence of the Average Composition
on the Position of the Coherent Miscibility Gap in the A1-Zn
System", Czech. J. Phys., B15, 848-857 (1965) in German.
(Thermo, Meta Phases)
65Mer: W. Merz, T. Anantharaman, and V. Gerold, "Structure
and Properties of A1-Zn Alloys Containing Guinier-Preston
Zones", Phys. Stat. Solidi, 8, K5-K8 (1965) in German. (Meta
Phases)
66Bon: A.F. Bonfiglioti and A. Guinier, "The Structure of
G. P. Zones in A1-ZnAlloys in the First Stage of the Formation",
Acta Metall., 14, 1213-1224 (1966) in French. (Meta Phases)
66Car: G.J.C. Carpenter and R.D. Garwood, "Hardness Rever-
sion and the Metastable Phase Boundary for G.P. Zones in
Aluminium-Zinc Alloys", J. Inst. Met., 94, 301-303 (1966).
(Meta Phases)
66Joh: A.A. Johnson, E.J. Hughes, and P. W. Barton, "The Sol-
vus Curve for Guinier-Preston Zones in A1-Zn Alloys", J. Inst.
Met., 94,186-187 (1966). (Meta Phases)
66Mer: W. Merz and V. Gerold, "Structural Investigations of Pre-
cipitation in Aluminium-ZincAlloys", Z. Metallkd., 57,607-615
(1966) in German. (Meta Phases)
66Raol: K.K. Rao and H. Herman, "Kinetics of the Decom-
position of a Quenched Aluminium-25wt.% Zinc Alloy", J. Inst.
Met., 94,420-424 (1966). (Meta Phases)
66Rao2: K.K. Rao, H. Herman, and E. Parthe, "The Structure
of a Metastable, Trigonal Transition Phase in Quenched
Aluminum-20 at.% Zinc", Met. Sci. Eng., 1, 162-166 (1966).
(Crys Structure, Meta Phases)
66Rao3: K.K. Rao, L.E. Katz, and H. Herman, "Decomposition
of Quenched AI-29 at.% Zn", Met. Sci. Eng., 1,263-280 (1966).
(Meta Phases)
*67Car: G.J.C. Carpenter and R. D. Garwood, "The Ageing of a
Quenched Aluminum-22.5 pct Zinc Alloy", Met. Sci. J., 1,
202-211 (1967). (Meta Phases)
67Ger: V. Gerold and W. Merz, "On the Decomposition of an
Aluminum-Zinc Alloy", Scr. Metall., 1, 33-35 (1967). (Meta
Phases)
67Kru: A. Krupkowski, R. Ciach, and J. Krol, "Decomposition
of the Alpha-Phase in the A1-Zn Alloys with 60-78 percent of
Zinc", Bull. Acad. Pol. Sci., Ser. Tech., 15(11), 25-29 (1967).
(Thermo)
67Lar: L.E. Larsson, "Pre-Precipitation and Precipitation
Phenomena in the A1-Zn System," Acta Met., 15, 35-44 (1967).
(Equi Diagram)
67Run: K.B. Rundman and J.E. Hilliard, ~'Early Stages of
Spinodal Decomposition in an Aluminum-Zinc Alloy", Acta
Metall., 15, 1025-1033 (1967). (Meta Phases)
*67Sim: M. Simerska and V. Synecek, "The Mechanism of Struc-
ture Transformations in Super-Saturated A1-Zn Alloys", Acta
Metall., 15,223-230 (1967). (Meta Phases)
67Str: B.G. Strongin, '~Phase Transformations in Alloys of Alu-
minum with Zinc", Fiz. Met. Metalloved., 28(2) 248-256 (1967)
in Russian; TR: Phys. Met. Metallogr., 23(2), 55-62 (1967). (Meta
Phases)
68Cah: J.W. Cahn, "Spinodal Decomposition", Trans. AIME,
242, 166-180 (1968). (Meta Phases; Review, Theory)
68Cia: R. Ciach, "Effect of the Zinc Content on the Rhombohedral
Distortion of the Transition Phase in A1-Zn Alloys", Scr.
