4234144 (1)

4;^^
^ ^ ^
ORNL-2548
Chemistry General
TID-4500 (15th ed.)
PHASE DIAGRAMS OF NUCLEAR REACTOR MATERIALS

R. E. Thoma, Editor
OAK RIDGE NATIONAL LABORATORY

operated
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ORNL-2548
Chemistry General
TID-4500 (15th ed.)
C o n t r a c t N o . W-7405-eng-26
REACTOR CHEMISTRY
DIVISION

R. E. Thoma, Editor
D A T E ISSUED
OAK RIDGE NATIONAL LABORATORY

Oak Ridge, Tennessee
operated by
UNION CARBIDE CORPORATION
for the
U.S. ATOMIC ENERGY COMMISSION
CONTENTS
INTRODUCTION
1. METAL SYSTEMS
1.1.
1.2.
1.3.
1.4.
The
The
The
The
System
System
System
System
Silver-Zirconium
IndiumZirconium
AntimonyZirconium
LeadZirconium
2. METAL-FUSED-SALT SYSTEMS
2.1.
2.2.
2.3.
2.4.
2.5.
The
The
The
The
The
Sodium Metal-Sodium Halide Systems

Potassium MetalPotassium Halide Systems
Rubidium Metal-Rubidium Halide Systems
Cesium MetalCesium Halide Systems
Alkali Metal-Alkali Metal Fluoride Systems
3. FUSED-SALT SYSTEMS
3.1.
3.2.
3.3.
3.4.
3.5.
3.6.
3.7.
3.8.
3.9.
3.10.
3.11.
3.12.
3.13.
3.14.
3.15.
3.16.
3.17.
3.18.
3.19.
3.20.
3.21.
3.22.
3.23.
3.24.
3.25.
3.26.
3.27.
3.28.
3.29.
3.30.
3.31.
3.32.
3.33.
The
The
The
The
The
The
The
The
The
The
The
The
The
The
The
The
The
The
The
The
The
The
The
The
The
The
The
The
The
The
The
The
The
System
System
System
System
System
System
System
System
System
System
System
System
System
System
System
System
System
System
System
System
System
System
System
System
System
System
System
System
System
System
System
System
System
LiF-NaF
LiF-KF
LiF-RbF
LiF-CsF
NaF-KF
NaF-RbF
KF-RbF
LiF-NaF-KF
LiF-NaF-RbF
LiF-KF-RbF
NaF-KF-RbF
NaBF^-KBF^
NaF-FeFj
NaF-NiFj
RbF-CaFj
LiF-NaF-CaFj
NaF-MgFj-CaFj
NaF-KF-AIFg
LiF-BeFj
NaF-BeF^
KF-BeFj
RbF-BeFj
CsF-BeFj
LiF-NaF-BeFj
LiF-RbF-BeFj
NaF-KF-BeFj
NaF-RbF-BeFj
NaF-ZnFj
KF-ZnFj
RbF-ZnFj
LiF-YFj
LiF-ZrF^
NaF-ZrF^
2
4
6
8
9
9
10
11
12
13
14
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
32
33
34
36
38
40
42
44
46
47
48
49
50
51
52
54
3.34.
T h e System K F - Z r F ^
56
3.35.
3.36.
T h e System R b F - Z r F ^
The System C s F - Z r F ^
57
58
3.37.
The System L i F - N a F - Z r F ^
60
3.38.
3.39.
The System N a F - K F - Z r F ^
T h e System N a F - R b F - Z r F ^
62
64
3.40.
3.41.
3.42.
3.43.
3.44.
3.45.
3.46.
3.47.
3.48.
The
The
The
The
The
The
The
The
The
System
System
System
System
System
System
System
System
System
NaF-CrFj-ZrF^:
NaF-CeF3-ZrF4
LiF-CeFj
NaF-HfF^
LiF-ThF^
NaF-ThF^
KF-ThF^
RbF-ThF^
BeFj-ThF^
T h e Section N a F - C r F j - Z r F ^
66
67
68
70
72
73
74
76
77
3.49.
T h e System B e F j - U F ^
3.50.
The System M g F ^ - T h F ^
78
79
3.51.
T h e System L i F - B e F j - T h F ^
80
3.52.
T h e System N a F - Z r F ^ - T h F ^
82
3.53.
T h e System L i F - U F g
84
85
3.54.
T h e System L i F - U F ^
3.55.
T h e System N a F - U F j
86
3.56.
3.57.
3.58.
3.59.
3.60.
The
The
The
The
The
88
90
91
92
93
System
System
System
System
System
NaF-UF^
KF-UF^
RbF-UF^
CsF-UF^
ZrF^-UF^
3.61.
T h e System S n F j - U F ^
94
3.62.
T h e System P b F j - U F ^
95
3.63.
3.64.
T h e System T h F - U F ^
The System L i F l N a F - U F ^
96
98
3.65.
T h e System L i F - K F - U F ^
3.66.
T h e System L i F - R b F - U F ^
102
3.67.
T h e System N a F - K F - U F ^
103
101
3.68.
T h e System N a F - R b F - U F ^
104
3.69.
3.70.
3.71.
3.72.
3.73.
3.74.
3.75.
3.76.
3.77.
3.78.
3.79.
3.80.
The
The
The
The
The
The
The
The
The
The
The
The
108
110
113
114
116
119
124
125
126
127
128
130
System
System
System
System
System
System
System
System
System
System
System
System
LiF-BeFj-UF^
NaF-BeF2-UF4
NaF-PbFj-UF^
KF-PbFj-UF^
NaF-ZrF^-UF^
LiF-ThF^-UF^
NaF-ThF^-UF^:
LiF-PuFj
LiCI-FeClj
KCI-FeClj
NaCI-ZrCI^
KCI-ZrCI^
T h e Section 2 N a F . T h F 4 - 2 N a F . U F 4
3.81.
T h e System L i C I - U C l 3
131
3.82.
3.83.
The System L i C I - U C I ^
T h e System N a C I - U C I g
132
133
3.84.
T h e System N a C i - U C I ^
134
4.
3.85.
The System K C I - U C I ^
135
3.86.
3.87.
3.88.
T h e System R b C I - U C I g
The System C s C I - U C I ^
T h e System K 3 C r F g - N a 3 C r F ^ - L i 3 C r F g
136
137
138
O X I D E A N D H Y D R O X I D E SYSTEMS
139
4.1.
4.2.
4.3.
4.4.
4.5.
The
The
The
The
The
139
140
141
142
143
4.6.
T h e System Ba(OH)2-Sr(OH)2
System
System
System
System
System
SiOj-ThOj
LiOH-NaOH
LiOH-KOH
NaOH-KOH
NaOH-RbOH
144
5. AQUEOUS SYSTEMS
145
5.1.
T h e System U O j - P j O ^ - H j O , 25C Isotherm
145
5.2.
T h e System U O j - H j P O ^ - H j O , 25C Isotherm
146
5.3.
The System U ( H P 0 4 ) 2 - C l 2 0 7 - H 2 0 , 25C Isotherm
147
5.4.
The System U 0 3 - N a 2 0 - C 0 2 - H 2 0 , 26C Isotherm
148
5.5.
Portions of the System T h 0 2 - N a 2 0 - C 0 2 - H 2 0 , 25C Isotherm
150
5.6.
5.7.
5.8.
5.9.
5.10.
The System N a 2 0 - C 0 2 - H 2 0 , 25C Isotherm

S o l u b i l i t y of Uranyl Sulfate in Water
T w o - L i q u i d - P h a s e Region of U O j S O , in Ordinary and Heavy Water
The System U O 3 - S O 3 - H 2 O
C o e x i s t e n c e Curves for T w o L i q u i d Phases in the System
UO2SO4-H2SO4-H2O
5 . 1 1 . T w o - L i q u i d - P h a s e Region of the System U O 2 S O 4 - H 2 S O 4 - H 2 O
5.12. T w o - L i q u i d - P h a s e C o e x i s t e n c e Curves for U O , R i c h Solutions in
the System U O 3 - S O 3 - H 2 O With and Without HNO3
5.13. S o l u b i l i t y of UO3 in H 2 S O 4 - H 2 O Mixtures
5.14. E f f e c t of E x c e s s H . S O . on t h e Phase E q u i l i b r i a in Very D i l u t e
153
156
158
160
164
166
167
168
5.15.
UO2SO4 Solutions
S e c o n d - L i q u i d - P h a s e Temperatures o f U O j S O . - L i j S O . Solutions
169
170
5.16.
S e c o n d - L i q u i d - P h a s e Temperatures for U O . S O . Solutions C o n t a i n i n g
5.17.
L i . , S O , or BeSO,
S e c o n d - L i q u i d - P h a s e Temperatures for BeSO^ Solutions C o n t a i n i n g UO3
171
172
5.18.
5.19.
T h e System N i S 0 4 - U 0 2 S 0 4 - H 2 0 at 25C
P h a s e - T r a n s i t i o n Temperatures in Solutions C o n t a i n i n g C u S O . ,
173
UO2SO4, a n d H j S O ^
The E f f e c t of CuSO, and N i S O , on P h a s e - T r a n s i t i o n Temperatures:
0.04 m U O j S O ^ ; 0.01 m H j S O ^
5 . 2 1 . T h e System U 0 3 ^ C u O - N i O - S 0 3 - D 2 0 at 300C; 0.06 m SO3
5.22. S o l u b i l i t y of Nd2(S04)3 in 0.02 m UO2SO4 Solution C o n t a i n i n g 0.005 m
174
H2SO4 (180-300C)
5.23. S o l u b i l i t y of La2(S04)3 in U O j S O ^ Solutions
5.24. S o l u b i l i t y of CdSO^ in UO2SO4 Solutions
5.25. S o l u b i l i t y of C s S O ^ in U O j S O ^ Solutions
5.26. S o l u b i l i t y of Y2(S04)3 in UO2SO4 Solutions
5.27. S o l u b i l i t y of Ag2S04 in U O j S O ^ Solutions
5.28. S o l u b i l i t y at 250C of BaSO^ in UO2SO4-H2O Solutions
177
178
179
180
181
182
183
5.20.
5.29.
S o l u b i l i t y of H2WO4 in 0.126
5.30.
Phase S t a b i l i t y of H2WO4 in 1.26 M UO2F2
and 1.26 M U O j S O ^
175
176
184
186
5.31.
T h e System U 0 2 ( N 0 3 ) 2 - H 2 0
188
5.32.
Phase E q u i l i b r i a of UO
(Aqueous System)
190
5.33.
S o l u b i l i t y of Uranium T r i o x i d e in Orthophosphoric A c i d Solutions
191
5.34.
S o l u b i l i t y of Uranium T r i o x i d e in Phosphoric A c i d at 250C
192
5 . 3 5 . S o l u b i l i t y of UO3 in H3PO4 Solution

5.36. The System U 0 2 C r 0 4 - H 2 0
5.37. V a r i a t i o n of L i 2 C 0 3 S o l u b i l i t y w i t h UO2CO3 C o n c e n t r a t i o n at Constant
193
194
CO Pressure (250C)
T h e System L i O - U O 3 - C O 2 - H 2 O at 250C and 1500 psi
The System T h ( N 0 3 ) 4 - H 2 0
H y d r o l y t i c S t a b i l i t y of Thorium N i t r a t e - N i t r i c A c i d and Uranyl
Nitrate Solutions
5 . 4 1 . The System T h 0 2 - C r 0 3 - H 2 0 at 25C
5.42. Phase S t a b i l i t y of T h 0 2 - H 3 P 0 4 - H 2 0 Solutions at High Concentrations
195
196
197
5.38.
5.39.
5.40.
of T h O j
vi
and HF in S t o i c h i o m e t r i c Concentrations
198
199
200

INTRODUCTION
This compilation presents the phase diagrams for possible materials for nuclear reactors
developed at the Oak Ridge National Laboratory over the period 195059.
It represents the
efforts of certain personnel in what are now the Chemical Technology, Metallurgy, Chemistry, and
Reactor Chemistry Divisions of ORNL.
This document also contains diagrams originated by
other installations under contract to ORNL during that interval. In addition, a few diagrams from
the unclassified
literature have been included when they form part of completed systems
sequences.
No general discussion of the principles of heterogeneous
phase equilibrium has been
included since excellent discussions are available in many well-known publications.
Equilibria
in several of the fused-salt systems presented below have been described in some detail in a
recent publication by Ricci.
Nor has any attempt been made to assemble the phase equilibrium
data on reactor materials available from many other sources.
For such information the reader is
referred to other recently published compilations of phase diagrams
and to the several new
works dealing specifically with nuclear reactor materials.

While some of the diagrams presented below are the result of fundamental researches, most
were obtained in support of the ORNL programs in development of fluid-fueled reactors.
Others
have been developed as a consequence of ORNL interests in reprocessing of nuclear fuels,

reactor
metallurgy, production of uranium and thorium from raw materials, and studies of
mechanisms of corrosion.
Much of the research effort was devoted to searches for systems of direct use as fluid fuels
or blanket materials; unpromising systems were often given only casual attention. The diagrams
in this collection, accordingly, vary widely in the degree of completeness of examination.
brief description of the status of the work is presented in each case; in a few cases, where no
detailed description of the system has been published, the available data have been included
with the diagram.
J. E. Ricci, Guide to the Phase
Diagrams
of the Fluoride
^ J . F . Hogerton and R. C. Grass ( e d s . ) . The Reactor

T . Lyman (ed.), Metals Handbook,
Systems,
Handbook,
ORNL-2396 (Nov. 19, 1958).
vol 2, AECD.3646 (May 1955).
American Society for Metals, Cleveland, Ohio, 1948.
F. A. Rough and A. A. Bauer ( e d s . ) . Constitution

1958).
of Uranium and Thorium
E. M. Levin, H. F . McMurdie, and F . P . Hall, Phase

Society, Columbus, Ohio, 1956.
Diagrams
E. M. Levin, H. F . McMurdie, and F . P . Hall, Supplement

American Ceramic Society, Columbus, Ohio, 1959.
Alloys,
for Ceramists,
to Phase
BMI-1300 (June 2,
The American Ceramic
Diagrams
for Ceramists,
The
B. Y a t e s , Materials for Use m Nuclear Reactors,

Information Bibliography,
IGRL-IB/R-15 (2nd e d . ) ,
1958.
o
H. H. Hausner and S. B. Roboff, Materials for Nuclear Power Reactors,
Reinhold Publishing Corp.,
New York, 1955.
O
B, Kopelman (ed.)# Materials
for Nuclear
Reactors,
McGraw-Hill Book Co., New York, 1959.
1. METAL SYSTEMS
1.1. The System SilverZirconium
J . 0 . Betterton, Jr., and D. S. Easton, " T h e Silver-Zirconium System," Trans, Met. Soc,
A/ME 212, 470-75(1958).
A detailed investigation was made of the phase diagram of silverzirconium, particularly in
the region 0 to 36 at. % Ag.
The system was found to be characterized by two intermediate
phases, Zr2Ag and ZrAg, and a eutectoid reaction in which the /S-zirconium solid solution decomposes into a-zirconium and Z r j A g .
It was found that impurities in the range 0.05% from the
iodide-type zirconium were sufficient to introduce deviations from binary behavior; with partial
removal of these impurities an increase in the a-phase solid solubility limit from 0.1 to 1.1 at. %
Ag was observed.
UNCLASSIFIED
ORNL-LR-DWG 18989
u S huLE PHASE
a- S NGLE PHASE WITH A TRACE OF SECOND PHASE
DAV TWO PHASE
THREE PHASE
FILLED SYMBOLS NDICATE METALLOGRAPHIC SAMPLES
WHICH WERE CHEMICALLY ANALYZED FOR SILVER CONTENT
-O-O ' V
V
SILVER (at %)
Fig.
at.
1.1a.
The
System
Silver-Zirconium
in
the
Eutectoid
Region
(0-6
% Ag).
UNCLASSIFIED
ORNL-LR-DWG 18988A
1400
""^
\
M,
_v\
1300 /3 + LIQ
LIQ
' + LIQ,
1200
1100
y+S
a:, 1000
/8+y
900
800
o
/
a+>
SINGLE PHASE
DAV TWO PHASE

FILLED SYMBOLS INDICATE METALLOGRAPHIC SAMPLES
700
WHICH WERE CHEMICALLY ANALYZED FOR SILVER CONTENT

10
15
20
25
30
SILVER (at %)
Fig.
l.lfe.
T h e System SilverZirconium in the Region 036 a t . % A g .
35
1.2.
The System IndiumZirconium

J . 0 . B e t t e r t o n , J r . , and W. K. N o y c e , " T h e E q u i l i b r i u m Diagram of IndiumZirconium in the
Region 0 - 2 6 at. pet I n , " Trans.

