Si-Zn

AI-O
*70Blo: M.M. Blouke, N. Holonyak, Jr., B.G. Streetman, and Inorganic Substances, Springer-Verlag, New York (1973).
H.R. Zwicker, "Solid Solubility of Zn in Si," J. Phys. Chem. (Thermo; Compilation)
Solids, 31, 173-177 (1970). (Equi Diagram; Experimental) 77Bar: I. Barin, O. Knacke, and O. Kubaschewski, Thermo-
70Rao: M.V. Rao and W.A. Tiller, "Excess Free Energies in the chemical Properties of Inorganic Substances (Supplement),
Ge, Si, and Ga Binary Systems--the a-Parameter Approach," Springer-Verlag, New York (1977). (Thermo; Compilation)
J. Phys. Chem. Solids, 31, 191-198 (1970). (Thermo; Theory) 77Gir: B. Girault, "Liquidus Curves of Various Silicon-Metal Sys-
72Seh: M. Schneider and M. Krumnacker, "Study of the Zinc- tems," C. R. Acad. Sci. Paris B, 284, 1-4 (1977) in French. (Equi
Silicon Phase Diagram," Neue Hiitte, 17, 519-521 (1972) in Diagram; Experimental)
German. (Equi Diagram; Experimental)
73Bar; I. Barin and O. Knacke, Thermochemical Properties of *Indicates k e y paper,

Si-Zn e v a l u a t i o n c o n t r i b u t e d by R. W. O l e s i n s k i a n d G . J . A b b a s c h i a n , D e p a r t m e n t of M a t e r i a l s Science a n d E n g i n e e r i n g , U n i v e r m t y of Florida, Gaines-

ville, Florida, 32611 This p r o g r a m w a s supported by ASM, u n d e r g r a n t No, FG 101-1 to the U n i v e r s i t y of Florida. T h e r m o d y n a m ] c calculations were made
by u s i n g the c o m p u t e r p r o g r a m developed by Drs. A. D. Pelton, W T. Thompson, a n d C.W. Bale, of McG]ll University, Montreal, Quebec L g e r a t u r e was
s e a r c h e d t h r o u g h 1983. Professor G, J. A b b a s c h i a n is ASM/NBS D a t a P r o g r a m C a t e g o r y Editor for b i n a r y silicon alloys,

The AI-O (Aluminum-Oxygen)System

26.98154 15.9994

By H. A. Wriedt
Consultant
which the deviations from stoichiometric composition are
Equilibrium Diagram unknown but small; and (4)the gas, g.
The equilibrium phases of the A1-O system are: (1)the The published diagrams [34Bau, 66Git, 68Yan] for the
liquid, L, which to the limits of existing experimental condensed phases were concerned only with the compo-
knowledge exists as two immiscible liquids, here termed sition range between 0 and 60 at.% O. There was general
"liquid (AI)," when Al-rich, and "liquid A1203," when agreement that no stable condensed phase exists that is
O-rich; (2) the fcc (A1) terminal solid solution, in which the richer in O than A1203. These diagrams showed no solid
solubility of O is unknown but small; (3)the trigonal solubility of O in solid A1 or deviation from stoichiometry
A1 oxide aA1203 (a alumina, sapphire, or corundum), for in A1203; portions of the liquidus curves, the boundaries of

Fig. 1 Assessed AI-O Phase Diagram (Condensed System)

Weight Percent Oxygen
1o 30 30 4O
2300 i L . . . . F ......... i . , .....
"..60
2100- ~4-6.5~7~~
Ll + L2 \
1900-
",~OJ
/ M.P.

59.5-I-0.5

1700-
O

1500-

e~ 13oo- LI+aAI303 aAla03

E
[.-.
llO0 -

900-

/ 660,452~
70~ j <3xI0-8,(AI) ,,,,880Oc ~1,0
(At) (A1)+aA1203
50O p . . . . . . . . . i . . . . . . . . i . . . . . . . i . . . . . . . . . i . . . . . . . . .

10 20 30 40 50 60
AI Atomm Percent Oxygen

H.A. Wnedt, 1985.

548 Bulletin of Alloy Phase Diagrams Vol. 6 No. 6 1985

 AI-O

Table 1 AI-O Three-Phase Equilibria and Other Transformations (Condensed System)

Compositions of the respective phases, Temperature, Reaction
Reaction at.% 0 ~ type

(A1,L)~(A1) + aA1203 . . . . . . . . . . . . . -<3 • 10 s <3 • 10 s 60 -660 Probably eutectic

A120~,L~(A1,L) + aA1203. . . . . . . . . . 59.5 -+ 0.5 -0.1 -60 2046.5 _+ 7.5 Monotectic
L ~ A1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0 660.452 Melting
L ~ A120~ . . . . . . . . . . . . . . . . . . . . . . . . . . 60 2054 Congruent melting