Metall., 2,575-580 (1968). (Meta Phases; Theory)
68Eli: A.M. Elistratov, G.V. Kleshchev, A.I. Sheinkman, D.V.
Shumilov, and V.A. Toldin, "The Nature of the Metastable
States in the Aging of A1Zn", Fiz. Tverd. Tela, 9(10), 2811-2819
(1968) in Russian; TR: Soy. Phys.-Solid State, 9(10), 2209-2215
(1968). (Meta Phases)
68Kar: B.K. Kardasev, S.P. Mikandrov, and J. Lasek,
"Temperature Dependence of Young's Modulus of Aluminum-
Zinc Alloys and Its Influence Upon the Metastable Coherent
Phase Diagram", Czech. J. Phys., B18, 275-283 (1968) in
Russian. (Meta Phases, Thermo)
68Kha: N.A. Khatanova and M. I. Zakharova, "Electron Micro-
scopic and X-Ray Diffraction Investigation of the Decom-
position of the Solid Solution in the Alloy A1-Zn", Fiz. Met.
Metalloved., 26(5), 955-957 (1968) in Russian; TR: Phys. Met.
MetaUogr., 26(5), 193-195 (1968). (Meta Phases)
Bulletin of Alloy Phase D i a g r a m s
Al-Zn
68Oht: M. Ohta, F. Hashimoto, and H. Maeda, "Initial Aging
of A1-Zn Binary Alloys", Nippon Kinzoku Gakkaishi, 32,
1097-1103 (1968) in Japanese. (Meta Phases)
69Ana: T.R. Anantharaman, "The Solvus for the Transition
Phase in Aluminium-ZincAlloys and Its Impact on the Latter's
Rhombohedral Distortion at Different Ageing Temperatures",
Scr. Metall., 3, 899-904 (1969). (Meta Phases)
*69Ard: A.J. Ardell, K. Nuttall, and R.B. Nicholson, "The De-
composition of Concentrated Aluminium-(28-59 pct) Zinc
Alloys", Inst. Met. Proc. Internat. Symp. on The Mechanism of
Phase Transformations in Crystalline Solids, Manchester, July
1968, 22-26 (1969). (Meta Phases)
69Boh P. Bolsaitis and P.M. Sullivan, "The Activity of Zinc in
Liquid Zn-A1 Alloys from Isopiestic Measurements", Trans.
AIME, 245, 1435-1438 (1969). (Thermo)
6 9 D o u l : D.L. Douglass, "Spinodal Decomposition in A1/Zn
Alloys-Part 2: X-Ray Diffraction Studies", J. Mat. Sci., 4,
130-137 (1969). (Meta Phases)
69Dou2: D.L. Douglass and T.W. Barbee, "Spinodal Decom-
position in A1/Zn Alloys-Part 3: Metallography and Electron
Microscopy", J. Mat. Sci., 4, 138-151 (1969). (Meta Phases)
69Mim: G. Mima, M. Yamagucha, and Y. Umakoshi, "On the
Aging of A1-40 at.% Zn Alloy at High Temperatures", Nippon
Kinzoku Gakkaishi, 33, 527-530 (1969) in Japanese. (Meta
Phases)
69Mur: M. Murakami, Y. Kawano, Y. Murakami, and M. Mor-
inaga, "On the Determination of the Spinodal Temperature in
an Aluminum-6.8 at.% Zinc Alloy", Acta Metall., 17, 1517-1521
(1969). (Meta Phases)
69Nik: T. Niklewski, P. Spigelberg, and K. Sunbulli, "The Solvus
Curve for Guinier-Preston Zones in A1-Zn Alloys: A Diffuse
X-Ray Study", Met. Sci., 3, 23-25 (1969). (Meta Phases)
69Pre: B. Predel and U. Schallner, "On the Thermodynamic
Properties of Binary Aluminium Alloys Containing Gallium
and Zinc", Z. Metallkd., 60(11), 869-877 (1969) in German.
