PHASE DIAGRAMS FOR CERAMISTS: SUPPLEMENT NO.

1
BY HOWARD F. MCMURDIEAND F. P. HALL*

INTRODUCTION
The original compilation of phase diagrams was made by 1 . P. Hall and Herbert
Insley and was published as the October, 1933, issue of The Journal of The American
Ceramzc Soctety. These authors then followed with a supplement, published as the
April, 1938, issue of the same Jozimal, and with another complete compilation which
was published as Part I1 of the Sovember, 1947, issue of this Journal.
The following compilation is the first supplement to the Sovember, 1947, issue. It
includes corrections of errorst and omitted diagrams as well as those published since
the 1917 compilation was printed.
It is to be understood that temperatures are given in degrees centigrade and the
compositions are given in weight percentage unless otherwise stated on the individual
diagram.

ERRATA, NOTES, AND COMMENTS

Page 6 (ii) and Page 7, Fig. 6. (Corrected Fig. 6. ander Findlay a n d A. N. Campbell, Phase Rule a n d
Note on caption t o Fig. 6 and first paragraph of Its Applications, 8th ed., pp. 114 and 121. Dover
(ii).) Publications, New York, 1945. x v +
313 pp. 163 +
In a two-component condensed system (constant figs.
Pressure), -k F = c + 1 and F = 3 - p. In Page 13, ( d ) , second paragraph, lines 6-9, should
order for t h e sys- read:
t e m t o be invari- . . . ; from d to 0 , t h e tangent intersects an
a n t ( F = O ) , three extension of A B - A , hence A crystallizes again a n d
phases must exist A B is partially resorbed; a t 0, A is once more par-
in equilibrium. tially redissolved while A B a n d C cryTtallize o u t ,
Such a condition, a n d t h e final products of crystallization are A , A B ,
however, can never a n d C.
B U exist i n a solid solu-
Cornposltlon
tion series as shown Page 23, Fig. 41.-System BaO-SiOz.
F I G . 6. (corrected).-Supersedes in Fig. 6, because In t h e reference hy P. Eskola, t h e date (122)
Fig. 6 , page 7. there are never should read (1922).
Binary systems with a single more t h a n two
solid solution: ( A ) ,system with phases present, i.e., Page 24, Fig. 47.-System CaO-SiO?.
a maximum melting point a t C,
which is not a compound; (5), solid solution and T h e compound 3CaO.SiOz is stable only i n t h e
system with a minimum melting liquid solution. temperature range of about 1300O t o lYOO°C. Above
point a t C, which is not a eutec- T h e system can a t 1900°, i t decomposes into a - 2 C a 0 . S i 0 2 and C a O ,
tic. n:) point become below 1300°C., i t decomposes into p-2CsO. SiOz
Handbuch der Metallphysik.
Edited by Georg Masing 1-01. invariant and t h e a n d CaO. E. T. Carlson, J . Research Natl. Bur.
11, Die heterogenen Gleichge- equilibrium curves Standards, 7 [5]893-903 (1931); R P 381.
wichte, by Rudolf 1-ogel, p. 241. must be continuous
Akademische Verlagsgesell- Page 25, Fig. 51.-System Fc-Fez03.
schaft, Berlin, 1937. in contrast t o a
invariant More recent work i n t h e system Fe-Fe203 is
shown in Fig. 510, page 156.
point (eutectic or peritectic) which is a point of dis-
continuity on t h e curve. Page 26, Fig. 52-System Fe-Fe304.
Such points designating maxima a n d minima, More recent work in the system Fe-Fe203 is
including t h e melting points of congruently melting shown in Fig. .Oli , page 156,
compounds, a t which t w o phases become identical i n
composition, are known as indifferent points. Alex- Page 29, Fig. 69.-System MgO-Zr02.
More recent work o n zirconia (Zr02) suggests t h a t
* The authors are, respectively, chief, Constitution and t h e temperature-stability relation shown o n this
Microstructure Section, Sational Bureau of Standards, diagram is doubtful.
Washington, D. C., and Director of Research, Pass and
Seymour, Inc., Syracuse, Yew York. Page 34, Fig. 92.-System SiOz-ZrOz.
t The authors wish to acknowledge the assistance of A revised a n d corrected diagram in t h e system
many friends in pointing out the errors that appeared
in the 1947 compilation of phase diagrams. SiOz-ZrOz is shown in Fig. 513, page S57.
154
 Phase Diagrams Supplement No. 1 155