Table 2 Crystal Structures and Lattice Parameters of Stable AI-O Phases (25 ~ 0.1 MPa)
Composition, Pearson Space Strukturbericbt Lattice parameters, nm
Phase at.% 0 symbol group designation Prototype a c Comment Reference
(A1) . . . . . . . . . . . . 0 cF4 F m 3m A1 Cu 0.40496 . . . . . . [King3]
aA1203. . . . . . . . . 60 hR 10 R3c D5, aAl203 0.51272 "'" a = 55016.7' [Pearson2]
0.47589 1.2991 "" [Pearson2]

the liquid miscibility gap, and a disputed solid oxide were
the subjects of these presentations. The present diagram
(Fig. 1) is largely qualitative, because of the lack of data on
the composition ranges of the solid and liquid phases. A
eutectic reaction near the melting point of A1 is specula-
tive, but probable; a monotectic reaction near the melting
point ofA1203 is established fairly well. The displacements
in temperature and composition of these three-phase
equilibria from the melting points of pure A1 and stoichio-
metric A1203 are believed to be slight, probably not
measurable for the eutectic. Data for the three-phase equi-
libria and the pure-metal transformation are summarized
in Table 1.
Terminal Solid Solution, (AI). At low hydrostatic pres-
sures, (A1), with a very limited range of compositions, ex-
hibits only the fcc structure (Table 2). Because A1 assumes
a hexagonal structure at hydrostatic pressures greater
than 20.5 GPa [King3], it is predictable that (A1) trans-
forms similarly at high pressures, but no specific studies
were reported.
The (A1) phase exists stably only at 02 fugacities less than
or equal to those in Table 3, at which it is saturated with
respect to aA1203. No credible measurement of the solu-
bility of O in (A1) was reported. The concentration of dis-
solved O in solid (A1) saturated with respect to aA1203 is
smaller than that in eutectic liquid (A1) (see section below)
and is probably not measurable with existing techniques.
Numerous determinations of O in A1 that were reported
fail to distinguish between dissolved O and O present as
oxide. The assertion of [30Har] that 0.64 at.% O is present
in solid solution in (A1) is obviously an error.
Liquid, AI-Rich. Liquid (A1) exists stably only at low 02
fugacities. At extremely low 02 fugacities, a short liquidus
branch is considered to exist for liquid (A1) coexisting with
solid (A1). Its terminus at a postulated eutectic (Table 1) is
displaced in concentration and temperature by a very
small, unknown amount from the melting point of pure A1.
No experimental data on this liquidus or the eutectic point
were found. The O content in liquid (A1) at the eutectic
temperature was estimated with other values along the
liquidus on the ~A1203 side in Table 4. The two values in
Table 4 differ by five orders of magnitude, but they indi-
cate that the O content of eutectic liquid (A1) is less than
3 • 10 -s at.% O. The O in solid (A1) at the eutectic is less
than that in liquid (A1) and the aA1203 is essentially stoi-
chiometric.
Table 3 Fugacities of 02 in Equilibrium
with aAl=03 and Solid or Liquid (AI) [78Cha]
Temperature, 02 fugacity, Temperature, 02 fugacity,
~ Pa ~ Pa
25 ............. 1 . 6 • 1 0 -'80 726.8 ........ 3 . 9 x 1 0 -43
226.8 ............ 1 . 7 x 1 0 lol 1226.8 ........ 1 . 7 • 1 0 23
660.5 ............ 2 . 5 • 1 0 -47 1726.8 ........ 1 . 0 x 1 0 -13
When it is O-saturated, liquid (A1) is in equilibrium with
solid aA1203, from the temperature of the eutectic to that
of the monotectic (Table 1). Calculated 02 fugacities corre-
sponding to the equilibrium along this liquidus are listed
in Table 3.
Liquid (A1) is saturated with respect to aA1203 at very low
concentrations of dissolved O. These amounts, as distinct
from those in suspended oxide, are ignored in industrial
practice as being too small to harm properties of cast A1. In
experimental work to determine O solubility in liquid (A1),
[22Czo] used gaseous 02 and estimated the amounts dis-
solved from the blowhole volumes observed after casting.
This technique for determining the liquidus branch is in-
valid. Analyses of specimens of A1 for dissolved O were
made by [28Jan], [31Low], [31Ste], [45Slo], [56Sch], and
[67Gib], with the values observed ranging from 0.0002 to
0.03 at.% O. Because the conditions of preparing these
materials were not adequately reported, conclusions may
not be drawn concerning the relationship of these O con-
centrations to those in oxide-saturated liquid A1.
Three recent publications contain relationships that allow
O concentrations along the liquidus between the eutectic
and the monotectic temperatures to be calculated. [8lOts]
and [82Lia] based their relationships on enthalpy/entropy
correlations estimated for O in other solvents; [81She]
based his on extrapolation of solubility data for Fe-rich
Fe-A1-O alloys. The concentration values on the liquidus
calculated with the [8lOts] and [81She] equations (Table
4), although quite different, are both possible; those of
[8lOts] are preferred because of the long extrapolation
involved in the method of [81She] and his identification of
the solid as A1304. The solubilities calculated with the
equation of [82Lia] for the standard Gibbs energy of solu-
tion of O in A1 are unacceptable because they are too large
and they decrease with increasing temperature. The liq-
uidus from the eutectic to the monotectic temperature
must still be regarded as quite uncertain.