(Thermo)
69Wah: R.P. Wahi and T.R. Anantharaman, "Study of Rever-
sion in Aluminium-Zinc Alloys Containing 20 and 30 at.%
Zinc", Current Sci., 38(1), 1-26 (1969). (Meta Phases)
70Cia: R. Ciach, "Reply to T. R. Anantharaman: The Solvus for
the Transition Phase in Aluminum-ZincAlloys and Its Impact
on the Latter's Rhombohedral Distortion at Different Ageing
Temperatures", Scr. Metall., 4, 39-42 (1970). (Meta Phases)
70Dut: J. Dutkiewicz, "Electron Microscopy Investigations of the
Alpha'-Phase Decomposition in A1Zn-50 Alloy", Bull. Acad.
Pol. Sci. Ser. Tech., 18(9), 57-61 (1970). (Meta Phases)
70Jon: R.D. Jones and K.G. Thomas, "The Decomposition of
Near-Eutectoid Zinc-Aluminum Alloys", Philos. Mag., 22,
427-430 (1970). (Meta Phases)
70Kau: L. Kaufman and H. Nesor, Computer Calculation of
Phase Diagrams, Academic Press, New York (1970).
70Sat: K.G. Satyanarayana, R.P. Wahi, and T.R. Anan-
tharaman, "Effect of Micro-Addition of Magnesium on Side-
Band Formation in Aluminium-Zinc Alloys", Current Sci.,
39(15), 335-339 (1970). (Meta Phases)
71Dob: A.V. Dobromyslov and N. N. Buinov,"X-Ray Diffraction
Study of the Decomposition of Supersaturated Solid Solutions of
A1 Alloys. Pt. 2. Existence of a Transition Phase During the
Aging of an A1-ZnAlloy", Fiz. Met. Metalloved., 32(6), 1277-1282
(1971) in Russian; TR: Phys. Met. MetaUogr., 32(6), 156-163
(1971). (Meta Phases)
71Mel: K.N. Melton and J.W. Edington, "Comments on
'Spinodal Decomposition in A1/Zn Alloys'", J. Mat. Sci., 6,
449-450 (1971). See also [69Doul, 69Dou2]. (Meta Phases)
71Mur: M. Murakami, O. Kawano, and Y. Murakami, "On the
Determination of the Solvus Temperature for Guinier-Preston
Zones in an A1-6.8 at.% Zn Alloy", J. Inst. Met., 99, 160-163
(1971). (Meta Phases)
71Pta: W. Ptak and L. Zabdyr, "Determination of Thermo-
dynamic Properties of A1-Zn Solutions by Electromotive Force
Measurements", Arch. Hutn., 16(3), 253-267 (1971) in Polish.
(Thermo)
71Ray: J. Raynal, R. Anthore, and R. Graf, "Diffuse X-Ray
Scattering Study of Pre-Precipitation in a Series of A1-Rich
Vol. 4 No. 1 1983 71
Al-Zn
Binary A1-Zn Alloys", C. R. Acad. Sci. Paris, 272, 1761-1764
(1971) in French. (Meta Phases)
71Urea: Y. Umakoshi, M. Yamaguchi, and G. Mima, "The
Characteristics of Phase Transformation During the Aging in
Aluminum-RichZinc Alloys at High Temperature", Trans. Jpn.
Inst. Met., 12, 7-12 (1971). (Meta Phases)
71Wah: R.P. Wahl and T.R. Anantharaman, "The Metastable
Miscibility Gap and Reversion in Aluminium-Zinc Alloys",
Trans Indian Inst. Met., 61-65 (1971). (Meta Phases)
72Hir: K. Hirano and H. Hori, "The Solvus Curve of the G.P.