Page 40, Fig. 113.-System Si02-KeO-91203. 4SiOs. Page 86, Fig. 286.-System Na2O-CaO-AI2O3-SiO2.
The eutectic temperature represented by the The field designated as diopside should be labeled
dashed horizontal line a t 1100°C. has been more anorthite.
accurately located a t I150 +
20°C. by the original
investigators. J. F. Schairer and N. L. Bowen, Page 90, Fig. 298.-System NazO. AI2O3.2SiOr-
Comet. read. SOC. gkal. Finlandc, KO. 20 (Eskola Vol.); CaO .A1203.2Si02.
Bz~ll.comm. gaol. Finlande, KO. 140, p. 67 (1947). Two fields are labeled carnegieite liquid. +
Page 67, Fig. 209.-Sysiem Ca0-Al2O3-SiO2. The lower of these fields should be carnegierite +
nephelite.
The compound desig~iated 3 C a 0 . 5A1203 is most
probably Ca0.2A1203. J. R. Goldsmith, J . Geol.,
56, 80-81 (1918). Page 119, Fig. 401.-System 2Fez03.P205-2Fe203.-
3P205.
Page 68, Fig. 213.-System 3Ca0.5A1203-2Ca0.-
The vertical line at approximately 3'77, Fe de-
A1203. SiOa.
notes a compound Fe20s.Pz05. This compound
The compound designated 3CaO. 5A41203 is most should be Fes03.P205.
probably CaO.2&03. J. K. Goldsmith, J . Geol., 56,
80-8 1 ( 1948).
Page 132, Fig. 450.-System H20-Ca0-Al2O3.
Page 83, Fig. 276.-System Zn0-A1203-SiOz. The reference was omitted and should read: L. S.
The positions of the boundary lines, isotherms, and KTells, u'.F. Clarke, and H. F. McMurdie, J . R e -
invariant points are given in mole percentage. The search S a t l . B u r . Standards, 30 [5] 403 (1943); K P
positions of the compounds are incorrectly given in 1539.
weight percentage. Their proper positions in mole
percentage are as follows: Page 134, Figs. 456 and 457.
ZnO Ah08 SiOz
The reference given is incorrect and should read:
2110.A120, 50 50
22110. SiOl 66'/3 331/3 H. von Wartenberg, H. J. Reusch, and E. Saran,
3A120a.2Si02 60 40 Z . anorg. u. dlgem. Chem., 230 [ 3 ] 267 (1937).
____ -

LIST OF ILLUSTRATIONS
GENERAL D I A G R A M S Fig. Page
Fig. Page 525 Na20 .A1?03.2SiOz-CaO .AlrOa. -
2SiOz--2Ca0. AlzOa. Si02 162
6 (corrected). 154 526 ( n.- for
A1?03.2SiOz-CaO. AlnOs
2SiO2-2CaO.Al?03.SiO:!
P\Ta20.

A. M E T A L O X I D E SYSTEMS glasses) 162

II. Systems Containing Two Oxides
System B, SYSTEMS C O N T A I N I N G N O N M E T A L OXIDES,
Fig. No. HALIDES, etc.
508 (13A) BaO-BzOd 156 I. Fluorides otily
509 (14A) BeO-SiO2 156
(23) Fe-02 ( a ) Two Fluorides
510 Fe-Fe,>Os 156 527 (4A) LiF-BeF2 162
511 (43) PbO-$id2 157 528 (8)
\ ,
NaF-B eF1 16%
512 (4SA) ZnO-BzOa 157 ( b ) T h k e Fluorides
513 (56) SiOZ-ZrOz 157 529 (2A) KF-NaF--MgF2

111. Systems Containing Three Oxides VII. Fluorides +

Metal Oxides
514 (9A) K20-ZnO-Si02 158 (b) Three Materials
515 (15) Li20-AIz0,-SiOz 158 (6) CaFz-CaO-SiOz
516 LiaO.SiOZ-LiQO .AliO:j. 4Si02 158 530 CaFp-CaO-2CaO. SiO, 163
517 Liz0 .SiOz-LizO .AlzOa 14Si02-Si 0 2 159
( n for glasses)
518 L i ? 0.SiOn-Liz0 .A1203.4SiOS-SiO2 159 D. LIQUIDUS CURVES
519 Li20.SiO?--LiZO.AlzO;,'4Si02-Si02 159
520 (53A) PbO-Bz03-Si02 160 11. Three-Oxide Complexes
52 1 Pb0-B203-SiO2 (more than 75% 160
PbO) (7) MgO-All0 $-Zr02
522 PbO--B&-SiOg ( nfor glasses) 161 531 ZrOz-MgQ 'A1203 and ZrOz 3 M g 0 . -
523 (60) ZnO-BsOs-SiO2 161 A1203 161

IV. Systems Containing Four Oxides F. TEMPERATURE-DEFORMATION D I A G R A M S

(10) Al2O8-SiO2-ZrO2
532 Al2Oa-Si0Z-Zr02. SiOz 161
156 Journal of The American Ceramic Society

A. METAL OXIDE SYSTEMS

II. Systems Containing Two Oxides

(1 3A) EaO-BnO3

1400 -

800 j ~ 0 0 . 4 ~L,
~ 0 2 Ba0;4B203 Ba0+2B203 dBaTB203 -
1450; Bo0.2B2O3 UBoOB20, 3 B 0 0 B 2 4
I I
0 20 40 60 80 100
8203 BaO
FIG.508.-System BaO-BtO3.
E. M. Levin and H. F. McMurdie, J . Research Natl.
Bur. Standards, 42 [2] 135 (1949); RP 1956.