Bulletin of Alloy Phase Diagrams Vol. 6 No. 6 1985 549

AI-O
Table 4 0 Concentrations in Liquid (AI) Saturated
with Respect to AI Oxide
Temperature, O concentration, at.% O
~ [8lOts]
660.5 ................... 2.9 • 10 s
726.8 ................... 1.6 x 10-7
926.8 ................... 8.8 x 10 6
1126.8 ................... 1.5 • 10 4
1226.8 ................... 4.7 x 10 4
1326.8 ................... 1.3 • 10 3
1526.8 ................... 6.6 x 10-3
1726.8 ................... 2.4 x 10 2
Note. Calculatmns from equations of [8lOts] from correlatmns and of
[81She] from extrapolations
Aluminum Oxide, aAl=O3, aAl203 is only one of several
identified polymorphic forms with the same stoichiometry.
A broad consensus holds that aA1203 is the only stable
form ofA1203 [Hansen]; that view has been accepted here.
(Forms of A1203 other than aA1203 are discussed in the
"Other Phases" section.) Deviations from the stoichiomet-
ric composition in aAl.~O3 were not determined or even
detected chemically. Compositions were not stated for the
nonstoichiometric compounds reported by [76Got].
At all temperatures up to its melting point, aA1203 has a
trigonal structure, which may be described alternatively
as hexagonal (Table 2). The unit cell dimensions in Table
2 are the selected values in the [Pearson2] and [Landolt]
compilations. These values were also quoted by [60Swa]
from his own work. No observation of a pressure-induced
phase transformation in aA1203 at 20 ~ was reported by
[65Har], who measured changes in the unit cell dimen-
sions over the pressure range from 0 to 30 GPa.
In the condensed system up to the monotectic temperature,
aA1203 can coexist stably only with (A1) or liquid (A1). At
O2 fugacities above those for its coexistence with those
phases, aA1203 is the only stable condensed phase. (Liquid
and solid O are not considered.)
The thermodynamic data. for aA1203 were compiled and
reviewed by [78Cha] and also compiled by [82Pan].
[78Cha] utilized subsequently published NBS data for the
heat capacity [82Dit]. Differences between [78Cha] and
[82Pan] values below the melting point of aA1203 were
slight; both compilations indicate a heat of formation of
- 1 6 7 6 kJ/mol A1203 at 25 ~
The melting point of aA1203 was measured by numerous
investigators. [63Sch] compiled the measurements from
1911 to early 1963 and converted the values to those on the
IPTS-48 temperature scale. Subsequently, determinations
were made by [63Che], [65Bla], [65Git], [66Kan], [66Sch],
[66Urb], and [67Sch]. The measurements of [67Sch],
which paid careful attention to environmental effects,
produced a value of 2054 ~ (IPTS-68) in vacuum. This
value was adopted in [78Cha] and [82Pan] and has been
accepted here.
There were only a few attempts to establish the liquidus
from the melting point of aA1203 to the monotectic tem-
perature. [34Bau] interpreted their experimental results
as indicating that this liquidus terminated 39 ~ below the
melting point of aA1203 at a eutectic point with 59.5 at.%
O, where solid A1203, liquid A1203, and a compound,
AlsO9, coexisted. These data and interpretation were dis-
550 Bulletin of Alloy Phase Diagrams Vol. 6
credited by [66Git| and [68Yan] on the grounds that the
melts were in contact with C (graphite). [68Yan] showed
that the liquidus found by [34Bau] resembles that for the
A1203-A14C3 system. [55Coc] reported r162 points" of
[81She]
mixtures of A1 and a A1._,O3held, in all but one instance, on
1.6 x 10 ,3 W or Ta supports. Apart from questions of contamination
5.1 x 10 ~2 from support material, it is unclear from the description of
1.6 x 10 8 the technique whether the observations were actually
5.1 • 10 6 points on the liquidus. In any case, they were described in
5.1 x 10 5
3.8 • 10 4 the paper as '~too scattered for construction of a phase
1.1 x 10 2 diagram." [66Git] observed the condition of aA120~-rich
0.16 mixtures of A1 and aA1203 after heating to high tem-
perature and quenching. Precautions were taken to avoid
contamination by the support and enclosure materials. A
monotectic 15 ~ below the melting point of aA120:~ was
established. The O concentration on the liquidus at its
monotectic terminus was reported to be 59.14 at.% O, al-
though it was stated that a higher concentration was pos-
sible. In experiments resembling those of 166Git], [68Yan]
found no measurable lowering of the melting point of
aA120~ with A1 addition, but confirmed the monotectic
(termed a '~eutectic") reaction and the existence of two
liquid phases in samples heated "a little above or below"
the melting point of aA1203. From the microscopically-
observed volume of (A1), precipitated from Al-saturated
liquid A1203 after cooling, the location of the aA1203 liq-
uidus at its monotectic terminus was found to be displaced
less than 0.0012 at.% from stoichiometric A1203 (60 at.%
O). Such a small displacement of the composition implies
that the monotectic temperature would be indistinguish-
able from the melting temperature of stoichiometric
aA1203. In the absence of a basis for choosing between
[66Git] and [68Yan], their mean, 59.5 +- 0.5 at.% O for
the liquid A1203 composition and 2046.5 -+ 7.5 ~ is used
in Table 1 and Fig. 1. Extrapolation of the expression of
[8lOts] used for the Tal=le 4 calculation beyond its stated
limits of applicability yields the value 0.13 at.% O for
the O concentration in liquid (A1) at the monotectic tem-
perature. The results of [68Yan] and [66Git] agree on the
absence of oxides other than A1203 in the equilibrium con-
densed system.
Other Phases
The solid oxides other than a A 1 2 0 3 may be grouped in two
classes: (1) those with the composition A1203, and (2) those
with other stoichiometries.
Forms of AI203 Other Than aAI203. In addition to amor-
phous A1203, there are at least five such varieties of crys-
talline A1203, but many more were reported. In the history
of classifying them, it was difficult to establish the dis-
tinct, reproducible varieties that are single phase rather
than mixtures and to determine which are strictly binary
compounds. Nomenclature was also confusing, because the
same phase at times was given different designations and
different phases the same designation. These types of
A1203 may develop by oxidation of A1, decomposition of
compounds containing A1 and O, or heat treatment of
other A1203 varieties in transition to aA1203. Certain
so-called "aluminas," notably /3 and ~, were not strictly
binary compounds [34Mor]; other types, such as /~, ,,
and ~, were observed only as thin films on A1. Certain
massive varieties may incorporate residual impurities,
especially H, but it was not shown that these impurities
are essential for metastability.
No. 6 1985
 AI-O