Zones m the Al-gn System", Nippon Kinzoku Gakkaishi, 36,
97-194 (1972) in Japanese. (Meta Phases)
*77,Joe: M.H. Jacchs, "The Morphology and Crystal Structure
of a New Precipitate in Rapidly Quenched Aluminium-Zinc
Alloys", Met. Sci. J., 6, 143-148 {1972). (Meta Phases)
7ZMe]: K N. Melton and J.W. Edington, "Spinodal Decom-
position in an Aluminium 29 at.% Zinc Alloy", Scr. Metall., 6,
501-502 (1972). (Meta Phases)
*7~-Riv: G. Rivaud, J. Guillot, and J. Grilhe, "Determination of
the Miscibility Gap by Resistivity Measurements-Al-Zn",
Scr. Metall., 6, 411-416 (1972). (Meta Phases)
7ZSeb: J Sebkova, M. Beranek, and J. Koritta, "Activity of Zn in
Liquid Al-Zn Alloy", Kovove Mater., 10(3), 234-239 (.!972) in
C~ech-(Thermo)
72Vel: J. Velisek, "Determination of Thermodynamic Functions
in the Aluminum-Zinc System by Quantitative Thermal
Analysis", Sb. Prednasek-Semin. Difuse Termodyn. Kovu
Slitin, 171-174 (1972) in Czech. (Thermo)
73Aga: S_ Agarwal and H. Herman, "Spinodal Decomposition in
Liquid Quenched A1-22 at.% Zn", Scr. Metall., 7, 503-508
(1973)- (Meta Phases)
73Aria: T.R. Anantharaman and K.G. Satyanarayana, "The
Metastable Solvus for Guinier-Preston Zones in Aluminum-
Zinc Alloys", Scr. Metall., 7, 189-192 (1973). (Meta Phases)
73But: E_ P. Butler, V. Ramaswamy, and P.R. Swann, 'Tn Situ
Observation of Cellular Precipitation in an A1-28 at.% Zn Alloy
by High Voltage Electron Microscopy", Acta Met., 21, 517-524
(1973). (Meta Phases)
73Mue: A. Muenster, "Critical Points and Higher Order Transi-
tions in Binary Alloys", Z. Phys. Chem., 86, 230-251 (1973).
(Equi D~agram; Theory)
73Nay: A K Nayak, "Thermal and Quantitative Thermal
Analysis of AI-Zn Alloys and Determination of the Equilibrium
Diagram of the Binary System", J. Inst. Met., 101, 309-314
(1973)-(Equi Diagram)
73Rob: R Roberge and H. Herman, "On the Mierostructure of
Liquid Quenched Monotectoid Al-Zn", J. Inst. Met., 101, 339
(1973) (Meta Phases)
73Smi: A. E W. Smith and G~A Hare, "Controlling the Zinc-
A[umin~um Eutectoid Reaction", J. Inst. Met., 101, 320-328
(i973) (Equi Diagram)
73Tru: W_ Truszkowski an~ J. Dutkiewicz, "Spinodal Decom-
position and Discontinuous Precipitation in the Aging of
Aluminium-ZincAlloys Within the Range of Miscibility Gap",
Bull. Acad Pot Sci. Ser. Tech, 21(10), 19-24 (1973). (Meta
Phases)
74Acu: R. Acuna and A. Bonfiglioli, "Experimental Study of
Random Fluctuation Effects on Spinodal-Like Decomposition of
Al-15 at% Zn", Acta Metall., 22, 399-408 (1974). (Meta Phases)
74All: J Allain and A. Naudon, "Small Angle X-Ray Scattering
Evidence of G.P. Zones Formed by Nucleation and Growth
in an A1-6.8 at.% Zn Alloy", Scr. Metall., 8, 831-836 (1974).
(Meta Phases)
74Ana: T R. Anantharaman, V. Ramaswamy, and E.P. Butler,
"Effect of Matrix Precipitation on Cellular Growth Kinetics
in an Al-28 at.% Zn Alloy", J. Mat. Sci., 9, 240-244 (1974).
(Meta Phases)
74Che: D_ Cheetham and F.R. Sale, "Enthalpy of Transforma-
tion and Interracial Enthalpy of a Zinc-AluminiumEutectoid
Alloy", Acta Metall., 22, 333-337 (1974). (Thermo)
74Cia: R- Ciach, R. Kroggel, H. Loeffler, and G. Wendrock,
"The Isochronous Phase Transformations of the A1-38 at.% Zn
Alloy at 273 ~ Arch. Hutn., 19, 183-190 (1974) in Czech.