(1 4A) BeO-siOp

2300

L tquid
2/00
FIG.510.-System Fe-FetOa, a t a total pressure of one
atmosphere. This represents more recent work than that
shown in Figs. 51 and 52.
L. S. Darken and R. W. Gurry, J . A m . Chem. SOC.,68

1700

/mo
110
___________-
I670 O

2BeOStO,+BeO
,
_ _ _ _I _ B_ _: I _------ I

ZBeQ~StO,+StO,~
-\i
[5] 799 (1946).

Be0 26eQ&O~--' 90,

0 20 40 60 80 100
FIG.509.-System BeO-SiOt.
R. A Morgm and F. A. Hummel, J . A m .
Ccrczm. Sac., 32 IS] 255 (1949).
 Phase Diagrams Supplement No. 1 157
(43) PbO-SiOn
(56) SiOs-ZrOn
I I I I I I
- - 28001 I I I I I I I I I 1
-
900 -
'.
'.

\
\
4 \
Liquid I \
I

4
\
( L) 2400 -1 I
\
\
\
-1 \
I \
Quartz I ZrOz SS \
2200 -I I +
Liquid
\
\
\
-I \
(L) \
I \
I 1
2000 - I I
I
I 1
700 -
I I
- I I
-

,I 1
Pb+O iZPb;SiOzi ZPbOSiO,
t
j34PbOSi0, f)l)PbO.SiO, Pb05,iOz Quartz

1600 - i ZrSiO, ZrSiO,+SiO2 08 %

l 6 O k i I I , I I I I I I I It
74Pb0.Si02 T4PbO.Si0,

0 10 ?a 30
FIG.513.-System SiOz-ZrOe. Revised and corrected dia-
Pb3 SiO,-- gram, superseding Fig. 92.
FIG.511.-Svstem PbO-SiO,
R. F. Geller, A. S. Creamer, and E. N. Bunting, J . Re- Revised by R. F. Geller and S. M. Lang, Xational Bu-
search Natl. Bur. Standards, 13 [2] 243 (1934); RP 705. reau of Standards.

(48A) ZnO-BnO3

' , " " ' " - I

ZnO
FIG. 512.--Svstcm ZnO-B1Oz.
E. Ingerson, G. W. Morey and 0. E. Tuttle, A m . J . Sci.,
246 [l] 38 (1948).
15s Journal of The American Ceramic Society

111. Systems Containing Three Oxides

(9A) Kn0-Zn0-SiOe
ZnO

1400 -
n
1300 - Liquid
- (L)

1200

---
1000 Li20.Si02+J3-Spodumene
I I I I I I I I I

0 20 40 60 80 100
Li20.Si02 Weight percent Li20.Al2O3.4SiO2
(Spodumene)
FIG.514.-System Kz0-Zn0-Si02. FIG.516.-Systeni LiaO.SiOz-LipO.AlzOs.4SiOs.
E. Ingerson, G. W. Morey, and 0. F. Tuttle, Am. J. Sci., Rustum Roy and E. F. Osborn, J . Am. Chem. Snc.., 71
246 [l] 33 (1948). [ 6 ] 2091 (1949).

(15) LinO-Als03-SiOn

P- LzOA4Q 8SiQ PETALITG

R- 40 A J ~ , ~ ~ ~ ~ I T ORTUOCLA~E"
U I U M
S- LsO Al,O, 4Sq SPOWMEM
C-L@ AI2OS2Sq UKQYPTITL

FIG.515 -System LizO-AI~O~-SiOz.

Rustum Roy and E. F. Osborn, J . Am. Chem. Snc., 71 [6] 2086 (1949).
 Phase Diagrams Supplement No. 1 159
(1 5) LinO-AIz03-SiOz (concf.)
SiO,
(1.459)

lUP66 PUA5CS

WPLL PUA515

Li20.Si0, Li20.AI20j4SiO2
(1.557) ,(1.517) FIG. 519.-Systeni LizO.SiOz-Li20.A1.0,9.4SiO~-Si02.
FIG. 517.-System Li20~Si0,-LizO~A1~03~4Si0~-Si0~, re- Phase relations just below 975 "C. showing three-phase
fractive indices of glasses. boundaries.
Rusturn Roy and E. F. Osborn, J . Am. Chem. SOC.,71 Rustum Roy and E. F. Osborn, J . IZna. Chrni. SOC.,71
[S] 2090 (1949). [ 6 ] 2095 (1949).