The
zirconium-rich
portion
Met. Soc. AlME 212, 3 4 0 - 4 2 (1958).

of the i n d i u m - z i r c o n i u m
phase diagram was determined as a
study of the e f f e c t of a l l o y i n g a t r i v a l e n t B-subgroup element, indium, w i t h zirconium in group

IVA.
The temperature of the a l l o t r o p i c t r a n s i t i o n was found to r i s e w i t h indium, terminating in a
p e r i t e c t o i d r e a c t i o n , |S(9.3% In) + y{22.4% In) ; ^ : : ^ - a ( 1 0 . 1 % In) at 1003C.
In this respect the
e f f e c t of indium is analogous to that of aluminum in z i r c o n i u m and titanium a l l o y s .
UNCLASSIFIED
ORNL-LR-DWG 18987
1300
1200
1100
1000
900
LiJ
Q.
800
700
600
500
6
INDIUM (at 7o)
Fig.
at. % In).
1.2a.
T h e System IndiumZirconium in the Peritectoid Region (013
BLANK
BLANK
UNCLASSIFIED
ORNL-LR-DWG 18983
1400
1300
1200
1100
UJ
ID
cr
Q.
1000
900
800
700
Fig. 1.3fe. The System Antimony-Zirconium in the Peritectoid Region ( 0 - 6 at. % Sb).
1.4.
The System LeadZirconium

G. D.
Kneip,
Jr.,
and J . 0 .
Betterton, Jr.,
cited
by
"Zirconium Equilibrium D i a g r a m s , " p 44383 in The Metallurgy
E. T .
Hayes
and W. L. O'Brien,
of Zirconium,
e d . by B. Lustman
and F. Kerze, Jr., McGraw-Hill Book C o . , New York, 1955.
UNCLASSIFIED
ORNL-LR-DWG 1375
1200
1100
/9
1000
LU
\A
o o
<r
900
UJ
Q_
c
c
=tll!
a+y
/
/ /
800
/3 + y
/
/
/
700
o îNf;LE PHASE
TWO PHASE
A THREIE PHASE
600
4
10
12
LEAD (at.%)
Fig.
1.4.
at. % Pb).
The System LeadZirconium in the Peritectoid Region (012
2. M E T A L - F U S E D - S A L T
2.1.
SYSTEMS
The Sodium MetalSodium Halide Systems

M. A . Bredig and J . E. Sutherland, " H i g h - T e m p e r a t u r e Region of the SodiumSodium H a l i d e
S y s t e m s , " Chem. Ann, Prog,
Rep. June 20, 1957, O R N L - 2 3 8 6 , p 119. Subsequent report on these
systems to be p u b l i s h e d .
UNCLASSIFIED
ORNL-LR-DWG. 21894A
< - MOLE FRACTION MX

.9 .8 .7 .6 .5 .4 .3 .2 .1
1200
iTson
\ \ I \
^ MOLE FRACTION MX
.9 .8 .7 .6 .5 .4 .3 .2 .1
"1 \ o COOLING CURVESJHIS WORK 1200
X EQUILIBRATION, MAB,JWJ,WTS
A EQUILIBRATION, HRB, MB
1100
1100
1080
lOOOii
1000
900
900
800
800
SOLID SALT + LIQUID METAL
700
700
600
600
1100
ONE LIQUID
ONE LIQUID
-1100
1033
1000
C
TWO LIQUIDS
900
NaBr - Na
800
740
700
700
SOLID SALT+ LIQUID METAL \
SOLID SALT + LIQUID METAL
600
I
I I I I I I I I
.1 .2 .3 .4 .5 .6 7 .8 .9
MOLE FRACTION OF M E T A L S
LJ
LJ
L >600
.1 .2 .3 .4 .5 .6 7 ,8 .9
MOLE FRACTION OF M E T A L H
Fig. 2 , 1 . The Sodium MetalSodium Halide Systems.
2.2. The Potassium MetalPotassium Halide Systems

J. W. Johnson and M. A. Bredig, " M i s c i b i l i t y of Metals with Salts in the Molten State. I I I . The
Potassium-Potassium Halide Systems," / . Phys. Chem. 62, 604 (1958).
Complete miscibility of metal and salt exists in the KXK systems, X = F, C I , Br, and I, at
and above 904, 790, 727, and 717C, that is, as close as +47, +18, - 7 , and +22 respectively,
to the melting points of the salts.
The asymmetry of the liquid-liquid coexistence areas,
especially of the fluoride and chloride systems, as indicated by the consolute compositions
(20, 39, 44, and 50 mole % metal, respectively), is largely explained by the difference in molar
volumes of salt and metal. At the monotectic temperature, the solubility of the solid salts in the
liquid metal, as well as of the metal in the liquid salt phase, is much larger than in the case of
the sodium systems.
UNCLASSIFIED
ORNL-LR-DWG 2(481B
10
20
30
Fig. 2.2.
10
40
50 6 0
mole % K
70
80
I W t
90
T h e Potassium MetalPotassium Halide Systems.
2.3. The Rubidium MetalRubidium Halide Systems

M. A. Bredig and J . W. Johnson, "RubidiumRubidium Halide Systems," Chem. Ann. Prog.
Rep. June 20, 1957, ORNL-2386, p 122; M. A. Bredig, J . E. Sutherland, and A, S. Dworkin,
"Molten
Salt-Metal
Solutions.
Phase Equilibria," Chem. Ann, Prog, Rep, June 20, 1958,
ORNL-2584, p 73. Subsequent report on these systems to be published.
UNCLASSIFIED
ORNL-LR-DWG. 32909A
800
790
/ RbF-Rb
^
XX
\ .
- ^ .
773
750
scr^xRb-qizRb
700
696
RbBr-Rb
650
\
\
600
550
25
50
75
MOLE % Rb METAL
F i g . 2.3. T h e Rubidium MetalRubidium H a l i d e Systems.
2.4.
The Cesium MetalCesium Halide Systems

M. A . B r e d i g , H. R. B r o n s t e i n , and W. T . Smith, J r . , " M i s c i b i l i t y
Salts.
II.
of L i q u i d Metals w i t h
The PotassiumPotassium F l u o r i d e and CesiumCesium H a l i d e S y s t e m s , " / .
Am,
Chem, Soc. 77, 1454 (1955).

M i s c i b i l i t y in a l l proportions of cesium metal w i t h cesium h a l i d e s at and above the m e l t i n g
points of the pure s a l t s , and of potassium metal w i t h potassium f l u o r i d e 5 0 above the m e l t i n g
point
of the s a l t , o c c u r s .
The temperature-concentration
range of c o e x i s t e n c e of t w o
liquid
phases decreases in going from sodium to potassium systems and disappears altogether for the
cesium s y s t e m s .
The s o l u b i l i t y of the s o l i d h a l i d e s in the corresponding l i q u i d a l k a l i m e t a l s ,
at a given temperature, increases greatly w i t h increase of atomic number of the m e t a l .
UNCLASSIFIED
ORNL-LR-DWG. 37011
25
F i g . 2.4.
12
50
MOLE % METAL
75
T h e Cesium MetalCesium Halide Systems.
^00
2.5.
The A l k a l i MetalAlkali Metal Fluoride Systems

M. A .
B r e d i g , J . E.
Sutherland, and A . S. D w o r k i n , " M o l t e n SaltMetal Solu
E q u i l i b r i a , " Chem, Ann. Prog.
Rep, June 20, 1958, O R N L - 2 5 8 4 , p 73,
UNCLASSIFIED
O R N L - L R - D W G . 31067A
1300
1200
1100
1000
900
800.
700
600
Fig. Z 5 .
25
50
MOLE % METAL
75
The Alkali M e t a l - A l k a l i Metal Fluoride Systems.
100
3.
3.1.
FUSED-SALT SYSTEMS
The System L i F - N a F
A. G. Bergman and E. P. Dergunov, "Fusion Diagram of L i F - K F N a F , " Compt. rend. acad.
sci.
U.R.S.S. 3 1 , 753-54 (1941).

The system L i F - N a F contains a single eutectic at 60 L i F - 4 0 NaF (mole %), m.p. 652C.
UNCLASSIFIED
ORNL-LR-DWG 2 0 4 5 7
1000
^
900
800
"
700
^^-^
/652C
600
500
LiF
10
20
30
40
50
NaF (mole%)
60
Fig. 3.1. The System LiFNoF.
14
70
90
NaF
3.2.
The System L i F - K F
A. G. Bergman and E. P. Dergunov, "Fusion Diagram of L i F - K F - N a F , " Compt. rend. acad.
sci. U.R.S.S. 3 1 , 753-54 (1941).

The system L i F - K F contains a single eutectic at 50 LiF50 KF (mole %), m.p. 492C.
UNCLASSIFIED
ORNL-LR-DWG 35483
40
50
60
KF(mole%)
Fig. 3,2. The System L i F - K F .
15
3.3.
The System L i F - R b F
C. J. Barton, T. N. McVay, L. M. Bratcher, and W. R. Grimes, unpublished work performed at
the Oak Ridge National Laboratory, 1951-54.

Preliminary diagram.
Invariant Equilibria
Mole % L i F
in Liquid
Invariant
Temperature
Phase Reaction
at Invariant Temperature
Type of Equilibrlun
(C)
44
470
Eutectic
L ^ ^ ^ R b F -I- LIF-RbF
47
475
Perltectic
L +LIF;^
^LIF-RbF
General characteristics of the system have been reported by E. P. Dergunov, " F u s i o n Diagrams of the Ternary Systems of the Fluorides of Lithium, Sodium, Potassium, and Rubidium,"
Doklady Akad. Nauk S.S.S.R. 58, 1369-72 (1947).
UNCLASSIFIED
ORNL-LR-DWG 16145
900
~-.^
' '
600
500
,,
II
<> \
'
Ji
<>
<
u_
-Q
cr
u.
40
50
60
LiF (mole % )
Fig. 3.3, The System L i F - R b F .
16
3.4.
The System L i F - C s F
C. J . Barton, L. M. Bratcher, T. N. McVay, and W. R. Grimes, unpublished work performed
at the Oak Ridge National Laboratory, 1952-54.

Invariant
Mole % CsF
In Liquid
Temperature
Type of Equilibrium
Phase Reaction
55
495 5
Perltectic
LIF +L ^=^LIF-CsF
63
475 5
Eutectic
L V
(C)
'LIF-CsF + CsF
UNCLASSIFIED
ORNL-LR-DWG 14632
900
800
\
700
600
^x
\
\
500
.^ ^^
400
V)
O
li_l
300
LiF
10
20
30
40
50
CsF (mole %)
60
70
80
CsF
90
Fig, 3,4. The System LiFCsF.
17
3.5. The System N a F - K F

sci.
U.R.S.S. 3 1 , 753-54 (1941).

The system N a F - K F contains a single eutectic at 40 NaF-60 KF (mole %), m.p. 710C.
UNCLASSIFIED
ORNL-LR-DWG 35484
50
60
KF(mole7o)
Fig, 3,5. The System N a F - K F .
18
3.6.
The System NaF.RbF

C. J. Barton, J . P. Blakely, L. M. Bratcher, and W. R. Grimes, unpublished work performed
at the Oak Ridge National Laboratory, 1951.

The system NaF-RbF contains a single eutectic at 27 NaF-73 RbF
(mole %), m.p. 675 + 10C.

UNCLASSIFIED
ORNL-LR-DWG 35711
1000
1
\
\
950
\
S.
"^
\
900
N,
850
LJ
a:
a:
0-
5
u
800
.*
y ^
^<
}
750
\
\
/
\^
\
700
NoF
10
20
30
40
50
50
y
\..^
/:
\A
'
70
80
\\
90
RbF
RbF (mole 7ol
Fig. 3.6. The System N a F - R b F .
19
3.7.
The System KF-RbF

C. J . Barton, J. P. Blakely, L. M. Bratcher, and W. R. Grimes, unpublished work performed

The system K F - R b F contains a solid solution minimum at 28 K F -
72 RbF (mole %), m.p. 770 + 10C.
(0
20
40
IT^^^
50
RbF (mole %)
^_^__^
60
Fig, 3.7. The System K F - R b F .
20
. *
3.8.
The System L i F - N a F - K F
sci.
U.R.S.S. 3 1 , 753-54 (1941).

The
system L i F - N a F - K F
contains a single eutectic at 46.5 L i F - 1 1 . 5 NaF-42.0 KF
(mole %), m.p. 454C.
UNCLASSIFIED
ORNL-LR-DWG 1!99A
NaF
990
Fig. 3,8, The System L i F - N a F - K F .
21
3.9. The System L i F - N o F - R b F

C. J. Barton, L. M. Bratcher, J . P. Blakely, and W. R. Grimes, unpublished work performed
The system L i F - N a F - R b F contains a single eutectic at 42 L i F - 6
NaF-52 RbF (mole %), m.p. 430 10C.
The composition and temperature of the ternary peri-
tectic point have not yet been determined.

General characteristics of the system have been reported by E. P. Dergunov, "Fusion Diagrams of the Ternary systems of the Fluorides of Lithium, Sodium, Potassium, and Rubidium,"
Dergunov lists the composition and tempera-
ture of the ternary eutectic as 46.5 L i F - 6 . 5 NaF-47 RbF (mole %), m.p. 426C.
Fig. 3.9. The System L i F - N a F - R b F .
22
3.10. The System L i F - K F - R b F

C. J. Barton, J . P. Blakely, L. M. Bratcher, and W. R. Grimes, unpublished work performed
The system L i F - K F - R b F contains a single eutectic at 40 L i F - 3 2 . 5
KF-27.5 RbF (mole %), m.p. 440 10C.

856
f485
845
Fig. 3.10. The System L i F - K F - R b F .
23
3.11.
The System N a F - K F - R b F
C. J . Barton, L. M. Bratcher, J . P. Blakely, and W. R. Grimes, unpublished work performed

The system NaFKFRbF contains a single eutectic at 21 NaF-5
K F - 7 4 RbF (mole %), m.p. 621 + 10C.
990
710
Fig. 3.11. The System N a F - K F - R b F .
24
856
3.12.
The System NoBF^-KBF^
R. E. Moore, J . G. Surak, and W. R. Grimes, unpublished work performed at the Oak Ridge
National Laboratory, 1957.
The system NoBF . - K B F ^ contains a single eutectic at 88 N a B F ^ -
12 KBF . (mole %), m.p. 355C.
The dotted line was obtained from thermal effects representing
incompletely understood solid-phase transformations of KBF . and NaBF^.
UNCLASSIFIED
ORNL-LR-DWG35487
700
600
500
5 400
300
200
100
10
20
30
Fig. 3.1Z
40
50
NoBF. (mole7o)
60
70
80
90
The System NoBF^-KBF^.
25
3.13.
T h e System N a F - F e F j
R. E. Thoma, H. A . Friedman, B. S. Landau, and W. R. G r i m e s , unpublished work performed

at the Oak Ridge N a t i o n a l Laboratory, 1957.
P r e l i m i n a r y diagram.
Invariant
Phase Reaction
Mole % F e F ,
in Liquid
Temperature
30
680
Eutectic
L ^ = ^ N a F + NaF-FeF2
50
783
Congruent melting point
L^=?
63
745
Eutectic
L ; = ^ NaF-FeF, + FeF,
Type of Equilibriun
(C)
NaF-FeFj
UNCLASSIFIED
900
'
\
HJ
800
> - ^ ~~-^
!
\
\
y^
/
i
v^
Uo
z.
500
30
40
50
FeFj (mole %)
60
Fig. 3.13. The System N a F - F e F _ .
26
X'
70
80
3.14.
R.
The System N o F - N i F j
E. T h o m a , H. A . Friedman, B. S. L a n d a u , and W. R. Grimes, unpublished work performed
at the Oak Ridge N a t i o n a l Laboratory, 1957.

invariant Equilibria
Invariant
Mole % N i F ,
in Liquid
Phase Reaction
Type of Equilibrium
Temperature
{C)
23
795
50
57
Eutectic
- N a F H-NaF-NiF,
1045
::^ NaF-NiF,
1040
Eutectic
L ^^^NoF-NiFj + NiFj
UNCLASSIFIED
ORNL-LR-DWG 22344
(300
noo
900
u.
lio
2
600
NoF
to
30
40
Fig. 3.14.
50
NiF2(mole %)
60
70
80
90
The System N a F - N i F - .
27
3.15.
The System R b F - C o F j
C. J. Barton, L. M. Bratcher, R. J. Sheil, and W. R. Grimes, unpublished work performed at

the Oak Ridge National Laboratory, 1956.
Invariant
Mole % C a F ,
Temperature
in Liquid
Type of Equilibrium
(C)
760
50
57
Phase
Reaction
Eutectic
L ^ = i R b F -I- R b F - C a F ,
1110
L ^ ^
1090
Eutectic
L ^ ^ ^ R b F - C a F j + CaFj
RbF-CaF,
UNCLASSIFIED
O R N L - L R - D W G 17668R
1500
o THERMAL ANALYSIS DATA

VISUAL OBSERVATION DATA
(300
(200
700
40
20
F i g . 3.15.
28
50
CaFj (mole7o)
60
T h e System R b F - C a F j .
90
CaF,
3.16. The System L l F - N a F - C a F 2

C. J. Barton, L. M. Bratcher, and W. R. Grimes, unpublished work performed at the Oak
Ridge National Laboratory, 1955-56.
The system L i F - N a F - C a F j contains a single eutectic at 53 L i F -
36 N a F - 1 1 C a F j (mole %), m.p. 616C.
UNCLASSIFIED
ORNL-LR-DWG (2779R
-1350-
TEMPERATURES ARE IN C
COMPOSITION IN mole7o
5
'730^
6(2
A ^zpr<\
T T ^.
^
>\ 6 6 0 . * ^
>, 663,620 \745
DV
/6(5
"625
700 /
LiF
845 '
720/
^
/
800
/
770
660,6(5 8 3 5 6(8
750
NaF
'990
Fig. 3.16. The System L i F - N a F - C o F ,
29
3.17. The System NaF-MgF2-CaF2

C. J. Barton, L. M. Bratcher, J . P. Blakely, and W. R. Grimes, unpublished work performed
Com position of L quid

(mole %)
T e mperature
T y p e of
Solids Present
(C)
Equilibrium
NaF
CaFj
MgFj
65
23
12
745
Eutectic
N a F , N a F - M g F j , and C a F j
35
28
37
905
Eutectic
C a F j , M g F j , and N o F - M g F j
UNCLASSIFIED
ORNL-LR-DWG 17575R
COIVIPOSITION IN mole 7o
TEMPERATURE IN C
F i g . 3.17a.
30
The System N a F M g F , C a F ~
The
minimum temperature along the quasi-binary section N a F - M g F 2 - C a F 2
occurs at the
composition 36 N a F - 3 6 M g F 2 - 2 8 C a F j (mole % ) , at 910C.