(Equi Diagram, Meta Phases)
72 B u l l e t i n of Alloy Phase D i a g r a m s Vol. 4
Provisional
74Jun: A. Junqua, J. Mimault, J. Delafond, and J. Grilhe,
"Distinction Between Nucleauon and Spinodal Decomposition
by Magnetic Susceptibility Measurements on an Al-15 wt.% Zn
Alloy", Scr. Metall, 8, 317-322 (1974) in French. (Meta Phases)
74Mue: A. Muenster, Stattsttcal Thermodynamics Vol. H,
Springer-Verlag, Berlin-Heidelberg-NewYork (1974). (Thermo;
Theory)
74Nau: A. Naudon and J. Allain, "On Nucleation-Growth and
Spinodal Decomposition in AI-6.8 at.% Zn", Scr. Metall., 8,
1105-1112 (1974). (Meta Phases)
*74Sim[: M. Simerska, V. Synecek, and V. Sima, "Solvus Line
of the Metastabie Rhombohedral Phase in the AI-Zn System far
AI-Rich Alloys", Czech. J. Phys., B24, 543-552 (I974). (MeSa
Phases)
"74Sim2: M. Simerska and P. Bartuska, "The X-Ray Diffraction
and Electron Microscopic Investigation of Stable and Meta-
stable Equilibria in Al-Rich AI-Zn Alloys", Czech. J. Phys,B24,
553-559 (1974). (Equi Diagram, Meta Phases)
*74Sire3: M. Simerska, V. Siren, and R Bartuska, ~tThe Forma-
tion of Rhombohedral Phase During the Slow Cooling of the
Al-Zn Solid Solutions", Czech J. Phys., B24, 654-659 (1974).
(Meta Phases)
75Barh T.L. Bartel and K B Rundman, "Decomposition in
A1-Zn Alloys: Part ]. Isothermal Decomposition in an A1-22 at.
pct Zn-0.1 at. pct. Mg Alloy", Met. Trans., 6A, 1887-1893 (1975).
(Meta Phases)
75Bar2: P. Bartuska, M. Simerska, and V. Sima,"Effect of Iron
and Silicon on Structure Transformations and on Micro-
hardness of A1-30 wt.% Zn Alloy Aged at 90 ~ Czech. J. Phys.
B, 25, 1139-1148 (1975). (Meta Phases)
75Def: D. de Fontaine, "Clustering Effects in Solid Solutions",
Treatise on Solid State Che~nistry, Vol. 5, Changes of State,
N. B. Hannay, Ed., Plenum Press (1975). (Meta Phases; Theory)
75Del: J. Delafond, A. Junqua, J. Mimault, and J.P. Riviere,
"Confirmation by Electric Resistivity of Two Mechanisms of
Zone Formation in A1Zn: Spinodal Decomposition and
Germination-Growth', Acta Metall., 23, 405-411 (1975) in
French. (Meta Phases)
75Gay: H. Gaye and C. H. P. Lupis, ~'Numerical Techniques for
the Calculation of Binary Phase Diagrams", Met. Trans. A, 6A,
1049-1056 (1975). (Thermo; Theory)
75Koj: T. Kojima, K. Kuribayashi, and M. Doyama, "The Effect
of Precipitation in AI-Zn Alloy on Positron Annihilation", Scr.