I 423'

FIG.518.-Systern LizO.SiO2-LisO .A1203. 4Si02-Si02.

Rustum Roy and E. F. Osborn, J . A m . Chem. SOL,71 [6] 2092 (1949).
160 Journal of The American Ceramic Society
 Phase Diagrams Supplement No. 1 161
(53A) PbO-Bp03-SiOn (concL)

do475 Lp.5 LC4 /.p

La& /$a5 L0S L059 db6j

Lt85 1.,505 Ib54 L059 465 lb72

443
L463
20 PP bo 8 Pb0
FIG. 522.-System Pb0-B2O3-SiOZ,average refractive indices of glasses.
R. F. Geller and E. N. Bunting, J . Research Natl. Bur. Standards, 23 [8] 279
(1939); R P 1231.

(60) ZnO-Bn03-SiOn IV. Systems Containing Four Oxides

(5) Nan0-Ca0-Aln03-SiOn
1600

1500

1400

1300

1200 L+,=
Ne+Mel+L\
I l l 1 I I I I I ’
ZnO SiO, 0 20 40 60 80 I(
FIG.523.-System ZnO-B203-SiOz. The curve repre- 2Ca0.AI,03~Si0, N0,O.A l,03. 2Si 0,
senting the composition of the lighter liquid layer, Lz,is
displaced from its proper position; LZ probably contains FIG.524.-System N a 2 0.A1208.2Si0~-2Ca0.AIZO~ .-
less thau 1% ZnO. SiOz, showing nonbinary nature (MEL = melilite, N E
E. Ingerson, G. W. Morey, and 0. F. Tuttle, A m . J . Sci., = nepheline CG = carnegieite).
246 111 39 (1948). R. G. Smalley, J . Geol., 55 [1]31 (1947).
1G2 Journal of T h e American Ceramic Society

(5) NanO-CaO-Aln03-Si02 (concl.)

CaO.AI20,. 2 Si 0, CaO,Al, ;2 sio,

.I:
2 C a 0 . A I,O,~SiO, Na20~A1,0,~2S i0,
FIG. 525.-System h-a,O. A1203.2SiOz-Ca0. AleOt.2Si0,- FIG. 526.-System P\'a,O. AlzO3.2SiOs-Ca0 .A1203.2SiOy-
2Ca0 .Al20~.SiO2. 2'2x0. A12Ot. SiO,, refractive indices of glasses.
J. R. Goldsmith, J . Geol., 55 [ 5 ] 389 (1947). J. R. Goldsmith, J . Geol., 55 [5] 388 (1947).

B. SYSTEMS CONTAINING NON-METAL OXIDES, HALIDES, etc.

I. Fluorides Only
( a ) T w o Fluorides
(8) NaF-BeFn

(4A) LiF-BeFe
600 I I I I I I

300
B e 5 +Li,BeF,
I 0 20 40 60
0 20 40 60 80 100 BeF, NaF(mol %) NQF+
BeF, LiF (mol %) LiF
FIG. 528.-System NaF-BeF2, high-BeFz, region (melting
FIG.527.-System LiF-BeF2. point of NaBeFt not determined).
D. M. Roy, Rustum Roy, and E. F. Osborn. To be pub- D. M. Roy, Rustum Roy, and E. F. Osborn. T o be
lished. published.
Phase Diagrams Supplement No. 1 163

0
0
0
164 Journal of The American Ceramic Society

D. LIQUIDUS CURVES F. TEMPERATURE-DEFORMATION

DIAGRAMS
II. Three-Oxide Complexes
(1 0) AlnO3-SiOn-ZrOn
(7) M3O-AlnO3-ZrOe

0 20 40 60 80 100
ZrO, (Wt.%)
FIG.531.--Systems MgO.ALOa-ZrO2 and 3Mg0.-
AI2O3-ZrO2 (fusion temperature of MgO-AlzO3 and
of 3Mg0.A1203with additions of ZrOa). FIG. 532.-System AleOa-SiOe-Zr02 .SiOz, cone-fusion
diagram of mixtures (numbers represent fusion point in
I. Ya. Sal'dau and N. A. Zhirnova, Bull. acad. terms of Orton cones).
xi. U.R.S.S., Classe sci. chim., 6 , 669 (1945). R.F. Rea, J . Am. Ceram. Soc., 22 [3] 96 (1939).