The
existence of the compound N a r - M g F j was previously reported by A. G. Bergman and
E. P. Dergunov, Compt.
Ternary
follows:
sci.
rend. acad. sci.
U.R.S.S. 3 1 , 755 (1941).
systems of alkali fluorides with MgF2 have been reported by Bergman et al.
the system L i F - N a F - M g F j by A . G. Bergman and E. P. Dergunov, Compt.
U.R.S.S.
rend.
as
acad.
3 1 , 755 (1941); the system L i F - K F - M g F 2 by A. G. Bergman and S. P. Parlenko,
Compt. rend.acad.
sci.
U.R.S.S. 3 1 , 8 1 8 - 1 9 (1941); the system N a F - K F - M g F 2 by A. G. Bergman
and E. P. Dergunov, Compt.
rend. acad. sci.
U.R.S.S. 4 8 , 330 (1945).
UNCLASSIFIED
ORNL-LR-DWG 12780
1500
1
1400
y
y
1300
y
LU
1
1
Q: 1200
^^
<
u
y
y
1100
Q.
- 1000
"^-900
800
NaMgFj
y'
10
^T..
20
30
40
50
60
70
80
90
CoFg
CoFg (mole 7o)
F i g . 3.17fc.
The Subsystem N a F ' M g F j - C a F j .
31
3.18.
The System N a F - K F - A I F 3

No study has been made at the Oak Ridge National Laboratory of the
phase relationships occurring within the system NaFKFAlF,.
Phase diagrams have been
reported for the AIF^ binary systems, N a F - A I F j [P. P. Fediotieff and W. P. Iljinsky, Z. anorg.
Chem. 80, 121 (1913); also N. A. Pushin and A. V. Baskow, ibid. 8 1 , 350 (1913)] and K F - A I F 3
[P. P. Fediotieff and K. Timofeef, Z. anorg. u. allgem. Chem. 206, 265 (1932)].
71000
Fig. 3.18. The System N a F - K F - A I F j .
32
3.19.
The System L i F - B e F j
This phase diagram is a composite from several published sources
and from unpublished
data derived at the Oak Ridge National Laboratory (R. E. Moore, C. J. Barton, R. E. Thoma,
and T. N. McVay) and at the Mound Laboratory (J. F. Eichelberger, C. R. Hudgens, L. V. Jones,
and T. B. Rhinehammer).
Thermal gradient quenching data (ORNL) and differential thermal
analysis data (Mound Laboratory) have served to corroborate this composite diagram.
Invariant
Mole % B e F j
T emperature
in L i q u i d
Phase
T y p e of E q u i l i b r i u m
Reaction
at I n v a r i a n t T e m p e r o t u r e
(C)
33.5*
454
Peritectic
-l-LiF^=^2LiF'BeF,
52
355
Eutectic
L^^2LiF.BeF2
280
Upper temperature of
2 L i F . B e F 2 + BeF2
+ BeFj
LiF-BeF,
s t a b i l i t y for L i F ' B e F j
* R e f 3.
Roy, Roy, and Osborn have reported the presence of the compound LiF-2BeF2 in the system
L i F - B e F j although neither the Mound Laboratory nor the ORNL data have indicated the existence of this compound.
' D . M . R o y , R. R o y , and E. F. O s b o r n , ; . Am. Ceram.
Soc. 3 7 , 300 (1954).
^ A . V . N o v o s e l o v a , Y u . P. Simanov, and E. I. Y a r e m b a s h , / . Phys.
John L. Speirs, The Binary and Ternary Systems

Beryllium
Fluoride:
Phase Diagrams and Electrolytic
29, 1952.
Chem. (U.S.S.R.)
2 6 , 1244 ( 1 9 5 2 ) .
Formed by Calcium Fluoride, Lithium Fluoride, and

Studies,
P h . D . t h e s i s . University of Michigan, May
\
\
L\
\
E eFg -t- L I Q U D
^
_2LiF-
3eFo\_
LIQUID
L F + 2 L i F - B e F2
2 L i F - B e F 2 + B e F g ( H I GH QUARTZ TYPE)
1
-I
10
20
30
F i g . 3.19.
2LiF-BeF2
i^
be^g
40
50
BeFj (mole 7o)
U F ' B e F 2 - l - BeFg (HIGH QUARTZ

.
60
YPE)
.
1
1
L ( F - B e F 2 + B e F 2 ( L O W QUARTZ TYPE;
70
80
90
BeFj
T h e System L i F - B e F ,
33
3.20.
D.
The System N a F - B e F 2
M. Roy, R. Roy, and E. F. Osborn, " F l u o r i d e Model Systems:
III.
T h e System N a F -
B e F j and the Polymorphism of Na2BeF4 and B e F j , " / . Am. Ceram. Soc. 3 6 , 185 (1953).
Invariant Equilibria*
Invariant
Mole % B e F j
in Liquid
T emperature
Phase Reaction
Type of Equilibrium
(C)
31
570
Eutectic
L ^=i
33.3
600
L ^==^ a-2NaF-BeF2
320
Inversion
a-2NaF-BeF2 ^
225
Inversion
a'-2NaF-BeF2 ^ = ^ 7-2NaF-BeF2
43
340
Eutectic
L I
' a-2NaF-BeF2 + /S-NaF-BeFj
50
376 + 5
L ;
' ^'-NaF-BeF2
55
365
Eutectic
L ^ = i ^ ' - N a F - B e F j + BeF2
NaF + a-2NaF-BeF2
a'2NaF-BeF2
*Roy, Roy, and Osborn did not list invariant equilibria; those shown are estimates made from the reportec
work and from experiments performed at the Oak Ridge National Laboratory.
34
o
Uo
z.
= HIGH QUA
N
1-
= LOW QUAF
S ? 3
= ORNL DAT
+
CD
U.
O
1
'
\
\
OJ 3yniva3dW3i
OJ
1
z.
Uo
Li_
O
5 =1
J li
U-
(HQ) + LIQU
CD
O
--
^"
V. ^
u
jj
/
QOJ
C2
L
C
L
C0."
u.
LL
m
u_
o
Z
OJ
+
X
-1
CO
m
u_
OJ
CD
Li_
D
u5^
OJ
1
o
Z
LJ_
"7
U.
O
CD
i.
Li_
D
Z
OJ
OJ
LL
0
3
UL
0)
u.
o
E
0)
CM
to
00
3.21.
R.
The System K F - B e F j
E. Moore, C. J . Barton, L. M. Bratcher, T. N. McVay, G. D. White, R. J. Sheil, W. R.
Grimes, R. E. Meadows, and L. A. Harris, unpublished work performed at the Oak Ridge National
Laboratory, 1955-56.
Invariant
Mole % BeF2
In Liquid
Type of Equilibrium
Temperature
(C)
Phase Reaction
19
720
Eutectic
L F = ^ K F + 3KF-BeF2
25
740
L F=^3KF-BeF2
27
730
Eutectic
L F = ^ 3KF-BeF2 + a-2KF-BeF2
33.3
787
L ^=â-2KF-BeF2
685
Inversion
a- 2KF-BeF2 ^ ^ / S - 2 K F - B e F 2
52
390
Peritectic
A2KF-BeF2 + L
59
330
Eutectic
L ^ ^
KF-BeF2 + /3.KF-2BeF2
66.7
358
L ^=^
a-KF-2BeF2
334
Inversion
a - KF-2BeF2
72.5
323
Eutectic
L ^^-KF-2BeF2+
^=^KF-BeF2
?=^^-KF-2BeF2
BeF2
This system has been reported by M. P. Borzenkova, A. V. Novoselova, Yu. P. Simanov,

V. I. Chernikh, and E. I. Yarembash, "Thermal and X-Ray Analysis of the K F - B e F j System,"
Zhur. Neorg. Khim. 1, 2071-82 (1956).
36
UNCLASSIFIED
ORNL-LR-DWG (7574R
^
800
y^
\^ - 2 K F
BeFj
700
600
500
^^
>^
^^
OJ
CD
Lu
C\J
Q.
ro
OJ
400
03,
,a-KF-2B
\
300
^
u^
CM
L_
CD
(M
GO
^
20
40
50
BeFj (mole %)
^
60
90
BeF,
Fig. 3.21. The System K F - B e F 2 .
37
3.22.
The System R b F - B e F j
R. E. Moore, C. J . Barton, L. M. Bratcher, T. N. McVay, G. D. White, R. J . Sheil, W. R.

Grimes, and R. E. Meadows, unpublished work performed at the Oak Ridge National Laboratory,
1955-56.
Invariant
Mole % B e F j
in Liquid
Ti emperature
Type of Equilibrium
(C)
Phase Reaction
16
675
Eutectic
L ^ ^ RbF-I- 3RbF-BeF2
25
725
L ^=^3RbF-BeF2
27
720
Eutectic
L ^=i3RbF-BeF2 + 2RbF.BeF2
33.3
800
L ^^2RbF-BeF2
50.5
442
Peritectic
L + 2RbF-BeF2 ^=^RbF.BeF2
61
383
Eutectic
L ^ ^ RbF-BeF2 + RbF.2BeF2
66.7
464
L ^=^RbF-2BeF2
81
397
Eutectic
L ^ = ^ RbF-2BeF + BeF
This system has also been reported by R. G. Grebenshchikov, "Investigation of the Phase
Diagram of the RbF-BeF2 System and of Its Relationship to the BaO-Si02 System," Do^/aJy
Akad. Nauk S.S.S.R. 114,316(1957).
90
BeF,
Fig. 3.22. The System RbF-BeF2.
39
3.23.
The System C s F - B e F j
0. N. Breusov, A. V. Novoselova, and Yu. P. Simanov, "Thermal and X-Ray Phase Analysis
of
the System CsFBeF2 and its
Interrelationships
with MeF and BeF2 Systems," Doklady
Akad. Nauk S.S.S.R. 118,935-37(1958).
Mole % B e F j
in Liquid
40
Invariant
Temperature
Phase Reaction
Type of Eqij i l ibrium
(C)
14
598
Eutectic
L F = ^ CsF -F/e.3CsF-BeF2
23.5
659
Peritectic
a-2CsF-BeF
617
Inversion
a-3CsF-BeF2 F = ^ /3-3CsF-BeF2
33.3
793
Congruent me Iting point
L F = ^ a-2CsF-BeF2
404
Inversion
a-2CsF-BeF2 F=^/3-2CsF-BeF2
48
449
Eutectic
L F = ^ a-2CsF-BeF2 -i-a-CsF-BeFj
50
475
L f = ^ a-CsF-BeF2
360
Inversion
a-CsF-BeF2 F ^ /S-CsF-BeF2
140
Inversion
/3-CsF-BeF2 F = ^ y - C s F - B e F j
58.4
393
Eutectic
L F = ^ a-CsF-BeF2-t-/3-CsF-2BeF2
66.7
480
L ;
450
Inversion
a-CsF-2BeF2 F=^/3-CsF-2BeF2
77.5
367
Eutectic
L f = i /3-CsF-2BeF2 + BeF2
+ L ; = ^ a-3CsF-BeF2
' a-CsF-2BeF2
UNCLASSIFIED
ORNL-LR-DWG 35481
900
800
X
/
700
/
/
.^
r\
600
-<"-
X^'
^
500
, / ^
400
\ w
300
OJ
m
o
200
<00
CsF
10
20
0)
u5^
CD
CD
a>
CD
OJ
U-
LL.
LL
O
OJ
30
F i g , 3.23.
40
50
BeF, (mole 7o)
60
70
80
90
BeF,
T h e System C s F - B e F 2 .
41
3.24.
The System L i F - N a F - B e F j
R. E. Moore, C. J . Barton, W. R. Grimes, R. E. Meadows, L. M. Bratcher, G. D. White, T. N.

McVay, and L. A. Harris, unpublished work performed at the Oak Ridge National Laboratory,
1951-58.
Composition of Liquid
(mole %)
Invariant
Temperature
Solids Present
at Invariant Point
Type of Equilibrium
BeF,
;c)
58
27
480
Eutectic
NaF, L i F , and 2NaF-BeF2
41
36
328
Eutectic
L i F , 2NaF-BeF2, and
LiF
NaF
15
23
2NaF-LiF-2BeF2
20
40
40
355
2NaF-LiF-2BeF^
53
42
318
Eutectic
NaF-BeF2, 2NaF-BeF2,
and 2NaF-LiF-2BeF^
31.5
31
37.5
315
Eutectic
2LiF-BeF2, L i F , and
2NaF-LiF-2BeF^
*lnvariant equilibria shown in the phase diagram by the intersections of dotted-line boundary curves
hove not been determined with sufficient precision to be listed in the table.
Minimum Temperature on Alkemade Lines

Composition of Liquid (mole %)
Temperature
Alkemade Line
BeF,
(C)
56
28
485
2NaF-BeF2-LiF
26
37
37
340
2NaF-LiF-2BeF2-LiF
11
44
45
332
NaF-BeF2-2NaF-LiF-2BeF2
16
45
39
343
2NaF-BeF2-2NaF-LiF-2BeF2
30.5
31
38.5
316
2LiF-BeF2-2KaF-LiF-2BeF2
LiF
NaF
16
Phase relationships of two of the ternary compounds in this system have been reported by
W. John ["Silicate Models. V. NaLi(BeF4), a Model Substance for Monticellite, CaMg(Si04),"
Z. anorg. u. allgem. Chem. 276, 113-27 (1954); "Silicate Models.
VI.
Na3Li(BeF4)2, a New
Compound in the Ternary System N a F - L i F - B e F 2 , and Its Relation to Merwinite, Ca3Mg(SiO^)2,"

Z. anorg. u. allgem. Chem. Ill,
42
274-86 (1954)].
(r Q tr
. ^ C/) UJ
: D. <
R X< ^J
U.
CO
u.
iil
CO
3.25.
The System L i F - R b F - B e F 2
T. B. Rhinehammer, D. E. Etter, C. R. Hudgens, N. E. Rogers, and P. A. Tucker, unpublished

work performed at the Mound Laboratory.
Invariant Equilibria and Singular Points
Corr iposition of
Liquid (molle %)
Temperature
Type of
(C)
Equilibrium
Solid Phases Present
LiF
RbF
BeF2
40.0
20.0
40.0
485
+5
33.3
33.3
33.3
544
Incongruent
melting point of
L1F.RbF.BeF2
33.0
8.0
59.0
295
Eutectic
2 L i F - B e F 2 , 2 L i F - R b F - 2 B e F 2 , and B e F 2
26.0
12.0
62.0
305- - 3 2 0
Peritectic
2 L i F - R b F . 2 B e F 2 , R b F . 2 B e F 2 , and B e F 2
12.0
29.0
59.0
334
Quasi-binary
eutectic
2 L i F - R b F . 2 B e F 2 and
11.0
34.0
55.0
300 5
Eutectic
2 L i F - R b F . 2 B e F 2 , R b F . B e F 2 , and RbF.2BeF 2
11.5
35.5
53.0
335
Peritectic
2 L i F - R b F - 2 B e F 2 , L i F - R b F - B e F 2 , and R b F . B e F 2
9.0
40.0
51.0
380
Peritectic
L1F.RbF.BeF2, 2RbF.BeF2,and
50.0
8.0
42.0
426
Peritectic
L i F , 2 L i F - R b F . 2 B e F 2 , and 2 L i F . B e F 2
41.5
19.5
39.0
473
Quasi-fainary
eutectic
L . F and 2 L i F . R b F . 2 B e F 2
35.0
25.5
39.5
470
Peritectic
L r F , 2 L i F . R b F . 2 B e F 2 , and L i F - R b F - B e F j
23.0
40.0
37.0
530
Peritectic
L i F , 2 R b F . B e F 2 , and L 1 F . R b F . B e F 2
30.0
35.0
35.0
544
5
+5
+5
Maximum on the
boundary
L i F and L i F . R b F - B e F . ,
41.0
39.5
19.5
640
+5
Quasi-binary
eutectic
L i F and 2 R b F - B e F 2
43.0
50.0
7.0
527
+5
Peritectic
L i F , 3 R b F . B e F 2 , and 2 R b F . B e F 2
43.0
54.0
3.0
470
Peritectic
L i F , L i F - R b F , and 3 R b F - B e F 2
43.0
55.0
2.0
462
Eutectic
L i F - R b F , R b F , and 3 R b F - B e F 2
44
+5
+5
+5
5
5
5
Congruent
melting point
2LiF.RbF-2BeF2
RbF-2BeF2
RbF.BeFj
UNCLASSIFIED
ORNL-LR-DWG 38H3
BeF2
TEMPERATURE C
COMPOSITION mole 7o
LigBeF^
RbjBeFg
LiRbFj P E
RbF
Fig. 3.25. The System Li F - R b F - B e F ,
45
3.26. The System N a F - K F - B e F 2