Metall., 9, 1071-1072 (1975) (Equi Diagram, Meta Phases)
75Lew: D.T. Lewandowski and K. B. Rundman, '~Decomposition
in AI-Zn Alloys: Part. [[. Decomposition During Continuous
Cooling", Met. Trans., 6,4, 1895-1900 (1975). (Meta Phases)
75Loe: H. Loemer and O. Simmich, "On the Calculation of the
Spinoda[ Curves in the AI-Zn System"~ Phys. Scat. Solidi(a),
30A, 495-590 (1,975). (Thermo; Theory)
75Sire: M. Simerska and V. Synecek, "The Kinetics of Forr~a~ion
and Decom!~sition of the Transition Rbombobedra] Phases in
the Al-30 wt.% Zn Alloy", Acta Cryst., A31, 185 (1975). (Meta
Phases)
75Ter: H. Terauchi, N. Sakamoto, K Osamura, and Y. Mur-
akami, 'r Angle X-Ray Critical Scattering in an A1-Zn
Alloy with the Critical Composition', Trans. Jpn. Inst. Met., 16,
379-383 (1975). (Equi Diagram)
75Veh J. Velisek, ~Determination of Thermodynamic Activities
in the A1-Zn System by Calorimetric Method", Kovove Mater.,
13(3), 303-313 (1975). (Thermo)
76Bar: P. Bartuska, qnvestigation of the Precipitation Pro-
cesses, in A1-35-75 wt.% Zn Alloys Annealed at 280 ~ Kovove
Mater., 14(3), 225-249 (1976) in Czech. (Meta Phases)
76Jun: A. Junqua, J. Mimault, and J. Delafond, "Study of Vari-
ous Domains of GP Zone Formation in the A1-Zn Phase
Diagram", Acta Metall., 24, 779-787 (1976) in French. (Meta
Phases)
76Loe: H. Loeffier and O. Simmich, "A Rough Approximation to
Calculate the Free Enthalpy of Mixing of the R-Phase in the
A1-Zn System", Bull. Acad. Pol. Sci. Ser. Techn., 24(5), 13-16
(1976). (Thermo; Theory)
77Bos: P.G. Boswell and G.A. Chadwick, "Eutectoid Decom-
position of Zn-A1 Splat-Quenched and Bulk Specimens", Acta
No. 1 1983
 Provisional
Metall., 25,779-792 (1977). (Thermo)
77Fla: A.M. Flank and A. Naudon, "In Situ Study by Diffuse
X-Ray Scattering of the Effect of Small Additions of Mg on the
Precipitation Mechanisms in an Al-15 wt.% Zn Alloy", J. Appl.
Cryst., 10,151-155 (1977) in French. (Meta Phases)
77Fum: M. Fumeron, J.P. Guillot, and A. Dauger, "Model of
Diffuse X-Ray Scattering by Guinier-Preston Zones for the Case
of Al-Zn", Phys. Stat. Solidi (a), 42,687-697 (1977) in French.
(Meta Phases)
*77Kro: R. Kroggel, H. Loeffier, and O. Kabisch, "Experimental
Investigations on the Position of the Coherency Spinodal Curve
in A1-Zn (15, 16, and 18 at.%) Alloys", Phys. Stat. Solidi, 40A,
K163-164 (1977). (Meta Phases)
77Lasl: G. Laslaz and P. Guyot, "Electron Microscope Study
of Decomposition of an AI-6.8 at.% Zn Alloy", Acta Met., 25,
277-285 (1977). (Meta Phases)
77Las2: G. Laslaz, G. Kostorz, M. Roth, P. Guyot, and R.J.
Stewart, "Interparticle Interference in Neutron Small-Angle
Scattering of A1-6.8 at.% Zn During Aging at 133 ~ Phys.
Star. Solidi(a), 41A, 577-583 (1977). (Meta Phases)
77Sat: K.G. Satyanarayana and K. Hirano, "Metastable Solvus
Curves and Structural Changes in A1-Zn Alloys", Trans. Jpn.
Inst. Met., 18,403-411 (1977). (Meta Phases; Review)
"77Sch: D. Schwahn, "Neutron Small Angle Scattering from the
Alloy A1-Zn Above the Critical Point", Kernforsch, Julich
GmbH (1977) in German. (Meta Phases)
77Siml: M. Simerska and P. Bartuska, "The Influence of
Quenching Rate on the Kinetics of Transformations of Meta-
stable Phases in the A1-30 wt.% Zn Alloy", Czech. J. Phys.,
B27,663-671 (1977). (Meta Phases)
77Sim2: M. Simerska and P. Bartuska, "Precipitation Sequences
and Transformation Kinetics in the A1-30 wt.% Zn Alloy Aged
Below 160 ~ Czech. J. Phys., B27, 655-662 (1977). (Meta
Phases)
78Aga: S.C. Agarwal and H. Herman, "Early-Stage Phase Sepa-
ration in Liquid-Quenched AI-7 at.% Zn", J. Mat. Sci., 13,
1549-1554 (1978). (Meta Phases)
78Cial: R. Ciach, J. Salawa, O. Kabisch, and G. Wendrock,
"Effect of the Miscibility Gap on the Segregation Structure and
Physical Properties of A1-Zn Alloys", Arch. Hutn., 23, 233-255
(1978) in German. (Equi Diagram)
78Cia2: R. Ciach, B. Dukiet-Zawadzka, and T. D. Ciach, "A Study
of the Homogenization Process of Aluminum-Zinc Alloys", J.