All the crystalline forms of A1203 are constructed of Table 5 Crystal Structures of Metastable AI=03
stacked, close-packed layers of O ions, with A1 ions and Polymorphs (25 ~ MPa)
vacancies distributed on the tetrahedral and octahedral
sites among these O ions. Polymorphism arises from the Pearson Space Strukturbericht
Phase symbol group designation Prototype
possibilities for different O-layer stacking sequences and
disorder therein, from variations in the distribution of A1 TA1203. 99 cF56 Fd3m Hll A12MgO4
ions on their two types of sites, and from ordering among 8A1203... 9. . . . . . . . 6A1203
the A1 ions and vacancies on those sites. Because of these ~A1203... "'" C 2/ m "'" flGa20~
possibilities, not only are cubic, hexagonal, and tetragonal KA1203(a) . . . . . . . . . . . .
xA1203... "'" P 6 J m c m or . . . . . .
structures formed, but also others of lower symmetry. Con- P 6 / m m m or
fusion arose from the multiplicity of variations, because P63/mmc
small-step changes may be manifested in specimens with
different histories. Tables 5 and 6 contain information on (a)Called v by [Pearson2]. T~usually denotes a form indistinguishable
from 7.
well documented and widely (but not universally) accepted
metastable polymorphs that occur as substantially pure,
massive crystals. Even here, the question of effects of re- Table 6 Lattice Parameters of Metastable AI203
sidual H in stabilizing structures formed at lower tem-
peratures, for example, especially in T and X aluminas, Polymorphs (25 ~ 0.1 M P a )
has not been resolved fully. Transformation of the meta- [-Lattice parameters, nm
stable varieties to a may be slow, even at temperatures Phase | a b c J Comment Reference
well above 1000 ~ TA1203...0.7911 . . . . . . . . . [Landolt]
Metastable A1203 phases were described in a voluminous 0.7859 . . . . . . . . . [Pearson2]
literature, which was reviewed by [34Mor], [59Kal], ~A1203...0.796 "" 1.170 "" [Landolt]
[63Torl], [65Ply], [67Dra], [67Sto], and [70Lip]. In addi- 0.795 "" 0.779 "" [Pearson2]
tion, thermodynamic data for 6A1203, 7Al203, and KA1203 0A1203...1.183 0.292 0.564 fl = 104~ [Landolt]
1.124 0.572 1.174 fl = 103020' [Pearson2]
were compiled and reviewed by [78Cha] and those for KAl~O3...0.971 "" 1.786 "" [Landolt,
TA1203 were compiled by [82Pan]. [78Sri] compiled heats Pearson2]
of formation for the K, T, and ~ forms. [Pearson2] and xA1203...0.556 "" 1.344 "" [Landolt,
[Landolt] listed structures and unit cell dimensions not Pearson2]
only for the "pure, massive" varieties, but also for varieties
that were observed only with significant impurity con-
tents or in thin films. certain reflections in the XRD patterns, but the source of
the reflections was not isolated chemically and analyzed.
Solid Oxides that are not AI203. At least eight varieties of The existence of AlsO9 was postulated by [34Bau] to
A1 oxide in this class were reported: A120, A1403, A10, explain the occurrence of a maximum in the liquidus
A].~O2, AlsOg, A1304, A14OG, and A102. It is possible that observed with (A1) + A1203 mixtures in a C(graphite) cru-
none of these phases exists, even metastably. The occur- cible. [66Git] and [68Yan] suggested that the maximum
rence of other oxide phases with undefined compositions was a feature of the A1-O-C system and that AlsO9 does
was also reported by [55Coc], [62Das], and [68Pie]. In not exist.
many instances, the substances reported were produced
in systems involving other elements, for example, with C A possible spinel-type oxide, A1304, was reported to have
or Si present. This raises the possibility that the products formed when A1 reacted with air [19Rho]. Claims that this
were not pure compounds of A1 and O. Sometimes, there oxide formed in the reaction of A1203 with C at high tem-
was insufficient product for chemical analysis or even for perature [57Fill and in Fe-rich Fe-A1-O melts [81She]
XRD in stress-free, isolated conditions. Therefore, identi- were also made. Other investigators who made these types
fications with a particular stoichiometry were often weak. of experiments did not report finding A1304.
The reviews by [63Tor2] and [68Mac] are still essentially
current. The review of [68Mac] listed the references in
which A1403, A1202, A1406, and A102 were postulated or
Gaseous Species
reported to have been prepared. Evidence regarding A120, Oxide species occur in vapors of the system as well as
A10, AlsOg, and A1304 is now discussed briefly. single-element O and A1 species. A voluminous literature
exists concerning these gaseous oxides, among which A120
[51Bell claimed to have produced solid A120 by reaction of and A10 were well documented, while A1202 and A10~
a mixture of A1203, SiO2, and C at temperatures above were also reported. (A120:~ was not shown to be signifi-
1800 ~ The product was not analyzed chemically. Crys- cant.) The literature concerning the gaseous oxides was
tals identified as A120 and A10 were reported by [54Hoc], reviewed by [63Tor2], [68Mac], and [78Sri]. [68Yan] cal-
who obtained XRD patterns at high temperatures, indi- culated concentrations of gaseous species at 1727 ~ for
cating cubic structures. The solid identified as A120 oc- various A1/O ratios. The thermodynamic data for A120,
curred only between 1100 and 1600 ~ the solid identified A10, A1202, and A1Q gases were compiled and reviewed
as A10 occurred only above 1500 ~ These results were by I78Cha] and also compiled by [82Pan].
not confirmed. [68Yan] suggested that the diffraction pat-
terns of [54Hoc] were those of A1 carbide and A1 ortho-
tantalate, produced by reactions with contaminants. Cited References
[74Yam] claimed that A120 and A10 were formed at the 19Rho: J. G. A. Rhodin, "Chemistry of Aluminum and Aluminum
boundary between A1203 and the metal in oxidizing A1 foil Alloys," Trans. Faraday Soc., 14, 134-149 I1919); cited by
at 300 ~ The presence of suboxides was inferred from [68Mac]. (Meta Phases; Experimental)