R. E. Moore, C. J . Barton, L. M. Bratcher, T. N. McVay, and W. R. Grimes, unpublished work
performed at the Oak Ridge National Laboratory, 1952-55.
Phase relationships within the system NaF-KFBeF2 have not yet
become so well defined at the Oak Ridge National Laboratory that the compositions and temperatures of the invariant points may be listed.
UNCLASSIFIED
O R N L - L R - D W G 3S114
2
\548
TEMPERATURE IN C
COMPOSITION IN mole %
^QO-
a^2y^
KF 2 BeF,
"-365 ,
NaF BeF,
^-390
KF 2 BeFj
350^
400,
-450-
if-340 ,
-500-
750^
A 2KF BeFj
^
535^^
v\
'oS^
A__Af-720
fE-GZQ
^50N
~g50
T A ^ J K F BeFj
ÔQ
750
s950_^
'800
NaF^
990
\L
\J_
Fig.
46
3.26.
\//
A^
T h e System N a F - K F - B e P ,
M.
KF
"856
3.27. The System N o F - R b F - B e F j

R. E. Moore, C. J . Barton, L. M. Bratcher, and W. R. Grimes, unpublished work performed
Con-iposition of
L i q i lid (mole %)
Temperature
Type of Equilibrium
(C)
Solids Present at Invariant Temperature
NaF
RbF
BeFj
20.5
68.5
11.0
610
Eutectic
R b F , N a F , and 3 R b F . B e F 2
50
37.5
12.5
640
Quasi-binary eutectic
3 R b F ' B e F _ and N a F
46
38
16
635
Eutectic
3 R b F - B e F 2 , 2 R b F - B e F 2 , and N a F
45
37
18
650
2 R b F ' B e F _ and N a F
37
33
30
570
Peritectic
2 R b F - B e F 2 , N a F , and 2 N a F . 4 R b F . 3 B e F 2
52
15
33
477
Eutectic
2 N a F ' 4 R b F . 3 B e F 2 , N a F , and 2 N a F ' B e F 2
33
33.7
33.3
580
Peritectic
2 R b F - B e F 2 and 2 N a F . 4 R b F . 3 B e F 2
51.7
15
33.3
480
2 N a F - 4 R b F ' 3 B e F 2 and 2 N a F B e F _
UNCLASSIFIED
ORNL-LR-DWG 22343R2
BE
BP
CM
IM
TE
TP
BINARY EUTECTIC
BINARY PERITECTIC
CONGRUENT MELTING POINT
INCONGRUENT MELTING POINT
TERNARY EUTECTIC
TERNARY PERITECTIC
TEMPERATURES
ARE IN C
BeFg
CM 5 4 3
COMPOSITION IN mole 7o
BE 3 9 5
BE 375
BP440
RbF BeF,
IM440
2RbF BeFp
CM 8 0 0
BE 720
BE 375
BE 3 3 5
2NaFBeF2
CM 5 9 5
3RbF BeFp
CM 725
BE 5 7 0
BE 675,
Fig. 3.27.
T h e System N a F - R b P - B e F j .
3.28.
The System N o F - Z n P j

Ridge National Laboratory, 1952.
Invariant
Mole % Z n F j
Temperature
in L i q u i d
(C)
33
635
50
748 + 10
69
685
Phase
Reaction
at I n v a r i a n t T e m p e r a t u r e
Eutectic
L ,
NaF - H N a F - Z n F j
Congruent m e l t i n g p o i n t
L ?=i
NoF-ZnFj
Eutectic
L ^ = i NaF-ZnFj + ZnFj
UNCLASSIFIED
DWG 14627 R
tOGO
900
6 00
5 00
4001-
20
30
F i g . 3.28.
48
40
50
60
Zn Fp (mole %)
The System N a F Z n F j .
3.29.
C.
The System K F - Z n F 2
J . Barton, L. M. Bratcher, and W. R. Grimes, unpublished work performed at the Oak

Invariant
Mole % ZnF
in Liquid
Temperature
21
670
30
Phase Reaction
Type of Equilibrium
(C)
Eutectic
L ? = ^ K F + 2KF.ZnF2
720 + 10
Peritectic
L -fKF-ZnFj ;=^2KF-ZnF2
50
850 + 10
L ^=^KF-ZnF2
80
740 5
Eutectic
L ^ = ^ K F - Z n F 2 + ZnF2
UNCLASSIFIED
DWG (4625R
1000
900
800
700
lij
600
500
400
300
40
50
60
ZnF,
ZnFj (mole7o)
Fig. 3.29. The System K F - Z n F - .
49
3.30.
The System R b F - Z n F j
C. J . Barton, L. M. Bratcher, and W. R. Grimes, unpublished work performed at the Oak

Invariant
Mole % Z n F j
in Liquid
Temperature
{C)
Phase Reaction
Type of Equilibrium
21
595 10
Eutectic
L ;^
32
620 10
Peritectic
L + R b F - Z n F j F = ^ 2RbF-ZnF2
50
730 10
L f=^RbF.ZnF2
70
650
Eutectic
L I
' R b F + 2RbF.ZnF2
' RbF.ZnF2 + Z n F j
UNCLASSIFIED
DWG 1 5 3 4 9 R
1000
900
800
^ j ^ ^ ^ ^
700
(J,
T^
600
^ ^
C
Nl
500
b_
Q:
C
Nl
UQ:
C\J
400
RbF
10
20
30
50
Fig. 3.30. The System RbF-ZnFjp
50
70
90
ZnF,
3.31.
The System L i F - Y F j
R.
E. Thoma, C. F. Weaver, and H. A. Friedman, unpublished work performed at the Oak

Invariant
Mol e
in
YF3
L i q uid
T emperature
Type of Equilibrium
(C)
Phase Reaction
19
695
Eutectic
L ^ ^ L i F + LiF-YFg
49
815
Peritectic
L + Y F g ^ ^ ^ L1F.YF3
UNCLASSIFIED
ORNL L R - D W G 38116
1400
1300
1200
1100
1000
900
800
700
500
Fig. 3.31. The System L i F - Y F 3 .
51
3.32.
The System L i F - Z r F ^
R. E. Moore, F. F. Blankenship, W. R. Grimes, H. A. Friedman, C. J . Barton, R. E. Thoma,

and
H. Insley, unpublished work performed at the Oak Ridge National Laboratory, 1951-56.
Invariant
Mole % Z r F ^
in Liquid
52
Temperature
Phase Reaction
Type of Equilibrium
(C)
=i L i F + a - 3 L i F - Z r F ^
21
598
Eutectic
L ^
25
662
L ^ - a-3LiF'ZrF^
475
Inversion
a-3L i P . Z r F ^ ^=^
470
Decomposition
/^-3L i F ' Z r P ^ ^ = ^ L i F + 2LiF-ZrF4
29.5
570
Eutectic
L ^
33.3
596
L f = =^2LiF-ZrF4
49
507
Eutectic
L^=
51.5
520
Peritectic
L + ZrF4 ^ = ^ 3 L i F . 4 Z r F 4
466
Decomposition
3LiF.4ZrF^ f = ^ 2LiF.ZrF4 + ZrF^
p.3UF-ZrF^
=â-3LiF.ZrF . + 2LiF.ZrF.
4
4
: ^ 2 L i F - Z r F 4 + 3LiF-4ZrF4
UNCLASSIFIED
ORNL-LR-DWG (6951
1
!1
11
>
LiF+ LIQUID
j - d - J L i F ZrF^ + LIOUID
'
Ji
V
^2LiF ZrF^+LIQUID
t!-3LiF ZrF^ + 2LiF ZrF^^^
^
X
Vi1
LiF+ a - 3 L i F ZrF^
,.,i.._
- L i r 1-p oLir-
'
irr-^
^
2LiF
+ LIQt in
ZrF^+LIQUID
/
\
F 4ZrF,+LIQUID
*^
\^ '
2LiF ZrF^+ 3L(F 4ZrF^
'
3LiF 4ZrF4+ZrF^
\
^3LiF
4ZrF,
2L;F ZrF^+/3-3LiF ZrF^^

M
2LiF ZrF,+ ZrF^
LiF+ 2LiF ZrF^
LiF
10
-J
CM
20
30
1
40
50
ZrF. (mole%)
60
70
80
90
Fig. 3.32. The System L i F - Z r F ^ .
53
3.33.
The System N c F - Z r F ^
C. J. Barton, W. R. Grimes, H. Insley, R. E. Moore, and R. E. Thoma, "Phase Equilibria

in the Systems N a F - Z r F ^ , U F ^ - Z r F ^ , and N a F - Z r F ^ - U F ^ , " / . Phys. Chem. 62, 665-76 (1958).
Invariant
Mole % ZrF^
in Liquid
T.emperature
Phase Reaction
Type of Equilibrium
(C)
20
747
Eutectic
L f = ^ N a F + 3NaF-ZrF,
25
850
L F=^3NaF.ZrF *
523
Invers ion
a-5NaF.2ZrF^ ^ = i /S-5NaF.2ZrF^
30.5
500
Eutectoid
a-5NaF-2ZrF^ss ^ ^ /3-5NaF.2ZrF^ +
+ 7-2NaF'ZrF^
34
640
Peritectic
L + 3NaF.ZrF^(sj:, ca. 27.5 mole %

ZrF.)^=â-5NaF.2ZrF.
39.5
544
Peritectic
L + a-5NaF.2ZrF^(ss, 30 mole %
ZrF.) = = f a-2NaF.ZrF,
4
533
Inversion
a-2NaF.ZrF, p=i/3-2NaF.ZrF
4
'
505
Inversion
/3-2NaF.ZrF^ ^ = ^ - y . 2 N a F . Z r F ^
40.5
500
Eutectic
46.2
525
L ^
49.5
512
Eutectic
L ^ = ^ 7NaF-6ZrF^ + 3NaF.4ZrF^
56.5
537
Peritectic
L + Z r F . = = = : 3NaF.4ZrF.
' 7 - 2 N a F . Z r F ^ + 7NaF.6ZrF^s5
7NaF-6ZrF.
*A determination of the crystal structure of 3NaF-ZrF . has been reported by L. A. Harris, " T h e Crystal
Structures of N o j Z r F ^ and N o g H f F ^ , " Acta Cryst. 12, 172 (1959).
54
01
n
I
CO
ui
59
en
1 o
NJ
-Ci
IV
"n
3NaF 4ZrF4
7NaF 6 Z r F ^
3NaF 2ZrF^
2NaF ZrF^
ZZrF^
3NaF ZrF^
^ ^
Sfc^
"J r
- ^ ^
_^
TEMPERATURE (C)
'
3.34.
The System K F - Z r F ^
C.
J . B a r t o n , H. I n s l e y , R. P. M e t c a l f , R. E. Thoma, and W. R. Grimes, u n p u b l i s h e d work
performed at the Oak Ridge N a t i o n a l Laboratory, 1 9 5 1 - 5 5 .

Invariant
Mole % ZrF^j
in Liquid
Temperature
Phase Reaction
Type of Equilibrium
{C)
14
765
Eutectic
L f = ^ K F + 3KF-ZrF^
25
910
L ^ = ^ 3KF-ZrF^
36
590
Peritectic
3KF-ZrF4 + L ^ = ^ 2 K F - Z r F 4
40.5
412
42
390
Eutectic
L F = ^ 3KF-2ZrF4 + K F - Z r F ^
50
475
L f = ^ KF'ZrF^
55
440
Eutectic
L ?==i K F - Z r F ^ + Z r F ^
?KF'ZrF
+L
^3KF'27rF
UNCLASSIFIED
ORNL-LR-DWG
1000
900
800
700
f r
\
600
500
ii5
1,^
400
Li_
U-
CO
:^
u5
U
M
OJ
^
Li5
N
LL
U-
300
20
30
Fig. 3.34
56
40
50
ZrF, (mole 7o!
T h e System K F - Z r F ^ .
70
80
18965
3.35.
R.
T h e System R b F - Z r F ^
E. Moore, R. E. T h o m a , C. J . B a r t o n , W. R. G r i m e s , H. I n s l e y , B. S. L a n d a u , and H . A .
F r i e d m a n , u n p u b l i s h e d w o r k performed at the Oak R i d g e N a t i o n a l L a b o r a t o r y ,

Preliminary
195556.
diagram.
Invariant E q u i l i b r i a
Invariant
Mole % Z r F ^
Phase
Type of Equilibrium
Temperature
Reaction
in Liquid
(C)
10
710
Eutectic
RbF + 3 R b F . Z r F ,
25
897
3RbF.ZrF,
34
620
Peritectic
:a-2RbF.ZrF,
L + 3RbF.ZrF.ss
4
460
Inversion
a-2RbF.ZrF^
^=:i/3.2RbF.ZrF_j
370
Lowered inversion
and decomposition
a-2RbF.ZrF4Ss F = ^
42
410
Eutectic
a-2RbF.ZrF .ss + 5RbF.4ZrF .
44.4
445
5RbF.4ZrF,
48
390
Eutectic
L F = ^ 5RbF.4ZrF^ + /3-RbF.ZrF^
50
423
L ^ = i a-RbF-ZrF .
391
Inversion
a-RbP-ZrF^ F = ^ /3-RbF.ZrF^
54
400
Eutectic
L ^ = i a - R b F - Z r F 4. + RbF.2ZrF 4.
57
447
Peritectic
L + ZrF^ ^ = ^ R b F . 2 Z r F ^
X ^N
x~~
%
a
\\
\ \
\ \
1 \
1Y
1 \
1
V
i-
1\
1
1
1
1
1
1
/3-2RhF-ZrF^SS
1
J3
nt
1
1
^--1^
V
N
\r -^
N/
CC
"'
az
Z r F , lmol67.)
F i g . 3.35. The System R b F - Z r F 4 .
57
3.36.
C.
The System C s F - Z r F ^
J . Barton, L. M. Bratcher, and W. R. Grimes, unpublished work performed at the Oak

Invariant
58
Phase Reaction
Mole % Z r F ^
in Liquid
Temperature
640
Eutectic
L ^ = ^ CsF + 3CsF.ZrF4
25
775
L ? = ^ 3CsF.ZrF^
35
520
Peritectic
L + SCsF-ZrF^ ^ = ^ 2CsF-ZrF4
40
420
Eutectic
L ^^=i 2CsF.ZrF^ + a-CsF-ZrF^
50
515
L ^ = ^ a-CsF-ZrF^
320
Inversion
a - C s F - Z r F ^ ^ ^ ^ /3-CsF.ZrF^
59
470
Eutectic
L ? = ^ a-CsF.ZrF_^ + ZrF^
Type of Equilibrium
(C)
I
N
Tl
CsF-Zr ^4
2CsF ZrF^
3CsF-ZrF^
TEMPERATURE (C)
3.37.
The System L i F - N a F - Z r F ^
F. F. Blankenship, H. A. Friedman, H. Insley, R. E. Thoma, and W. R. Grimes, unpublished

work performed at the Oak Ridge National Laboratory, 1953-59.
invariant Equilibria
^mol V)
LiF
NaF
Temperature
Type of
Invariant
Solids Present
ZrF,
37
52
11
604
Eutectic
NaF, L i F , and 3 N a F . Z r F ,
55
22
23
590
Eutectic
a - 3 L i F . Z r F , , 3NaF.ZrF,ss, and L i F
32
36
32
450
Peritectic
/S-SLiF-ZrF,, 3tâF.ZrF^ss,
31
35
34
448
Peritectic
3NaF.ZrF,, a-5NaF.2ZrF,ss, and 2 L i F . Z r F ,
31
34.5
34.5
445
Peritectic
2 N a F . Z r F , , a-5NaF.2ZrF4Ss, and 2LiF.ZrF4
26
37
37
425
Eutectic
2 N a F . Z r F , , 7NaF.6ZrF,, and 2LiF.ZrF4
29
25.5
45.5
449
Eutectic
7NaF.6ZrF,, 2HaF.4ZrF^ss.
29
24.5
46.5
453
Peritectic
3NaF.4ZrF,S5, 3LiF.4ZrF,ss, and 2 L i F . Z r F ,
28
24
48
475
Peritectic
3NaF.4ZrF,ss, 3LiF.4ZrF,ss, and Z r F ,
60
and 2 L i F . Z r F ,
and 2LiF.ZrF4
UNCLASSIFIED
O R N L - L R - D W G 38115
TEMPERATURE IN C
II
iNoF
INDICATES SOLID SOLUTION
3LiF 4ZrF,
4ZrF^/-537
-P-520
f-507
-512
7 NaF- 6ZrF^
fP-544
/-640,
2NaF-ZrF4-;;,
f-570
5NaF 2ZrF4~
3NaF-ZrF4
-605
E- 747-
-652
Fig. 3.37.
LiF
845
The System L i F - N a F - Z r F , .
61
3.38. The System N o F - K F - Z r F ,