Mat. Sci., 13, 2676-2686 (1978). (Equi Diagram)
78Loe: H. Loeffier, O. Kabisch, and R. Kroggel, "About a Re-
lation Between Microhardness and the Average Radius of the
Guinier-Preston Zones in A1-Zn Alloys", Phys. Stat. Solidi(a),
49A, 299-303 (1978). (Meta Phases)
78Pel: J.M. Pelletier, J. Merlin, and R. Borrelly, "Study of the
Development of A1-Zn Solid Solutions by Measurements of
Thermo-Electric Power", Mat. Sci. Eng., 33(1), 95-100 in
French. (Meta Phases)
*78Sch: D. Schwahn and W. Schmatz, "Neutron Small Angle
Scattering from the Alloy A1-Zn Above the Critical Point", Acta
Metall., 26, 1571-1578 (1978). (Meta Phases)
*78Sim: M. Simerska, P. Bartuska, and V. Synecek, "Struc-
ture Transformations in Supersaturated A1-Zn Alloys", Acta
Crystallogr. A: 34($4), $304 (1978). (Meta Phases)
78Toh V.A. Toldin, A. A. Burykin, and G. V. Kleshchev, "Natural
Aging of Aluminum-Zinc Alloys with a High Zinc Concen-
tration", Fiz. Met. Metalloved., 45(2), 342-346 (1978) in Russian;
TR: Phys. Met. Metallogr., 45(2), 97-106 (1978). (Meta Phases)
79Bos: P.G. Boswell, "Solidification Models for High Cooling
Rates", Met. Forum, 2(1), 40-54 (1979). (Meta Phases)
79Cia: R. Ciach, H. Loeffler, J. Salawa, and G. Wendrock,
"Modulated Structures and Position of the Coherent Spinodal
Curve in A1-Zn (22 at.%)-Cu(x) Alloys", Phys. Star. Solidi,
53(a), 441-446 (1979). (Meta Phases)
Al-Zn evaluationcontributedby Joanne L. Murray, Center forMaterials Science,National Bureau ofStandards.This work was jointlyfunded by the Defense
Advanced Research ProjectAgency (DARPA) and the National Bureau of Standards through the Metallurgy Division and through the Officeof Standard
Reference Data. The author wishes to thank John W. Cahn for many valuable discussionson many aspectsof thissystem. Literature searched through 1980.
Dr. Murray and Dr. A.J. McAlister are the A S M / N B S Data Program Category Editors for binary aluminum alloys.
Bulletin of Alloy P h a s e D i a g r a m s
AI-Zn
79Fab: H.G. Fabian, R. Kroggel, H. Loeffier, and O. Simmich,
"On the Description of the Growth and Decomposition Kinetics
of Supersaturated Alloys", Phys. Stat. Solidi(a), 56A, 143-148
(1979). (Meta Phases)
79Fum: M. Fumeron, J.P. Guillot, A. Dauger, and J. Caisso,
"Study of Diffuse X-Ray Scattering by Guinier-Preston Zones
and the Effect of Their Shape, in a 6.8 at.% Zn Alloy", Phys.