Bulletin of Alloy Phase Diagrams Vol. 6 No. 6 1985 551

AI-O
22Czo: J. Czochralski, "The Solubility of Gases in Aluminum," Z.
Metallkd., 14(7), 277-285 (1922) in German. (Equi Diagram;
Experimental)
28Jan: G. Jander and W. BrSsse, "Quantitative Separations and
Determinations Through Volatilization with Hydrogen Chlo-
ride. 6th Report: On the Quantitative Determination of the
Oxygen Content of Aluminum Alloys," Z. Angew. Chem., 41,
702-704 (1928) in German. (Equi Diagram; Experimental)
30Har: T. Harada, "Oxygen in Aluminum and a Method for Its
Determination," Mem. Fac. Eng. Kyoto Imp. Unw., Ch~kashige
Anniv. Vol., 237-243 (1930}; Chem. Abst., 25, 2660 (1931). (Equi
Diagram; Experimental)
31Low' H. LSwenstein, "On the Oxygen Content of Aluminum
and Methods for its Determination," Z. Anorg. Chem., 199,
48-56 (1931) in German. (Equi Diagram; Experimental)
31Ste: R. Sterner-Rainer, "On the Occurrence of Small Amounts
of Gases and Oxides in Aluminum and A1-Alloys," Z. Metallkd.,
23, 274-282 (1931) in German. (Equi Diagram; Experimental)
34Bau: E. Baur and R. Brunner, "On the Surfaces of Melting in
the System Aluminum, Aluminum Oxide, Aluminum Carbide,"
Z. Elektrochem., 40(3), 154-158 (1934) in German. (Equi Dia-
gram; Experimental; #)
34Mor: G.W. Morey, "The Crystalline Form of Alumina," Bull.
Am. Ceram. Soc., 13, 79-80 (1934). (Crys Structure; Review)
45S1o: H.A. Sloman, "The Application of the Vacuum Fusion
Method to the Determination of the Oxygen, Hydrogen and
Nitrogen Contents of Non-Ferrous Metals, Alloys and Pow-
ders," J. Inst. Met., 71,391-414 (1945). (Equi Diagram; Experi-
mental)
51Bel; M. C. Beletskii and M.B. Rapoport, "Investigation of Be-
havior of Aluminum Compounds at High Temperatures," Dokl.
Akad. Nauk SSSR, 80, 751-754 (1951) in Russian. (Equi Dia-
gram; Experimental)
54Hoc: M. Hoch and H.L. Johnston, "Formation, Stability and
Crystal Structure of the Solid Aluminum Suboxides: A120 and
A10," J. Am. Chem. Soc., 76, 2560-2561 (1954). (Equi Diagram,
Crys Structure; Experimental)
55Coc: C.N. Cochran, "Aluminum Suboxide Formed in Reac-
tion of Aluminum with Alumina," J. Am. Chem. Soc., 77,
2190-2191 (1955). (Equi Diagram; Experimental)
568ch: H. Schmitt and H. Wittner, "Origin of the Nonmetallic
Impurities in Aluminum and Their Influence on Its Further
Working," Z. Erzbergbau Met., 9(9), 417-421 (1956) in German.
(Equi Diagram; Review, Experimental)
57Fil: N.E. Filonenko, I.V. Lavrov, O.V. Andreeva, and R.L.
Pevzner, "On the Alumina-Derived Spinel AIO 9Al~O3," Dokl.
Akad. Nauk SSSR, 115(3), 583-585 (1957) in Russian. (Equi
Diagram; Experimental)
59Kal: A.M. Kalinina, "The Polymorphism and Thermal Con-
versions of Aluminum Oxide," Zh. Neorg. Khim., 4(6),
1260-1269 (1959) in Russian; TR: Russ. J. Inorg. Chem., 4(6),
568-573 (1959). (Crys Structure; Review, Experimental)
60Swa: H.E. Swanson, M.I. Cook, T. Isaacs, and E.H. Evans,
Nat. Bur. Stand. Circular 539, 2, 20-23 (1960). (Crys Structure;
Review, Compilation)
62Das: E.M. DaSilva and P. White, "Electrical Properties of
Evaporated Aluminum Oxide Films," J. Electrochem. Soc.,
109(1), 12-15 (1962). (Crys Structure; Experimental)
63Che: V. Ya. Chekhovskoi and V.A. Petrov, "Melting Point of
Corundum," Izment. Tekh., (9), 26-28 (1963) in Russian; TR:
Meas. Tech. (USSR), (9), 751-753 (1963). (Equi Diagram; Ex-
perimental)
638ch: S.J. Schneider, "Compilation of the Melting Points of the
Metal Oxides," Nat. Bur. Stand. Monograph 68, 6-9 (1963).
(Equi Diagram; Compilation)
63Torl: K. Torkar, "Investigations of Aluminum Hydroxides and
Oxides, 12th Rep.: Final Results, Especially in the Field of the
Gamma Oxide," Monatsh. Chem., 94, 110-123 (1963) in
German. (Crys Structure; Review, Experimental)
63Tor2: N. A. Toropov and V. P. Barzakovskii, High Temperature
Chemistry of Silicates and Other Oxide Systems, Izv. Akad.
Nauk SSSR, Moscow (1963); TR: Consultants Bureau, New
York, 157-166 (1963). (Equi Diagram, Meta Phases, Thermo;
Review)