R. E. Thoma, C. J . Barton, H. Insley, H. A. Friedman, and W. R. Grimes, unpublished work
Composition of
""'
i
^
Invariant
Temperature
ZrF,
Type of Equilibrium
Solids Present at Invariant Point
NaF
KF
(C)
34
58
695
Eutectic
NaF, K F , and 3 K F - Z r F ,
45
38
17
720
Eutectic
NaF, SKF-ZrF,, and 3 N a F . 3 K F . 2 Z r F ,
61
19
20
710
Eutectic
NaF, 3 N a F - Z r F , , and 3 N a F . 3 K F . 2 Z r F ,
52
17
31
Peritectic
3 N a F . Z r F , , 3NaF-3KF.2ZrF,, and
48
18
34
Peritectic
33
32
35
Peritectic
12
51
37
Peritectic
S K P . Z r F , , 2 K F . Z r F , , and
NaF.KF.ZrF,
40
21
39
Peritectic
5NaF.2ZrF,, 2 N a F . Z r F , , and
NaF.KF.ZrF,
3 N a F . Z r F , , N a F - K F ' Z r F , , and
5NaF.2ZrF,
3NaF.3KF.2ZrF,, S K P . Z r F , , and
NaF-KF.ZrF,
NaF.KF.ZrF.
39
21
40
11
49
40
10
48
42
Peritectic
385
Peritectic
2 N a F . Z r F , , 7NaF.6ZrF,, and
NaF.KP.ZrF,4
2 K F . Z r F , , 3 KCF
F . 2 Z r F , , and
Eutectic
NaF.KF-ZrF,
4
3 K F . 2 Z r F , , K F - Z r F , , and
NaP.KP.ZrF,
4
K F . Z r F , , N a P . K P . Z r F , , and
2NaF.3KF.5ZrF,
4
NaF-KF.ZrF ., 7 N a F . 6 Z r F . , and
4
4
2NaF.3KF.5ZrF,
4
7NaF.6ZrF,, 3 N a F . 4 Z r F , , and
2NaF.3KF.5ZrF.
15
40
45
Eutectic
22
33
45
Peritectic
25
25
50
Eutectic
21
29
51
Eutectic
3NaF.4ZrF ., Z r F , , and
2NaF.3KF.5ZrF^
20
30
50
2NaF.3KF.5ZrF.
432
*Three solid phases have been observed routinely in the composition region 3050 mole % ZrF . which
have not been identified as to composition. Whether these exhibit primary phases at the liquidus surface has
not yet been determined.
**Compositions of invariant points shown by the intersection of dotted boundary curves are approximate.
62
UNCLASSIFIED
ORNL-LR-DWG35480
TEMPERATURE INC
COMPOSITION IN mole7
2NaF 3KF 5ZrF,

NoF KF ZrF^
3NaF 3KF 2ZrF,
3NaF 4ZrF^
P 537
512
7NaF 6ZrF,
500
P54A
P 640
2NaF ZrF^ / 7 5 0
5NaF 2ZrF
3KF ZrF,
3NaF ZrE,
747 A
765
Fig.
between
3.38.
The
System
the
and
40
30
mole
NaF-KF-ZrF,.
% ZrF,
r e l a t i o n s h i p s in t h i s p o l y t h e r m a l
The
compositions
isotherms
have
been
for
the
omitted
temperatures
in order
600,
650,
and
700C
not to o b s c u r e t h e p h a s e
projection.
63
3.39.
R.
The System N a F - R b F - Z r F ,
E. Thoma, H. I n s l e y , H. A . Friedman, and W. R. Grimes, unpublished work performed at
the Oak Ridge National L a b o r a t o r y , 1 9 5 1 - 5 6 .

C o m p o s i t i o n of
"^
L i q u i d (mole %)
^
NaF
RbF
ZrF,
i
i
Invariant
-r
.
Temperature
T y p e of Equi l i b r i u n
Solids Present at Invariant
Point
(C)
23
72
643
Eutectic
N a F , R b F , and 3 R b F . Z r F .
50
27
23
720
Eutectic
N a F , 3 R b F . Z r F , , and 3 N a F . Z r F ,
37
32
31
605
Eutectic
3N
MaaFF .. ZZ r F , , 33Rb
R b F . Z r F , , and
NaF.RbF.ZrF,
39
26
35
545
Peritectic
3 N a F . Z r F , , 5 N a F . 2 Z r F , , and
NaP.RbP.ZrF^
36.3
24.2
39.5
427
Peritectic
5 N a F . 2 Z r F , , 2 N a F . Z r F , , and
NaF-RbF.ZrF.
4
34.5
24
41.5
424
Peritectic
2 N a F . Z r F , , N a F - R b F . Z r F , , and
3NaF.3RbF.4ZrF,
34
23.5
42.5
422
Peritectic
2 N a F . Z r F , , 7 N a F . 6 Z r F , , and
3NaF.3RbF.4ZrF,
33
23.5
43.5
420
Eutectic
7 N a F . 6 Z r F , , 3 N a F . 3 R b F - 4 Z r F , , and
NaF-RbF.2ZrF.
4
28.5
21.5
50
443
Eutectic
28
21.5
50.5
446
Peritectic
23.5
39.5
37
470
Peritectic
21
40
39
438
Peritectic
3 N a F . 4 Z r F , , 7 N a F . 6 Z r F , , and
NaF.RbF.2ZrF.
4
3 N a F . 4 Z r F , , Z r F , , and
NaF.RbF.2ZrF.
4
N a F . R b F . Z r F , , 2 R b F . Z r F , , and
3RbF.ZrF,
4
N a F . R b F . Z r F , , 2 R b F - Z r F , , and
3NaF-3RbF-4ZrF,
50
42
400
Eutectic
3 N a F - 3 R b F - 4 Z r F , , 2 R b F - Z r F , , and
5RbF.4ZrF,
4
8.5
47
44.5
395
Eutectic
3 N a F - 3 R b F - 4 Z r F , , 5 R b F - Z r F , , and
NaF-RbF-2ZrF,
6.2
45.8
48
380
Eutectic
N a F - R b F - 2 Z r F , , 5 R b F - 4 Z r F , , and
RbF-ZrF,
42
53
398
Eutectic
N a F - R b F - 2 Z r F , , R b F - Z r F , , and
RbF.2ZrF,
6.5
39
54.5
423
Peritectic
Z r F , , N a F . R b F . 2 Z r F , , and
RbF.2ZrF,
33.3
33.3
33.3
642
Congruent m e l t i n g point
NaF.RbF-ZrF.
25
25
50
462
NaF.RbF-2ZrF .
64
Minimum Temperatures on Alkemade Lines

Composition of Liquid (mole %)
Temperature
Alkemade Line
NaF
RbF
ZrF,
(C)
24.75
24.75
51.5
455
NaF.RbF.2ZrF,-ZrF,
44
50
402
NaF.RbF-2ZrF.-RbF.ZrF.
7.5
46.5
46
405
NaF-RbF-2ZrF,-5RbF.4ZrF,
8.5
48.5
43
405
3NaF-RbF.4ZrF.-5RbF.4ZrF,
28
28
44
435
3NaF.RbF.4ZrF.-NaF.RbF.2ZrF,
22
40
38
442
3NaF.3RbF.4ZrF,-2RbF.ZrF,
29
41.5
49.5
450
NaF.RbF.2ZrF,-7NaF.6ZrF,
37
24.5
38.5
610
NaF.RbF.ZrF,-3NaF.ZrF,
47
28
25
732
3NaF-ZrF,-3RbF-ZrF,
36
48
16
777
NaF-3RbF.ZrF,
30
36.7
33.3
598
NaF-RbF.ZrF,-3RbF.ZrF,
NaF RbF 2ZrF^
TEMPERATURE IN "C
3NaF 3RbF 4ZrF
NaF RbF ZrF.
RbF 2 Z r ^
P447
400
RbF-ZrF, 423
f 390
5RbF 4ZrF,445
-/'620
2Rbi- ZrF.
3RbF ZrF. 897
Fig. 3.39. The System N a F - R b F - Z r F , .
65
3.40.
The System N a F - C r F j - Z r F , : The Section NoF-CrFj - Z r F ,
R. E. Thoma, H. A. Friedman, B. 5. Landau, and W. R. Grimes, unpublished work performed

No invariant equilibria occur for compositions lying on the section
NaF.CrFj-ZrF,.
UNCLASSIFIED
ORNL-LR-DWG 19367R
900
"
ZrF4+LIQUID
^^^'^
\
\ ^
\
CrF^-Zr F4 -F LIQUID
NaF- CrFj f LIQUID
600
- ^
a-NaF- CrFj -2ZrF4

+ LIQU ID
CM
cr-NoF- CrFj- 2ZrF4 + ZrF4

NaF- CrFj + a-NaF-CrFj ZZrF^
O
2
500
NaF-CrFj-l /3-NaF-CrF 2 - 2 Z r F 4
400
NaF CrF2
10
20
30
F i g . 3.40.
66
/3-NaF CrF2-2ZrF4 -FZrF4
40
50
ZrF4 (mole 7o)
60
T h e Section N a F . C r F j - Z r F , .
ZrF.
3.41.
The System N o F - C e F g - Z r F ,
W. T. Ward, R. A. Strehlow, W. R. Grimes, and G. M. Watson, "Solubility Relationships of

Rare Earth Fluorides and Yttrium Fluoride in Various Molten N a F - Z r F , and N a F - Z r F , - U F ,
Solvents," / . Chem. Eng. Data (in press).
UNCLASSIFIED
ORNL-LR-DWG 29164R
CeF3(1387C)
ZrF^(918C)
Fig. 3.41a. The System N a F - C e F , - Z r F , .

UNCLASSIFIED
ORNL-LR-DWG 29165R
PROBABLE NaF- ZrF^ PRIMARY PHASE FIELDS
A ZrF
'4
B 3NaF-4ZrF4
C 7NaF-6ZrF^
20 .
D 2NaF-ZrF,
" """'
""4
E5NaF-2ZrF4
F SNoF- ZrF^
A 20
16
\ ;
"
Fig. 3.416. The System N a F - C e F j - Z r F , in the Region 30-70 Mole % NaF,

0-20 Mole % C e F j , 30-70 Mole % Z r F , .
67
3.42.
The System L i F - C e F j
C. J. Barton, L. M. Bratcher, R. J. Shell, and W. R. Grimes, unpublished work performed at

Preliminary diagram. The system L i F - C e F j contains a single eutectic at 81 L i F - 1 9 CeF
(mole %), m.p. 755 + 5C.
68
ON
Tl
a
3
(/I
<
H
-I
3a
lO
tp
V,
TEMPERATURE (C)
S-^
"\
r^P
3.43.
The System N a F - H f F ,
R.
E. Thoma, C. F. Weaver, T . N. McVay, H. A . Friedman, and W. R. Grimes, unpublished
work performed at the Oak Ridge National Laboratory, 1 9 5 6 - 5 8 .

Invariant
Phase Reaction
Mole % H f F ,
in Liquid
Temperature
18.5
695
Eutectic
L F = ^ NaF-f 3NaF.HfF,
25
863
Congruent me Itiing poi nt
L f=^3NaF.HfF,*
34
606
Peritectic
L + 3NaF.HfF, ^ = ^ a.5NaF.2HfF,
535
Inversion
a-5NaF.2HfF, ^==i:/3-5NaF.2HfF,
35
586
Peritectic
L + a-5NaF.2HfF, p = ^ ;S-2NaF.HfF,
Be low 350
Inversion
/S.2NaF.HfF, ^ ^
Type of Eq ui librium
(C)
'V-2NaF.HfF
Be low 350
7-2NaF.HfF,
^ ?-2NaF-HfF
43
510
Eutectic
L ^ = ^ /3-2NaF.HfF, + 7NaF.6HfF,
45
531
Peritectic
L + NaF.HfF, ^ = ^ 7 N a F . 6 H f F ,
50
557
Congruent me It ing poiint
L F = ^ NoF.HfF,
53
535
Eutectic
L ^
NoF.HfF, + H f F ,
*A determination of the crystal structure of 3NaF.HfF has been reported by L. A. Harris, "The Crystal
Structures of NogZrF^ and NajHfF^," Acta Cryst. 12, 172 (1959).
70
UNCLASSIFIED
ORNL-LR-OWG 35488
1050
^
950
850
V
(
750
A fN.
\
v
,
650
N^
v^
/ " ^
li?
450
I
CM
U.
\g
u?
o
z
in
o
z
1^
350
NQF
20
30
40
50
60
70
80
90
Fig. 1 4 3 . The System NaF-HfF^.
71
3.44.
The System L i F - T h F ^
R. E. Thoma, H. Insley, B. S. Landau, H. A. Friedman, and W. R. Grimes, "Phase Equilibria

in the Fused Salt Systems L i F - T h F ^ and N a F - T h F ^ , " / . Phys. Chem. 63, 1266-74 (1959).
Invariant
Mole % T h F ^
in L i q u i d
Phase
Temperature
Reaction
at I n v a r i a n t Temperature
(C)
23
568
Eutectic
L ^ ^
LiF + 3LiF.ThF^
25
573
Congruent m e l t i n g point
3LiF.ThF^
29
565
Eutectic
^ ^
SLiF'ThF. + 7LiF.6ThF
4
4
30.5
597
Peritectic
LiF.2ThF^ + L
42
762
Peritectic
LiF.4ThF. + L F=^
4
62
897
Peritectic
ThF. + L
4
F=^
7LlF.6ThF^
LiF.2ThF^
4
LiF.4ThF.
4
UNCLASSIFIED
ORNL-LR-DWG 26535A
1150
l^
1050
cr 850
<
cr
^
950
^
/
^
750
1
650
\^
^
r^ /
550
31. i F - T h F ^ - 7 L i F - 6 T h
\ -
_i"
U P 2ThF
4
450
LiF
10
20
30
F i g . 3.44.
72
40
50
60
ThF^(mole7o)
70
The System L i F - T h F ^ .
80
90
ThF^
3.45.
The System N o F - T h F ,

in the Fused Salt Systems L i F - T h F , and N a F - T h F , , " / . Phys. Chem. 63, 1266-74 (1959).
Invariant
Mole % T h F ^
in L i q u i d
Phase R e a c t i o n
Temperature
(C)
21.5
645
Peritectic
NaF + L ^
^ a-4NaF.ThF,
22.5
618
Eutectic
L ^=^
604
Inversion
a-4NaF.ThF,
558
Decomposition
/ S - 4 N a F . T h F , ; = ^ N a F -f 2 N a F . T h F ,
33.3
705
L ^
37
690
Eutectic
L ^ ^
40
712
L ^
41
705
Eutectic
L ^ = ^ 3 N a F . 2 T h F , 4- a - N o F - T h F ,
683
Decomposition
3NaF.2ThF
45.5
730
Peritectic
NaF.2ThF, + L ? = ^ a-NaF.ThF,
58
831
Peritectic
T h F , + L ?=:^NaF.2ThF,
a-4NoF.ThF, + 2NaF.ThF,
^=i/3.4NaF.ThF,
^ 2NaF.ThF,
2NaF.ThF, + 3NaF.2ThF,
^ 3NaF.2ThF,
2NaF.ThF,+ a-NaF.ThF,
UNCLASSIFIED
ORNL-LR-DWG 28528AR
1150
-7
1050
950
\
\
cc 850
<
cr 750
Q_
/
.
\
)
L/
UJ
650
550
Y^
,^
^x
/
I\
\
\
\
\;^
^^
LL
o
4NaF-ThF4-'
2NQ ^ThF^-
450
NaF
10
20
30
40
50
60
70
80
90
ThF4
T h i ^ (mole 7c,)
F i g . 3.45.
The System N a F - T h F , .
73
3.46.
The System K F - T h F ^
W. J. Asker, E. R. Segnit, and A. W. Wylie, " T h e Potassium Thorium Fluorides," / . Chem.