Stat. Solidi(a), 53,605-610 (1979) in French. (Meta Phases)
79Sat: T. Sato, Y. Kojima, and T. Takahashi, "A Study on the
Temperature Limit for G. P. Zone Formation in A1-Zn Alloys",
Trans. Jpn. Inst. Met., 20,475-482 (1979). (Meta Phases)
79Zahl: A. Zahra, C. Y. Zahra, and J.-C. Mathieu, "Calorimetric
Aging Study of an Al-15 pct Zn Alloy", Z. Metallkd., 70(10),
54-56 (1979). (Meta Phases)
79Zah2: A. Zahra, C. Y. Zahra, and J.-C. Mathieu, "Calorimetric
Aging Study of an Al-10 pct Zn Alloy", Z. MetaUkd., 70(10),
669-673 (1979). (Meta Phases)
80Acu: R.J. Acuna, "Pre-Precipitation of Al-Zn Alloys in the
Range 30 to 40 wt.% Zn", J. Mat. Sci., 15, 20-24 (1980), (Meta
Phases)
80Cha: K. Chattopadhyay, S. Lele, and P. Ramachandrarao, "On
the Occurrence of Twinned Dendrites in Rapidly Solidified Alu-
minium Alloys", J. Cryst. Growth, 49(2), 322-324 (1980). (Meta
Phases)
80Duk: B. Dukiet-Zawadzka, "The Problem of Micro-Hetero-
geneities in Aluminum-Zinc Alloys", Pol. Akad. Nauk Pr. Kom.
Metal.-Odlew, Metal.,28,25-59 (1980) in Polish. (Equi Diagram)
80Fum: M. Fumeron, J.P. Guillot, A. Dauger, and J. Caisso,
"Diffuse X-Ray Scattering Study of the Internal Structure of
G.P. Zones in an A1-6.8 at.% Zn Alloy. Comparison with the
alpha'R Phase", Scr. Metall., 14,189-194 (1980). (Meta Phases)
80Lui: N. Luiggi, J. P. Simon, and P. Guyot, "Residual Resistivity
During Clustering in A1-Zn Solid Solutions", Acta Metall., 28,
1115-1122 (1980). (Meta Phases)
80Pra: P.R. Prasad and R. Prasad, "Determination of Metastable
Zone-Boundary of G. P. Zones in A1-Zn Alloys by Hardness Re-
version Technique", Trans. Ind. Inst. Met., 33(1), 82-84 (1980).
(Meta Phases)
81BAP: "Melting Points of the Elements", Bull. Alloy Phase Dia-
grams, 2(1), 145-146 (1981).
81Def: D. de Fontaine, "Ordering Instabilities and Pretransi-
tional Effects", Met. Trans., 12A, 559-566 (1981). (Thermo;
Theory)
81Loe: H. Loeffler, V. Synecek, M. Simerska, G. Wendrock,
P. Bartuska, and R. Kroggel, "On the Mode of Decomposition
of A1-Zn Alloys", Phys. Star. Solidi(a), 65, 197-204 (1981).
(Meta Phases; Review)
81Satl: K.G. Satyanarayana, "Metastable Solvus Curves in
Al-Zn Alloys. I. The Guinier-Preston Zones", J. Mat. Sci., 16,
1233-1239 (1981). (Meta Phases; Review)
81Sat2: K.G. Satyanarayana, "Metastable Solvus Curves in
A1-Zn Alloys. Pt. 2. The Transition Phase", J. Mat. Sci., 16,
1240-1248 (1981). (Meta Phases; Review)
8lUng: T. Ungar, J. Bendvai, and I. Kovacs, "Determination of
the Spinodal Temperature in a Series of A1-Zn (6-21 at.%)
Alloys", Philos. Mag. A, 43(4), 927-934 (1981).
82Hen: M. Hennion, D. Ronzaud, and P. Guyot, "Kinetics of Un-
mixing in A1-Zn Single Crystals Studied by Neutron Small
Angle Scattering", Acta MetaU., 30, 599-610 (1982). (Meta
Phases)
82Paw: A. Pawlowski and W. Truszkowski, "Cellular Dissolution
in the Aged Aluminium-40% Zinc Alloy", Acta Metall., 30,
37-50 (1982). (Meta Phases)
82Vij: M. Vijayalakshmi, V. Seetharaman, and V.S. Raghuna-
than, "On the Various States of Spinodal Decomposition in an
A1-38 at.% Zn Alloy", J. Mat. Sci., 17, 126-134 (1982).
*Indicateskey pape~
Vol. 4 No. 1 1983 73