552 B u l l e t i n of Alloy P h a s e D i a g r a m s Vol. 6
65Bla: P.E. Blackburn, "Thermodynamics of Condensed and
Vapor Phases in the Binary and Ternary Systems of Be-B-O,
A1-B-O, Si-O, A1-Be-O and A1-B-F," NASA Rep., AD618523
(1965). (Thermo, Equi Diagram; Experimental)
65Git: G. Gitlesen and K. Motzfeldt, "The Melting Point of Alu-
mina and Some Related Observations," Acta Chem Scand,
19(3), 661-669 (1965). (Equi Diagram; Experimental)
65Har: H. V. Hart and H. G. Drickamer, "Effect of High Pressures
on the Lattice Parameters of A1203," J. Chem. Phys., 43(7),
2265-2266 (1965). (Pressure; Experimental)
65Ply: L. M. Plyasova and L. M. Kefeli, "The Structure of Alumi-
num Oxides," Kinet. Katal., 6(6), 1080-1084 (1965) in Russian;
TR: Kinet. Catal. (USSR), 6, 975-979 (1965). (Crys Structure,
Experimental)
66Git: G. Gitlesen, O. Herstad, and K. Motzfeldt, "Chemical In-
vestigations Concerning the Carbothermic Reduction of Alu-
mina," Selected Topics in High Temperature Chemistry, T.
F0rland, Ed., Universitetsforlaget, Oslo, Norway, 179-196
(1966). (Equi Diagram; Experimental; #)
66Kan: P.B. Kantor, E.N. Fomichev, and V.V. Kandyba,
~'Melting Point of Corundum as a Secondary Reference Point of
the Temperature Scale," Izmerit. Tekh., (5), 27-29 (1966) in
Russian; TR: Meas. Tech. (USSR), (5), 615-617 (1966). (Equi
Diagram; Experimental)
66Seh: S.J. Schneider and C.L. MeDaniel, "The Melting Point of
A120~ in Vacuum," Rev. Int. Hautes Temp. Rdfract., 3, 351-361
(1966). (Equi Diagram; Experimental)
66Urb: G. Urbain and M. Rouannet, "Secondary Points of Refer-
ence in the Practical Scale of Temperatures, Experimental De-
termination of the Temperature of Fusion of Alumina," Rev. Int.
Hautes Temp. R~fract., 3, 363-369 (1966) in French. (Equi Dia-
gram; Experimental)
67Dra: A.L. Dragoo and J.J. Diamond, "Transitions in Vapor-
Deposited Alumina from 300 to 1200 ~ J. Am. Ceram. Soc.,
50(11), 568-574 (1967). (Crys Structure; Experimental)
67Gib: D. Gibbons, G. Olive, E Sevier, and J.E. Deutschman,
"Determination of the Oxygen Content of Aluminum by 14
MeV-Neutron Radioactivation Analysis," J. Inst. Met., 95(9),
280-283 (1967). (Equi Diagram; Experimental)
67Seh: S.J. Schneider and C.L. McDaniel, "Effect of Environ-
ment Upon the Melting Point of A1203," J. Res. Nat. Bur.
Stand., A., 71A(4), 317-333 (1967). (Equi Diagram; Experi-
mental)
67Sto: L. Stoica, "Alumina. Characteristics and Structural Data
Obtained by X-Ray Diffraction," Rev. Rom. Chtm., 18, 543-551
(1967) in Romanian. (Crys Structure; Review)
68Mac: K.J.D. Mackenzie, "The Oxides of Aluminlum Other
than Al:O3," J. Br. Ceram. Soc., 5, 183-193 (19681. (Meta
Phases; Review)
68Pie: J.M. Pierard, "Analysis of Solids by Determination of
Properties Related to Their State of Aggregation," Ind. Chtm.
Belge, 33(Spec. No.), 151-154 (1968) in French; Chem. A bst , 70.
31184n (1969). (Meta Phases; Experimental)
68Yan: H. Yanagida and F. A. KrSger, "The System AI-O," J. Am.
Ceram. Soc., 51(12), 700-706 (1968). (Equi Diagram, Crys
Structure, Thermo; Experimental; #)
70Lip: B. C. Lippens and J.J. Steggerda, Physical and Chemical
Aspects of Adsorbents and Catalysts, B.G. Linsen, Ed., Aca-
demic Press, New York, 171-211 (1970). (Crys Structure, Meta
Phases; Review)
74Yam: S. Yamaguchi, "Note on the Aluminum Suboxides," J.
Appl. Phys., 45(7), 3207-3208 (1974). (Crys Structure, Meta
Phases; Experimental)
76Got: V. Gotovac and B. Lovre~ek, "Electrical Properties of Non-
stoichiometric A12+.O3,"Fiz~ka Yugosl., 8 (Suppl.), 63-64 (1976).
(Meta Phases; Experimental)
78Cha: M. W. Chase, Jr., J. L. Curnutt, R. A. McDonald, and A. N.
Syverud, "JANAF Thermochemical Tables, 1978 Supplement,"
J. Phys. Chem. R e f Data, 7(3), 793-940 (1978). (Thermo; Com-
pilation)
78Sri: R. D. Srivastava and M. Farber, "Thermodynamic Proper-
ties of Group 3 Oxides," Chem. Rev., 78(6), 627-638 (1978).
(Thermo; Review)
8lOts: S. Otsuka and Z. Kozuka, "Thermodynamic Study of
No. 6 1985