Soc. 1952,4470-79.
This system has also been reported by A. G. Bergman and E. P. Dergunov, Doklady
Akad.
Nauk S.S.S.R. 53, 753 (1941) and by V. S. Emelyanov and A. J. Evstyukhin, " A n Investigation
of Fused-Salt Systems Based on Thorium Fluoride -
II.
N a F - K F - T h F ^ , N a F - T h F ^ , and K F -
T h F ^ , " / . Nuclear Energy 5, 108-14 (1957).
Invariant
Phase Reaction
Mole % ThF^
in Liquid
Temperature
14
694
Eutectic
L <=^KF+/3-5KF.ThF^
635
Inversion
a-SKF-ThF^ ;;
712
Pentectic
L + 3KF.ThF^ ^ = ^ a-5KF.ThF^
25
865
L I
570
Decomposition
3KF.ThF^ ^ = : i / 3 . 5 K F . T h F ^ + / 3 . 2 K F . T h F ^
31
691
Eutectic
L ^ = i 3 K F . T h F ^ + a-2KF.ThF^
747
Pentectic
L + KF-ThF^ ^ = ^ a-2KF.ThF4
645
Inversion
n.9KF.ThF
50*
905
L ^=^KF.ThF^
56
875
Eutectic
L ^ = i KF.ThF^ + KF-2ThF^
66
930
Pentectic
L + KF.3ThF^ ^ = ^ K F . 2 T h F ^
75
990
L ^=^KF.3ThF^
78
980
Eutectic
L ^ = ^ KF-SThF^ + ThF^ss
Type of Equilibrium
(C)
^/3-5KF.ThF^
'-SKF-ThF^
^ /^.9KF.TIiF
*lt has been shown that the compound labeled by Asker et al, has the actual formula 7KF'6ThF ., cf. R.
E. Thomo, Crystal Structures of Some Compounds of UF. and ThF, with Alkali Fluorides, ORNL CF-58-1240 (December 11, 1958).
74
7s
KF-ThF^
ZKF-ThF^
SKF-ThF^
3KF-T IF,
::r;;
KF- 3ThF4
KF-ZThF^
^
^
<
--
'
"
TEMPERATURE (C)
<
3.47.
The System R b F - T h F ^
E.
P. Dergunov and A. G. Bergman, "Complex
Formation Betv/een A l k a l i Metal
and Fluorides of Metals of the Fourth Group," Doklady
Fluorides
Akad. Nauk S.S.S.R. 60, 391-94 (1948).
Invariant
Mole % T h F ^
in Liquid
Phase
Type of Equilibrium
Temperature
Reaction
(C)
15
664
Eutectic
L F = ^ RbF + 3 R b F . T h F ,
4
25
974
37
762
Eutectic
L F = ^ 3RbF.ThF . + R b F - T h F .
4
4
50
852
L ^ = ^ RbF-ThF^
54
848
Eutectic
L ^ = : ^ RbF-ThF^ + RbF.3ThF^
75
1004
L ^ = ^ RbF.3ThF^
80
1000
Eutectic
L ^ = ^ RbF-3ThF4 + T h F ^
f = ^ SRbF-ThF^
UNCLASSIFIED
ORNL~LR-DWG 20461
1114^
1004
9" 4 0
1000
y
^
o 900
,..
r~/
8;
\
E 800
u ^SO
848
762
664
1
SI
Li.
rO
RbF
\0
20
\
30
40
li_
J3
Li.
X)
Q:
Q:
50
ThF. (mole % )
60
Fig. 3.47. The System R b F - T h F ^ .
76
70
90
ThF.
3.48. The System B e F j - T h F ^

R. E. Thoma, H. Insley, H. A. Friedman, and C. F. Weaver, "Phase Equilibria in the Systems BeF2-ThF4 and L i F - B e F 2 - T h F 4 , " paper to be presented at the 136th National Meeting
of the American Chemical Society, Atlantic City, N. J . , Sept. 13-18, 1959.
The system BeF2-ThF4 contains a single eutectic at 98.5 BeF2-1.5 ThF4 (mole %), m.p.
526 3C.
1200 I
UNCLASSIFIED
ORNL-LR-DWG 24551
1
1
,
1
noo
^^.^=
1000
<~>
^ ^ ^ ^ ^
.,
^^
UJ
QL 9 0 0
<
-^y"
S 800
'" 700
y~
y
^
70
^
80
600 J500 I
BeF2
^
10
^
20
^
30
1
40
^
50
^
60
Thf^ (mole7o)
Fig. 3,48. The System B e F j - T h P .
^
90
1
ThF^
3.49. The System BeF2-UF4

T. B. Rhinehammer, P. A. Tucker, and E. F. Joy, Phase Equilibria
in the System
BeFUF,,
MLM-1082 (to be published).

The system BeF2-UF4 contains a single eutectic at 99.5 B e F - - 0 . 5
UF^ (mole %), m.p. 535 2C.
UNCLASSIFIED
ORNL LR DWG 28598
1100
'
'
' "T~
'
1 '
'
1 '
-
1000 LIQUID
900
^ ^ ^ ^ - - ^
. ^ - ^
800
UF4+LIQUID
UJ
<
STOO
UJ
600
-J
500 3QHIGH^'^Z + ' - ' O " " '

0HlGHBeF2 + UF4
400
0
BeF2
10
20
1
30
Fig. 3.49.
78
40
50
60
MOLE PERCENT UF4
The System BeF2-UF4.
70
80
1
90
100
UF4
3.50.
The System MgF2-ThF4
J.
0 . Blomeke, An Investigation
actors,
of the ThF .Fused
Salt Solutions
for Homogeneous
Re-
ORNL-1030 (June 19, 1951) (declassified with deletions).

Invariant
Mole % T h F 4
in L i q u i d
Phase
T emperature
Reaction
at I n v a r i a n t Temperature
(C)
25
915
Eutectic
L F = ^ ThF4 + MgF2-2ThF4
33.3
937
40
925
Eutectic
L f = i M g F 2 ' 2 T h F ^ + MgF2
^==^MgF2'2ThF4
UNCLASSIFIED
1200
1100
^
1000
900
XN
vA
^^
'
V\
)
o
800
1-
5
700
600
ThF^
10
20
30
F i g . 3.50.
40
50
MgFg (mole %)
T h e System MgF
60
70
80
90
MgF.
-ThF^.
79
3.51.
The System L I F - B e F 2 - T h F 4
R. E. Thoma, H. Insley, H. A. Friedman, and C. F. Weaver, "Phase Equilibria in the Systems B e F 2 - T h F 4 and L i F - B e F 2 - T h F 4 , " paper to be presented at the 136th National Meeting
of the American Chemical Society, Atlantic City, N. J . , Sept. 13-18, 1959.
(mole %)
ThF,
Invariant
Temperature
(C)
Type of
Invariant
Solids Present
at Invariant Point
LiF
BeF,
15
83
497+4
Peritectic
ThF^, LiF.4ThF4, and BeF^
33.5
64
2.5
455 4
Peritectic
LiF.4ThF^, LiF.2ThF^, and BeF
47
51.5
1.5
356+6
Eutectic
2LiF.BeF2, LiF.2ThF^, and BeF2
60.5
36.5
433 5
Peritectic
LiF.2ThF^, 3LiF.ThF^ss, and

2LiF.BeF.,
65.5
30.5
444 4
Peritectic
L i F , 2LiF.BeF2, and
3LiF.ThF,ss
4
63
30.5
6.5
448+5
Peritectic
3LiF.ThF^ss, 7LiF.6ThF4, and

LiF.2ThF,
UNCLASSIFIED
ORNL-LR-DWG 37420A
TEMPERATURE IN C
7LiF 6Thl^
3LiFThF. ss
400 I
f
400
450
370
Fig. 3.51a. The System L i F - B e F 2 - T h F 4 .
80
L i m i t * of Single-Phase 3 L I F - T h F 4 Solid Solution

C o m p o s i t i o n (mole %)
LiF
BeF 2
ThF4
75
25
58
16
26
59
20
21
A three-dimensional model of the system L i F - B e F _ - T h F . is shown in Fig. 3.516
Fig. 3L5U.
Model of the System L i F - B e F 2 - T h F 4 .
81
3.52.
The System N a F - Z r F 4 - T h F 4
R. E. Thoma, H. Insley, B. S. Landau, H. A. Friedman, and W. R. Grimes, unpublished work

"^
^
(mole
%)
^
NoF
ZrF,
ThF,
4
i
Invariant
T
..
Temperature
(C)
X
Type
otI ct q u i li-u
i b nu m
Solids Present
* Invariant Point
77
20
645
Peritectic
NaF, a-4NaF.ThF4, and 3NaF.ZrF4
75.5
2.5
22
618
Eutectic
a-4NaF.ThF^, 2NaF-ThF4, and

3NaF.ZrF,
63
31*
683
Decomposition point
3NaF.2ThF , 2NaF.ThF., and
of 3NaF.2ThF. in
4
ternary system
NoF-ThF.
4
65.5
21.5
13
622
Peritectic
2NaF.ThF^, 3NaF.ZrF^, and

NaF-ThF^
65.5
24.5
10
615
Peritectic
SNaF-ZrF^, NoF-ThF^, and

a-5NaF.2ZrF4
64.5
25.5
10
593
Peritectic
a-5NaF.2ZrF^, NaF-ThF4, and

NaF.2ThF,
4
58
38
538
Peritectic
a-5NaF.2ZrF4, a-2NaF.ZrF^, and

NaF.2ThF^
58
40
495
Eutectic
/3-2NaF.ZrF^, NaF-2ThF^, and

7NaF.6ZrF^-3NaF.2ZrF^ss
53
42
510
Peritectic
NaF.2ThF^, Th(Zr)F^ss , and

7NaF.6ZrF^-3NaF.2ThF4ss
49.5
48
2.5
505
Eutectic
7NaF.6ZrF^, 3NaF.4ZrF^, and

Zr(Th)F^ss
*Approximate composition.
Note:
The boundary curve maximum on the Alkemade line 7NaF-6ZrF4ThF4 is unlikely to
f a l l exactly on this line, because pure ThF4 does not occur along this line.
solid
solutions with both Z r F . and NaF-2ThF., it is not readily determined on which side of
the Alkemade line this maximum occurs.
82
Since ThF4 forms
frjJZt7-dDN
Z5-d
EVS-3
t'jJZg-dDN/
oog-3
^t^^-d
Ot'9-d
''dJZ-dDNE
"d-iZ-dDNE
''d'lZ dONg
Zt'Z-S
u.
IL
N
u.
zE
10
a.
iil
00
CO
3.53. The System L i F - U F 3

C. J . Barton, V. S. Coleman, L. M. Bratcher, and W. R. Grimes, unpublished work performed
at the Oak Ridge Notional Laboratory, 1953-54.
The system L i F - U F g contains a single eutectic at 73 L i F - 2 7 U F ,
(mole %), m.p. 770C.
UNCLASSIFIED
ORNL-LR-DWG 2 9 2 3
1000
//
950
//
900
//
850
/
o
800
IxJ
tr
3
<
/
o
750
UJ
a.
UJ
H
700
650
600
Ip
550
c)
o
500
10
20
30
40
UFj (mole %)
Fig. 3.53. The System L i F - U F . .
84
50
60
70
3.54.
The System L i F - U F ^
C. J . Barton, H. A. Friedman, W. R. Grimes, H. Insley, R. E. Moore, and R. E. Thoma, "Phase

Equilibria
in the Alkali FluorideUranium Tetrafluoride Fused Salt Systems:
I.
The Systems
L i F - U F ^ and N a F - U F 4 , " / . Am. Ceram. Soc. 4 1 , 63-69 (1958).

Invariant
Mole % UF^
in Liquid
Temperature
(C)
Type of Equilibrium
Phase Reaction
at Invariant Temperoture
470
Decomposition
4LiF.UF4 ? = = L i F + 7LiF-6UF^
26
500
Peritectic
LiF + L
27
490
Eutectic
40
610
Peritectic
L + LiF.4UF
57
775
Peritectic
L + U F ^ f = ^ LiF.4UF_j
4LiF.UF,
4LiF.UF^ +7LiF.6UF^
7LiF.6UF,
UNCLASSIFIED
O R N L - L R - D W G (7457
noo
j
1000
^ 800
\
/
700
;
\
600
500
^
u5
4LiF U F ^ - /
to
_)
Li_
400
10
20
40
60
80
UF.
Fig. 3.54. The System L i F - U F 4 .
85
3.55.
The System N a F - U F g
C. J . B a r t o n , V . S. C o l e m a n , T . N. McVay, and W. R. Grimes, unpublished work performed

at the Oak Ridge N a t i o n a l L a b o r a t o r y , 1 9 5 3 - 5 4 .
86
Mole % UF3
1nvariant
Te mperature
in Liquid
(C)
27
715
Eutectic
L : ^
35
775
Peritectic
L + U F g ^
595
Inversion
a-NoF-UFg ^ = i /S-NaF-UFg
Type of Equilibrium
Phase Reaction
NaF + a . N a F . U F 3
a-NoF-UFg
UNCLASSIFIED
ORNL-LR-DWG 2924R
1
1
1
1
1
1
o MIXTURES P R E P A R E D IN SEALED CAPSULES
MIXTURES PREPARED IN OPEN CRUCIBLES
1100
1000
MIXTURES PREPARED IN OPEN
r^K1
[STIRRER-EQUIPPED CRUCIBLES
900
1 1 IX
800
<
LU
IN A HELIUM ATMOSPHERE
t^^
'
/:i_____L_
. ^ ' ^ ^
700
/ K
600
i>
0 i!
.]
1
r~'
"
^t
^}
9
LL
500
400
0
10
15
NaF
20
25
30
35
40
45
50
UF3 (mole 7o)
F i g . 3.55.
The System N a F - U F ,
87
3.56.
The System N a F - U F 4
C. J . Barton, H. A. Friedman, W. R. Grimes, H. Insley, R. E. Moore, and R. E. Thoma, "Phase

Equilibria
in the Alkali Fluoride-Uranium Tetrafluoride Fused Salt Systems:
I.
The Systems
L i F - U F 4 and N a F - U F 4 , " / . Am. Ceram. Soc. 4 1 , 63-69 (1958).
Invariant
88
Phase Reaction
Mole % UF^
in Liquid
Temperature
21.5
618
Eutectic
L ^ = ^ a - 3 N a F . U F ^ + NaF
25
629
L ^=:ia-3NaF-UF^
528
Inversion
a-3NaF.UF^ ^ = : i / 3 . 3 N a F . U F ^
497
Decomposition
/3.3NaF.UF^ f = i NaF + 2NaF.UF^
28
623
Eutectic
L \
32.5
648
Peritectic
L + 5NaF.3UF^ ^ = ^ 2NaF.UF4
37
673
Peritectic
L + 7NaF.6UF.4 ^= = i 5 N a F - 3 U F4.
630
Decompos ition
5NaF.3UF^ ^ = ^ 2NaF.UF4 + 7NaF.6UF^
46.2
718
L ^;
56
680
Eutectic
L ^ ^ 7NaF-6UF4 + UF4
660
Upper stability limit

of NaF.2UF^
7NaF.6UF4 + UF^ ,
Type of Equilibrium
(C)
' a-3NaF.UF^ + 2NaF.UF^
' 7NaF-6UF^
^ NaF.2UF4
OO
vO
Z
a
n
I
a
3
lA
><
(/I
en
3 S
o
o
o
o
NaF-2UF4
7NaF-6UF4
5NaF-3UF4
2NaF-UFt
3NaF-UF i
r
I
(
o
o
-NJ
o
o
00
TEMPERATURE (C)
3.57.
The System K F - U F ^

II.
The Systems K F - U F 4
and R b F - U F ^ , " / . Am. Ceram. Soc. 4 1 , 538-44 (1958).

Invariant
Mole % UF^
in Liquid
Phase Reaction
Type of Equilibrium
Temperature
(C)
15
735
Eutectic
KF + 3 K F . U F ,
25
957
3KF.UF,
608
Decomposition
2KF-UF^ ^ = : i 3KF.UF^ + 7KF.6UF^
35
755
Peritectic
3KF.UF^ + L I
38.5
740
Eutectic
L F = ^ 2 K F - U F . + 7KF.6UF .
4
4
46.2
789
L p=i7KF.6UF4
54.5
735
Eutectic
L \^ = ^ 7KF.6UF, + KF-2UF,
4
4
65
765
Peritectic
UF^ + L ^==iKF-2UF^
' 2KF-UF^
UNCLASSIFIED
ORNL-LR-DWG 28526
1100
^
1000
o 900
800
/
\
<
^ 700
y^
LJ
f [N
\
h-
\
^
^^
/
/
\^^
D
L
Nsi
C
Ld
600
r>
500
OJ
LL
LL
rO
1^
400
KF
10
20
30
40
50
60
Uf^ (mole 7o)
Fig. 3.57. The System K F - U F 4 .
90
70
80
90
UF^
3.58.
R.
libria
The System RbF-UF4

E. Thoma, H. Insley, B. S. Landau, H. A. Friedman, and W. R. Grimes, "Phase Equi
in the A l k a l i Fluoride-Uranium Tetrafluoride Fused Salt Systems:
11. The Systems K F -
UF4 and R b F - U F 4 , " } ' ^ ' " - ^'eram. Soc. 4 1 , 538-44 (1958).
Invariant
Mole % U F ^
Temperature
in Liquid
Phase Reaction at
Type of Eqj i l i b r ium
Invariant Temperature
(C)
10
710
Eutectic
L ^ = ^ R b F + 3RbF-UF4
25
995
L^=^3RbF-UF,
38
818
Peritectic
L + 3RbF-UF4 ? = ^ 2RbF.UF4
43.5
675
Eutectic
L ^
44
693
Peritectic
RbF.UF . + L ^ = ^ 7RbF-6UF .
50
735
55
714
Eutectic
L ,
56.5
722
Peritectic
RbF.3UF4 + L f = ^ 2RbF.3UF4
57
730
Peritectic
RbF-6UF4 + L ^ = ^ RbF.3UF4
70.5
832
Peritectic
UF
2RbF-UF4+ 7RbF-6UF4
4
F=^RbF-UF^
^RbF'UF^ + 2RbF-3UF4
+ L .
^ RbF-6UF
UNCLASSIFIED
ORNL-LR-DWG 28525
1100
^
1000
/
/
^ 900
o
LJ
cc 8 0 0\
u 700
600
3
Ll_
500
400
RbF
<f
u5"
Q-
cc-
10
20
\N
^
/~\>^
u5
3
u5 rO
LL
LL
J2
-Q
(\J
1^
,,*
u5
3
ro
3
ID
ii
-D
30
40
50
60
70
80
90
UF.
UF4 (mole % )
Fig. 3.58. The System RbF-UF4.
91
3.59.
The System CSF-UF4
C. J . Barton, L . M. Bratcher, J . P. Blakely, G. J . Nessle, and W. R. Grimes, unpublished