Oxygen in Liquid Elements of Group Ib to VIb," J. Jpn. Inst.
Met., 22(8), 558-566 (1981). (Thermo; Experimental, Theory)
81She: V. E. Shevtsov, "Thermodynamics of Oxygen Solutions in
the Fe-A1 System," Izv. Akad. Nauk SSSR, Met., (1), 60-65
(1981) in Russian; TR: Russ. Met., (1), 52-57 (1981). (Thermo;
Theory)
82Dit: D. A. Ditmars, S. Ishihara, S. S. Chang, and G. Bernstein,
"Enthalpy and Heat-Capacity Standard Reference Material:
Synthetic Sapphire (aAl~O~) from 10 to 2250 K," J. Res. Nat.
AI-O
Be-O
Bur. Stand., 87(2), 159-163 (1982). (Thermo; Experimental)
82Lia: W.W. Liang, "Prediction of Solubility of Oxides in Liquid
Fe-A1-O, Co-A1-O, Ni-A1-O and Cu-A1-O Alloy," Z. Metallkd,,
73, 369-375 (1982). (Thermo; Theory)
82Pan: L.B. Pankratz, Thermodynamic Properties of Elements
and Oxides, Bull. 672, U.S. Bur. Mines (1982). (Thermo; Com-
pilation)
# Indicates presence of a phase diagram.

A1-O evaluation contributed by H.A. Wriedt, 148 Washington Street, Pittsburgh, PA 15218. This work was supported by Amerman Society for Metals.
Literature searched through 1983. Part of the bibliographic search was provided by ASM. Dr. Wrmdt is the ASM/NBS Data Program Category Editor for
binary oxygen alloys.

The Be-O (Beryllium-Oxygen) System

9.01218 15.9994

By H. A. Wriedt
Consultant

Equilibrium Diagram t r a g o n a l s t r u c t u r e (flBeO) a t h i g h e r t e m p e r a t u r e s ; and

(4) the gas. The peroxide, BeO2, is u n s t a b l e even at mod-
The e q u i l i b r i u m p h a s e s of the Be-O system are: (1)the e r a t e l y e l e v a t e d 02 fugacities; it is questionable w h e t h e r
liquid; (2)the t e r m i n a l solid solution based on Be with it has been p r e p a r e d at all. A r e p o r t e d solid oxide, Be20,
very limited range, which has a cph s t r u c t u r e (aBe) at and a monoclinic form of Be a r e not e q u i l i b r i u m phases.
lower t e m p e r a t u r e s a n d a bcc structure (flBe) a t h i g h e r The crystal structures of phases r e p o r t e d in the l i t e r a t u r e
t e m p e r a t u r e s ; (3)the Be oxide compound, b e r y l l i a or bro- are listed in Tables 1 and 2.
mellite, BeO, for which deviations from the stoichiometric No published d i a g r a m was found for t h i s system. The lo-
composition are u n k n o w n a n d small, and which has a hex- cations of t h e liquidus and of t h r e e - p h a s e equilibria in-
agonal structure (aBeO) a t lower t e m p e r a t u r e s a n d a t e - volving liquid are unknown; even the types of t h r e e - p h a s e
equilibria a r e unknown, a l t h o u g h a eutectic reaction a t
Table 1 Be-O Crystal Structure Data
low O concentrations was r e p o r t e d [32Slo]. D a t a for t h e
Struktur- three-phase t r a n s i t i o n s r e q u i r e d for d i a g r a m c o n t i n u i t y
Composition, Pearson bericbt Space and for t h e t r a n s i t i o n s in pure Be a n d BeO are given in
Phase at.% 0 symbol designation group Prototype
Table 3. A l a r g e l y schematic d i a g r a m is shown in Fig. 1 for
Stable (0.1 MPa) the r a n g e 0 to 50 at.% O.
(aBe) . . . . . 0 hP2 A3 P6Jmmc Mg
(flBe) . . . . . 0 cI2 A2 Im3m W Terminal Solid Solution, (Be). Solid (aBe) or (flBe) exists
aBeO . . . . . 50 hP4 B4 P63mc SZn stably only at O2 fugacities less t h a n or equal to those in
(wurtzite) Table 4, at which it is s a t u r a t e d w i t h respect to solid BeO.
flBeO . . . . . 50 tP6? C4? P4Jmnm O2Ti Although calculated with the a p p r o x i m a t i o n t h a t Be ac-
(rutile)? tivity is u n i t y in the s a t u r a t e d solutions, these fugacity
Other phases values are not affected appreciably, because the solubility
(Be) . . . . . . . 0 . . . . . . Clcl or ... of O in (Be) is very small at these t e m p e r a t u r e s .
C 12/c 1 At 0.1 M P a and t e m p e r a t u r e s from a m b i e n t up to 1270 ~
Be20? . . . . . 33.3 cF12 C1 Fm3m CaF2
the stable c r y s t a l l i n e form of pure Be is cph aBe, and from.

Table 2 Be-O Lattice Parameter Data

Composition, Temperature, Lattice parameters, nm - -
Phase at.% 0 ~ I a b c I Comment Reference

Stable (0.1 MPa)

(aBe) . . . . . . . . . . . . 0 20.5 0.22858 ~ 1 7 6 1 7 6
0.35843 ... [63Mac]
(/3Be) . . . . . . . . . . . . 0 1260 0.25515 . . ~
. . . . . . [62Sin]
aBeO . . . . . . . . . . . . 50 21 0.26979 ~ 1 7 6
0.43772 ... [62Bel]
flBeO . . . . . . . . . . . . 50 2103 0.475 , ~
0.274 "" [65Smi]
Other phases
(Be) . . . . . . . . . . . . . . 0 (a) 0.549 0.610 0.410 fl = 98.5 ~ [81Fuk]
Be~O? . . . . . . . . . . . . 33.3 (a) 0.5413 . . . . . . . . . [59Amo]
(a) Presumably room temperature, but unspecified.

Bulletin of Alloy P h a s e D i a g r a m s Vol. 6 No. 6 1985 553