Invariant
Phase Reaction
Mole % UF^
in Liquid
Temperature
7.5
650
Eutectic
L ^ = ^ C s F + 3CsF.UF4
25
970
L F=^3CsF.UF4
34
800
Peritectic
L + 3CsF.UF . ? = ^ 2 C s F . U F .
41
695
Eutectic
L ^ = ^ 2 C s F . U F . -t-a-CsF-UF.
50
735
550
Inversion
725
Eutectic
Type of Equilibrium
{C)
53
Lf==â-CsF.UF^
a-CsF-UF^ ^ ^ yS-CsF-UF4
L ^ = i a - C s F - U F 4 + UF^
UNCLASSIFIED
ORNL-LR-DWG. 18915
1 1 00
'
^
1000
9 00
<P
Lj800
K
IT
Ul
Q.
S 7 00
1-
6 00
u.'
3
U.
5 00
D
IL.
1
40
1
50
UF4 (mole
60
%)
Fig. 3.59. The System C s F - U F ^ .
92
3.60. The System ZrF4UF4

C. J . Barton, W. R. Grimes, H. Insley, R. E. Moore, and R. E. Thoma, "Phase Equilibria
in the Systems N a F - Z r F ^ , UF4-ZrF4,and N a F - Z r F 4 - U F 4 , " / Phy^- Chem. 62, 665-76 (1958).
The system ZrF . - U F 4 forms a continuous series of solid solutions having a minimum melting
temperature of 765C at 77 ZrF4-23 UF4 (mole %).
1050
700 I
UF^
UNCLASSIFIED
ORNL-LR-DWG ( 9 8 8 7
,
,
'
'
10
20
30
40
50
60
70
80
90
ZrF^
ZrF^ (mole 7o)
Fig. 3.60. The System Z r F . - U F
3.61.
B.
The System SnF2-UF4

J. Thamer and G. E. Meadows,
The Systems UF^-SnF^
and PuF^-SnF^,
LA-2286
(July 1959).
Invariant
Mole % UF4
in Liquid
Phase Reaction
Temperature
(C)
Type of Equilibriun
0.5
212
Eutectic
4.5
340
Peritectic
L + SnFj-UF^
7.8
371
Peritectic
L + UF. ^=r^SnF..UF.
4 ^
2
4
SnF2 + 2SnF2-UF^
2SnF2'UF^
UNCLASSIFIED
ORNL-LR-DWG 36864
MOO
900
800
>/
^
/
700
y"^
400
-^
350
UJ
tr
^ A '
300
./
Q
u
a
.^
h-
, /
o^n
-^/
. A SOLUBILITIES BY FILTRATIC)M
A LIQUIDUS POINTS FROM Dl A
HEATING CURVES
r^
^X
'
CC)OLING C URVES
500
(50
<
UF,( nole 7.)
400
/
300
200
/
Li53
05
100
20
40
50
60
Fig. 3.61. The System SnF2-UF4.
94
80
90
10
3.62.
The System PbF2-UF4
C. J . Barton, L. M. Bratcher, J . P. Blakely, G. J. Nessle, and W. R. Grimes, unpublished

Mole % U F ,
Invariant
Temperature
Phase Reaction
Type of Equilibrium
in Liquid
(C)
14.3
920
:6PbF2-UF4
35
835
Eutectic
^6PbF2-UF4 + 3PbF2-2UF4
40
840
i3PbF2-2UF^
62
762 10
Eutectic
:3PbF2-2UF4+ UF4
The eutectic at quite high PbF2 concentrations is not shown on this diagram.
The authors
examined thermal data but found no evidence of a eutectic thermal effect.
UNCLASSIFIED
DWGI4633R
1050
UF4 (mole7o)
Fig. 3.62. The System P b F - - U F
3.63. The System T h F ^ - U F 4

C. F. Weaver, R. E. Thoma, H. A. Friedman, an( I H. Insley, "Phase Equilibria in the Systems
UF4-ThF4 and L i F - T h F 4 - U F 4 , " paper presented at the 61st National Meeting of the American
Ceramic Society, Chicago, I I I . , May 17-21, 1959.
The system T h F 4 - U F . forms a continuous serie s of solid solutions without a minimum.
96
UNCLASSIFIED
ORNL-LR-DWG 279(3
1200
2- 1100
UJ
cc
I5IOOO
CC
UJ
^, 900
800
Thf^
T h f ^ - U I ^ SOLID SOLUTION
10
20
30
Fig. 3.63.
40
50
60
UFÎmoleô)
70
80
90
Uf^
The System ThF4-UF4.
97
3.64.
The System L i F - N o F - U F ^

UF4,"
III.
The System N a F - L i F -
/ . Am. Ceram. Soc. 42, 21-26 (1959).
Complosition of L Iquid
(mole %)
Invariant
Tlemperature
Type of
Equil ibrium

at Invariant Point
NaF
LiF
UF4
(C)
60
21
19
480
Eutectic
2NaF-UF^, NaF, and L i F
65
13
22
497
Peritectic
/3-3NaF.UF_^, 2NaF.UF^, and NaF
65.5
27.5
470
Peritectic
7LiF.6UF^ss,* 4 L i F . U F 4 , and L i F
35
37
28
480
Eutectic
2NaF-UF_j, 7NaF.6UF^ss, and L i F
57
13
30
630
Peritectic
2NoF.UF., 5NaF.3UF., and 7NaF.6UF .ss

4
4
4
24.3
43.5
32.2
445
Eutectic
7NaF-6UF^ss, L i F , and 7LiF.6UF^ss
24.5
29
46.5
602
Eutectic
NaF.2UF^, 7LiF.6UF4Ss, and 7NaF.6UF^ss
24.3
28.7
47
605
Peritectic
NaF.2UF^, L i F . 4 U F ^ , and 7LiF.6UF^ss
23.5
28
48.5
640
Peritectic
UF^, NaF.2UF^, and LiF.4UF4
37.5
10.5
52
660
Peritectic
UF4, NaF.2UF^, and 7NaF.6UF^ss
*The compounds 7LiF.6UF^ and 7NaF>6UF4 as they occur in the ternary system are members of the so
solution 7 L i F . 6 U F ^ - 7 N a F . 6 U F
98
UNCLASSIFIED
O R N L - L R - O W G 28214R
UF,
1035
TEMPERATURE IN "C
NaF 2 U F .
750
E680
'700
650^
7 N a F -eUF^
5NaF -SUF,
,. ,
iiiiiiiiiiiTmimMiiiiiiumv i L I F - 6 U F ,
650
600
r700
P673
P610
550
500,
P648
E623
3 N a F - UF,
4 L i F - UF4
Fig,
3.64a.
T h e System L i F - N a F - U F
UNCLASSIFIED
ORNL-LR-DWG 29791
725
700
675
o
o
650
Q:
3
h-
<
cr
LU
Q.
7LiF'6UF^
Fig. 3.64fe. The Join 7 N a F . 6 U F . - 7 L i F . 6 U F , .

4
100
3.65.
The System L l F - K F - U F ^
C. J . Barton, J . P. Blakely, L. M. Bratcher, and W. R. Grimes, unpublished work performed

Preliminary diagram. The system L i F - K F - U F . has not yet been defined at the Oak Ridge
National Laboratory with sufficient precision to permit the temperatures and compositions of the
invariant equilibria to be listed.
Fig. 3.65.
The System L i F - K F - U F
101
3.66.
The System L i F - R b F - U F ^
C. J . Barton, J . P. Blakely, L. M. Bratcher, and W. R. Grimes, unpublished work performed

Phase relationships within the system L i F - R b F - U F . have not yet
UNCLftSSIFlEO
ORNL-LR-OWG 28634R
UF4 (035
TEMPERATURE IN C
COMPOSITION IN moleVo
900
7L.F 6UF.
3RbF UP.
RbF
790
A^ V
-E-450
All
,V\ V
Fig. 3.66. The System L i F - R b F - U F ^ ,
102
LiF
845
3.67. The System N a F - K F - U F ^

R. E. Thoma, C. J . Barton, J. P. Blakely, R. E. Moore, G. J. Nessle, H. Insley, and H. A.
Friedman, unpublished work performed at the Oak Ridge National Laboratory, 1950-58.
Preliminary
diagram.
Phase relationships within the system N a F - K F - U F ^ have not yet
990
Eim
856
Fig. 3.67. The System N a F - K F - U F
103
3.68.
The System N o F - R b F - U F ^
R. E. Thoma, H. Insley, H. A. Friedman, and W. R. Grimes, unpublished work performed at

Composition of L iquid
(mole %)
NGF
104
RbF
Invariant
Temperature
UF4
{C)
Type of
Equilibrium
S.olid Phases Present
at Invariant Point
18
73
670
Eutectic
RbF, N G F , and
I
3RbF.UF^
46
33
21
470
Eutectic
NoF, NaF.RbF.UF^, and 3RbF.UF4
44
33
23
500
Perltectic
NaF.RbF.UF^, 2RbF.UF^, and 3RbF.UF4
45
30
25
485
Perltectic
NaF, 2NaF. U F . , and NaF.RbF.UF.

4'
4
52
23
25
500
Decomposition
3NaF.UF4, NaF, and 2NaF.UF4
41
26
33
555
Perltectic
2RbF.UF4, 2NaF.UF ., and NaF.RbF.UF .

4
4
57
35
630
Decomposition
2NaF.UF^, 5NaF.3UF^, and 7NaF.6UF^
33
30
37
535
Eutectic
2RbF.UF^, 2NaF.UF^, and 7RbF.6UF^
32
29
39
540
Perltectic
7RbF.6UF^ , 2NaF.UF4, and 7NaF.6UF4
26
27
47
620
Eutectic
7RbF.6UF^ , 7NaF.6UF^, and RbF.UF^
25
25
50
630
Eutectic
7NaF.6UF_j , RbF.UF^, and 2RbF.3UF_^
27
22
51
633
Perltectic
7NaF.6UF_j , 2RbF.3UF4, and RbF.3UF^
33
14
53
655
Perltectic
7NaF.6UF^ , RbF.3UF^, and RbF.eUF^
42
55
678
Perltectic
7NaF.6UF^ , RbF.6UF^, and UF^
2 RbF 3UF4
730
RbF UF4
7RbF 6UF,
Fig. 3.68a. The System N a F - R b F - U F ^ .

UNCLASSIFIED
ORNL-LR-DWG I7665R
1000
SRbF-UF^-F LIQUID
300
/
/
3UF4 + LIOUIC
2R1: F-UF^ -f LIQUI 3
/
600
2NaFUF4-
^
2NaF-UF4 4 2RbF-UF4
500
3
2N 3F UF^ + NaF RbF
LL
UF^
NoF- R b F - U F^ -1- 2 R b F - U F
(r
X)
OJ
400
2:
(0
30
40
50
60
66 7
RbF ( m o l e % )
Fig. 3.68fe. The Section 2NaF.UF^-2RbF.UF^.
105
UNCLASSIFIED
ORNL LR DWG 17666
Fig. 3.68c. The Section NaF-NaF.RbF-UF^.
106
UNCLASSIFIED
O R N L - L R - DWG 1766 7R
^
^
3 R b F - U F , -I- L l O tJID
^
y^
^ 2
u5
3
2RbF
RbF
UF^ 1- 2 N o F
UF, -^ LIQUID
UF4 -f L I Q U I D
NaF
RbF
UF4 -1- 2 R b F
UF4 -I- LIQUID
NaF
RbF
UF4 + 3RbF
U F , -1- LIQUID
NlaF RbF
UF, \ 3RbF
UF,
Li_
=3
tt
Li_
ro
z:
333 35
50
55
RbF (mole7o )
Fig. 3.68a!. The Section 3RbF.UF .-NaF.RbF-UF

4
107
3.69. The System L i F - B e F j - U F ^

L. V. Jones, D. E. Etter, C. R. Hudgens, A. A. Huffman, T. B. Rhinehammer, N. E. Rogers,
P. A. Tucker, and L. J. Wittenberg, Phase Equilibria
in the LiFBeFUF
Ternary Fused Salt
System, MLM-1080 (Aug. 24, 1959).
./-iiicL
Fig. 3.69a. The System L i F - B e F j - U F
108
UNCLASSIFIED
MOUND L4B NO
5 6 - H - 2 9 (REV)
(mole %)
LIF
BeFj
72
Temperature
(C)
Type of Equltlbrlun
480
Perltectic (decomposition

UF^
22
4 L I F . U F . , L i F , and 7 L i F . 6 U F ,
of 4 L I F . U F ^ In the
ternary system)
69
23
426
Eutectic
L i F , 2LlF.BeF2, and 7LiF.6UF_j
48
51.5
0.5
350
Eutectic
7LiF.6UF^, 2LIF.BeF2, and B e F j
45.5
54
0.5
381
Perltectic
LIF.4UF^, 7LlF.6UF^, and B e F j
29.5
70
0.5
483
Perltectic
U F , , L i F . 4 U F , , and B e F .
The minimum temperature in the quasi-binary system 2 L i F . B e F - 7 L i F . 6 U F
occurs at 65
L i F - 2 9 B e F 2 - 6 UF^ (mole %) at 438C.

A three-dimensional model of the system L i F - B e F . - U F , is shown in Fig. 3.69^.
Fig. 3.69fe. Model of the System L i F - B e F j - U F ^ ,
109
3.70. The System N c F - B e F j - U F ^

J. F. Eichelberger, C. R. Hudgens, L. V. Jones, G. Pish, T. B. Rhinehammer, P. A. Tucker,
and L. J . Wittenberg, unpublished work performed at the Mound Laboratory, 195657.
Composition of
Liquid (mole %)
NaF
Temperature
(C)
Type of Equilibrium
Solid Phases Present at

BeF,
UF,
74
12
14
500
Peritectic (decomposition of
SNoF-UF. in ternary system)
3NaF.UF ., NaF, and 2NaF.UF .
72.5
17
19.5
486
Eutectic
NaF, 2NaF.UF4, and 2NaF.BeF2
64.5
26.5
630
Peritectic (decomposition of
5NaF.3UF . In the ternary
system)
5NaF.3UF,, 2 N a F . U F , , and 7NaF.6UF.
57
42
378
Perltectic
2NaF.BeF2, 2NaF.UF4, and 7NaF.6UF^
56
43.5
0.5
339
Eutectic
2NaF.BeF2, NaF.BeF2, and 7NaF-6UF4
43.5
55.5
357
Eutectic
7NaF.6UF^, B e F j , and NaF.BeF2
41
58
375
Perltectic
7NaF.6UF4, NaF.2UF4, and BeF2
26
63
409
Peritectic
NaF.2UF^, NaF.4UF^, and B e F j
44
18
38
665
Perltectic
7NaF.6UF^, UF^, and NaF.2UF4
40
47
13
548
Perltectic
UF^, NaF.2UF4, and NaF.4UF4
27
72
498
Perltectic
UF^, BeF2, and NaF.4UF4
The minimum temperature in the quasi-binary system 2NaF.BeF2-2NaF.UF. occurs at 66.7

L i F - 2 5 BeF28.3 U F , (mole %) at 528C. The minimum temperature in the quasi-binary system
NaF.BeF2-7NaF.6UF4 occurs at 50.5 NaF-48.5 BeF2-1.0 UF^ (mole %) at 367C.
A three-dimensional model of the system N a F - B e F j - U F , has been constructed by the
authors and is shown in Fig. 3.70b.
110
UNCLASSIFIED
MOUND LAB NO
5 6 - 1 1 - 3 0 (REV)
ALL TEMPERATURES ARE IN C

E =
P =
EUTECTIC
PERITECTIC
; PRIMARY PHASE FIELD
7M oF 6UF^
5 NoF 3 U F ,
5NaF 3 U F , | - ^
2 NoF UF,^
P
/ ^
'A
-^
^
\ ys
3NaF UF, j i \
3 NoF UF, Y""^^^
\1 6 0 0
Fig. 3.70a.
The System N a F - B e F j - U F ^ .
in
UNCLASSIFIED
PHOTO 47483
Fig. 3.70fe. Model of the System N a F - B e F j - U F ^ .
112
3.71.
The System N a F - P b F 2 - U F 4
C. J . Barton, J . P. Blakely, G. J . Nessle, L. M. Bratcher, and W. R. Grimes, unpublished

phase relationships within the system N a F - P b F 2 - U F , .
UNCLASSIFIED
ORNL-LR-DWG 20455R
TEMPERATURE IN C
COMPOSITION IN mole
Die 7o
/
/ \
9O0/
/
/A
/(
\/~~Sy \ / A
\
\>\
/Nh
y \
\ \
\ /
\ /
/\
/\
7N0F-6UF4 (
5NoF-3UF4/
ZNoF-UF,
"65o,
Ôol
"^Sn
JÔn
10~
NaF
990
0%A
Az
Fig.
3.71.
ISSn
~*5o
~"*0n
PbF^
815
T h e System N a F - P b F j - U F ^ .
3.72. The system K F - P b F j - U F ^

C. J . Barton, J . P. Blakely, G. J . Nessle, L. M. Bratcher, and W. R. Grimes, unpublished
phase relationships within the system K F - P b F j - U F ^ .
114
UNCLASSIFIED
DWG l i S M A
TEMPERATURE IN C
COMPOSiTION IN mole 7c
KF 2UF,
7KF 6UF
2KF UF,
3KF-UF4
PbFj
815
Fig, 3.72. The System K F - P b F j - U F ^ .
115
3.73. The System N a F - Z r F ^ - U F ^

C. J . Barton, W. R. Grimes, H. Insley, R. E. Moore, and R. E. Thoma, "Phase Equilibria
in the Systems N a F - Z r F ^ , U F ^ - Z r F ^ , and N a F - Z r F ^ - U F ^ , " / . Phys. Chem. 62, 665-76 (1958).
UNCLASSIFIED
ORNL-LR-DWG 19886R
UF4
1035
Fig. 3.73a. The System N a F - Z r F ^ - U F ..
116

(mole %)
Temperature
{C)
Solids Present
at Invariant Point
Type of Equilibrium
NaF
ZrF^
UF^
69.5
4.0
26.5
646
Maximum temperature
of boundary curve
3NaF.(U,Zr)F^ and 2NaF.UF^
68.5
5.5
26.0
640
Peritectic
3NaF.(U,Zr)F^, 2NaF.UF^,
and 5NaF.3UF,ss
4
65.5
12.0
22.5
613
Peritectic or
decomposition
3NaF.(U,Zr)F^, 5NaF.3UF^ss,
and 7NaF.6{U,Zr)F,
64.0
27.0
9.0
592
Perltectic
3NaF.(U,Zr)F^, 5NaF.2ZrF^ss,
and 7NaF.6(U,Zr)F,
61.5
34.5
4.0
540
Perltectic
5NaF.2ZrF^:r5, 2NaF.ZrF_j,
and 7NaF.6(U,Zr)F,
50.5
47
2.5
513
Peritectic
7NaF.6(U,Zr)F^, (U,Zr)F4,
and 3NaF.4ZrF,
UNCLASSIFIED
ORNL-LR-DWG19888
750
5:
650
550
LIQUIDUS POINTS FROM THERMAL GRADIENT QUENCHING EXPERIMENTSSOLIDUS POINTS FROM THERMAL GRADIENT QUENCHING EXPERIMENTS
LIQUIDUS POINTS FROM THERMAL ANALYSIS
INITIAL COMPOSITION OF FILTRATION MIXTURES
FILTRATION RESIDUE COMPOSITIONS
FILTRATE COMPOSITIONS
500
20
3NaF-ZrF.
ZrF. (mole %\
Fig. 3.73fc. The Subsystem 3NaF.UF4-3NaF.ZrF^.
117
ORNL-LR -DWG 17669A
800
750
700
^
650
600
550
^ ^ ^
500
7NoF- 62rF4
(0
40
50
60
7NoF- 6UF4 (mole %)
Fig. 3.73c. The Subsystem 7NaF.6ZrF^-7NaF.6UF^.
118
80
90
7NaF-6UF.
3.74.
The System L i F - T h F ^ - U F ^
C. F. Weaver, R. E. Thoma, H. Insley, and H. A. Friedman, "Phase Equilibria in the Systems

U F ^ - T h F ^ and L i F - T h F ^ - U F ^ , " paper presented at the 61st National Meeting of the American
Ceramic Society, Chicago, I I I . , May 1 7 - 2 1 , 1959.
-
LiF
(mole %)
1
ThF,
UF,
4
4
,
Invariant
T
.
Temperature
(C)
Type of
"^
Equilibrium
Solids Present at Invariant Point
72.5
7.0
20.5
500
Peritectic
L i F , 3 L l F . ( T h , U ) F 4 , and 7 L i F . 6 ( U , T h ) F ^
72.0
1.5
26.5
488
Eutectic
L i F , 4 L i F . U F 4 , and 7 L i F . 6 ( U , T h ) F ^
19
609
Perltectic
7 L i F . 6 ( U , T h ) F ^ , L i F . 2 ( T h , U ) F ^ , and L i F . 4 ( U , T h ) F ^
53
18
A three-dimensional model of the system L i F - T h F ^ - U F ^ is shown in Fig. 3.74c.
UNCLASSIFIED
ORNL-LR-DWG 28215AR2
1111
PRIMARY-PHASE AREAS
TEMPERATURE IN C
(a) UF^-ThF^ (ss)

(b) LiF-4UF4-LiF 4ThF^(ss)
(c)
(d)
(e)
(f)
LiF ZThtUjF^Css)
7LiF 6UF4-7L1F SThF^tss)
3LiFTh(U)F4(ss)
LiF
P897 ,
7LiF 6ThF.
/762
P597
E565
3LiFThF,
f 568
1035
F i g . 3.74a.
The System L i F - T h F ^ - U F ^ .
119
UNCLASSIFIED
ORNL-LR-DWG 35503R
{a)
LIQUID + 3 L i F - T h F 4 ss
[b]
LiF-FLIQUID
ic)
LiF-F 3 LiF-ThF^ ss + LIQUID
id)
L I F - l - 7 L i F - 6 T h f ^ - T L i F - G U F ^ ss + LIQUID
ie)
4 L i F - U F 4 - | - LIQUID + LiF
if)
4LIF-UF4 -I- LIQUID
{g)
4 L i F - U f ^ + 7 L i F - 6 T h F 4 - 7 L i F - 6 U F ^ ss + LIQUID
(/?)
SLiF-ThF^ss
(/)
3LiF-ThF4
(/)
LiF 4- 7 L i F - 6 T h F 4 - 7 L I F 6UF4 ss
Or)
LiF-F 4 L I F - U F 4 -F 7 LiF 6 ThF4 - 7 L i F 6UF4SS
(/)
4 L i F - U F 4 + 7 L i F - 6 T h F 4 - 7 L I F - 6UF4SS
ss -F 7 L i F SThF^ - 7 L i F 6UF4 ss + L i F
575
1
1
A THERMAL DATA
550
QUENCH DATA
0 TIE LINE DATA
.
> LIQUID
i
525
'i
L
, V(C)
500
1
ie)
if)
9)
(/.)
1
V
475
T
1
450
/
10
UF4 (mole
Fig. 3.74fc. The System L i F - T h F ^ - U F ^ :
15
20
%)
The Section at 75 Mole % L i F .
25
-(/)
UNCLASSIFIED
ORNL-LR-DWG 27917
850
800
750
700
UJ
650
600 =
550
500
Fig. 3.74c.
The System L i F - T h F ^ - U F ^ :
The Section at 53.8 Mole % LiF.
121
UNCLASSIFIED
ORNL-LR-DWG 3 5 5 0 6 R
{a)
U F 4 - T h F 4 ss + LIQUID
{i>)
L1F-4UF4-LiF-4ThF4-l-LIQUID
[ e ) UF4-ThF4 ss + LIQUID + L i F - 4 U F 4 - L i F - 4ThF4 ss

(d)
L i F - 2ThF4 ss 4- LIQUID + LiF- 4UF4 - L i F 4ThF4 ss
{e)
L i F - 4 UF4 - L i F - 4ThF4 ss + LIQUID -F 7 L i F - 6 UF4 - 7 L i F - 6ThF4SS
[f)
L i F - 2ThF4SS
[g)
L i F - 4 U F 4 - L i F - 4 T h F 4 ss + 7 L i F - 6 U F 4 - 7 L i F - 6 T h F 4 ss
(A) L i F - 4 U F 4 - L i F - 4 T h F 4 ss + 7 L i F - 6 U F 4 - 7 L 1 F 6ThF4 s s + L i F - 2ThF4 ss

1100
1000
900
800
UJ
Q_
700
600
500
30
40
UF4 ( m o l e 7o)
F i g . 3.74rf.
122
T h e System L i F - T h F ^ - U F ^ :
T h e Section at 3 3 . 3 Mole % L i F .
I
<
UNCLASilFiED
PHOTO 34246
VS;i'f^H.V
k. i
I
:5?SS^-
UP-tURj+UF,
Fig. 3.74e. Model of the System L i F - T h F ^ - U F ^ .
123
3.75.
R.
The System N a F - T h F ^ - U F ^ :
The Section 2NaF.ThF4-2NaF.UF4
E. Thoma, H. Insley, H. A. Friedman, and C. F. Weaver, unpublished work performed at

UNCLASSIFIED
ORNL-LR-DWG 34986
725
^0^700
1
2NaF ThF^ + LIQUID
\ ^
^---S-2NaF-U(Th)F.
/ S O L I D SOLUTION AND LIQUID
675
_/
VJ
5NaF 3UF4
AND L I Q U I D ^
* - - < . .
\
N
" ^ - ^
^.*
650
5NaF-3UF4
K
\
- 625
u
(r
^V
A.
1 600
UJ
+ S - 2 N a F - U ( T h ) F ,I
SOLID SOLUTIONS-'"^
AND LIQUID-'^'^
0 2 - 2 ^ JaF Th(U)F^
LU
/'
+ S-2NaF-U(Th)F^
\
\
V\ ^
\
S-2NaF-U(Th)F^
SOLID SOLUTION
575
\
\
550
/32-2NaF-Th(U)F4
SOLID SOLUTION
\
\
\
\
525
Ron
2NaF-ThF4
10
15
20
25
UF^ (mole 7o)
Fig. 3.75. The Section 2NaF.ThF4-2NaF.UF4.
124
30 2NaF-UF.
3.76.
The System L i F - P u F j
C. J. Barton and R. A. Strehlow, "Phase Relationships in the System Lithium FluoridePlutonium Fluoride," paper presented at the 135th National Meeting of the American Chemical
Society, Boston, Mass., Apr. 5 - 1 0 , 1959.
The system L i F - P u F g contains a single eutectic at 80.5 L i F - 1 9 . 5 P u F , (mole %), m.p.
743C.
UNCLASSIFIED
ORNL-LR-DWG 34817
1500
1425C~^
1400
y"
1300
1y . " ^ '
^^
1200
^'
^ 1100
cc
UJ
Q_
1000
LiJ
900
800 ^
700
o L
>
^~~~~~^ ^43C
LiF
10
fco-0c > - o m r
20
30
40
50
60
PuFj (mole %)
70
80
90
PuFj
Fig. 3.76. The System L i F - P u F , .
125
3.77, The System L i C U F e C l j

C. Beusman, Activities
in the KClFeCl- and LiClFeCl2 Systems,
ORNL-2323 (May 15,
1957).
The system LiCIFeCL forms a continuous series of solid solutions with a minimum at 60
L i C I - 4 0 FeCl2 (mole %), m.p. 540C.
UNCLASSIFIED
ORNL-LR-DWG. 20942
700
30
40
50
MOLE %
60
Feci,
Fig. 3.77. The System L i C I - F e C l j -
126
70
80
90
100
3.78. The System K C i - F e C i j

C. Beusman, Activities
in the KClFeCL
and LiClFeCl2
Systems, ORNL-2323 (May 15,
1957). A nearly identical diagram to this one has been reported by H. L. Pinch and J . M. Hirshon,
"Thermal Analysis of the Ferrous Chloride-Potassium Chloride System," / . Am. Chem. Soc.
79, 6149-50 (1957).
Invariant
Phase Reaction
Mole % F e C l j
Temperature
in Liquid
(C)
35
385
Peritectic
L + KCI
255
Inversion
a . 2 K C | . F e C I2, ^F=^/6-2KCI-FeCI
A---..^-.-. = - . 2
39
355
Eutectic
50
400
300
Inversion
a-KC|.FeCI
53
390
Eutectic
L ^ = ^ a - K C I - F e C l 2 + FeCl2
Type of Equilibrium
:a-2KCl.FeCL
^ a-2KC|.FeCL + a-KCI-FeCL
a-KCI-FeCL
^=^^.KCI.FeCL
UNCLASSIFIED
ORNL-LR-DWG. 20940R
677
40
50
MOLE %
60
70
80
90
100
FeCL
Fig. 3.78. The System K C I - F e C I ,
127
3.79. The System NaCI-ZrCl4

C. J. Barton, R. J. Sheil, and W. R. Grimes, unpublished work performed at the Oak Ridge
11 I or T r-i
Mole % Z r C I .
, . ..
in Liquid
28.0
Invariant
Temperature
Type of Equilibrium
5 3(C)
5+5
Peritectic
445 + 5
535+5
Decomposition
Peritectic
525 + 5
Eutectic
626 + 5
525 + 5
370+5
626 + 5
352 5

Eutectic
Inversion
Peritectic
312 + 5
352 5
312+5
Inversion
Peritectic
Eutectic
Phase Reaction at Invariant Temperature
L + NaCI = = : ^ 3NaC|.ZrCI .
^
3NaC|.ZrCI^F=^^NaCI + a . 2 N a C | . Z r C I ^
28.5
33.3
L ^ = i 3 N a C | . Z r C l 4 + a.2NaC|.ZrCl4
L^
Cl.2NaC|.ZrCI .
a.2NaCI'ZrCI^^
58
Â2NoC|.ZrCI^
L +/3.2NaC|.ZrCl4?==^ a..3NaCI'4ZrCl4
a.3NaCI'4ZrCl4^=^/3.3NaCI'4ZrCI^
63
312+5
Eutectic
L f=^-yS.3NaC|.4ZrCl4 + ZrCI^
Previous reports on the system N a C I - Z r C I . have been made by N. A. Berlozerskts and 0 . A.

Kucherenko, Zhur. Priklad.
Khim. 13, 1552 (1940), I. S. Morozov and B. G. Korshunov, Zhur.
Neorg. Khim. 1, 145(1956), and H. H. Kellogg, L. J. Howell, and R. C. Sommer, Physical Chemical Properties of the Systems NaClZrCl,,
NYO-3108 (April 7, 1955).
128
KClZrCl,,
and NaClKClZrCl,,
Summary Report,
UNCLASSIFIED
O R N L - L R - D W G 17671
900
50
60
ZrCI. (mole 7o)
Fig.
3.79.
T h e System
NaCI-ZrCI^.
129
3.80.
The System K C i - Z r C I ^
C. J . Barton, R. J . S h e i l , and W. R. Grimes, unpublished w o r k performed at the Oak Ridge

N a t i o n a l L a b o r a t o r y , 1955.
Invariant
Mole % ZrCI^
in Liquid
Phase Reaction at
Type of Equilibrium
Temperature
(C)
23
600 5
Eutectic
L ^ = = i K C I + 2KC|.ZrCl4
33.3
790 5
L,^^^2KCl'ZrCl4
48
565 5
Peritectic
L + 2KC|.ZrCl4^=â.7KCl'6ZrCI^
222+4
Inversion
a.7KC|.6ZrCl4^=:^/3-7KCI'6ZrCl4
65
225 + 4
Eutectic
L ^ = ^ a . 7 K C l ' 6 Z r C l 4 + ZrCI^
Some phase w o r k on t h i s system has been reported by H. H. K e l l o g g , L . J . H o w e l l , and R. C.
Sommer,
mer.
Physical
Physical
KCl-ZrCl^,
Chemical
Chemical
Summary Report,
Properties
Properties
of the
Systems
Systen
NaCl-ZrCl.,
KCl-ZrCl.,
and
NaCl
NYO-3108 ( A p r i l 7, 1955).
UNCLASSIFIED
ORNL-LR-DWG 46(52
800
^
700
N,
V.
600
- .i
> < ^s^
'N^
-1
500
'
S 1
o:
cU- 1
\V
UJ 1
>
h2
^
S^
\\
V
>
,
\
U1-
c
300
O "
ID '
t\J
--f
200
\ /
.
-' } - * .w-.
1*^"r -
100
KCI
(0
20
30
40
50
60
ZrCI^ (mole %)
Fig, 3.80. The System KCI-ZrCI^.
130
70
80
90
ZrCI.
3.81.
The System LiCl-UCl3
C. J . Barton, A. B. Wilkerson, and W. R. Grimes, unpublished work performed at the Oak

Preliminary diagram. The system L i C I - U C l 3 contains a single eutectic at 75 L i C l - 2 5 UCI3
(mole %), m.p. 495 5C.
UNCLASSIFIED
DWG 2 2 2 5 2
900 I
1
10
1
20
L_
30
40
50
60
70
80
90
UCI3
400
300 I
LiCI
UCI3 (mole %)
Fig. 3.81.
The System LiCI-UCIg.
131
3.82. The System LiCi-UCI^

C. J . Barton, R. J. Sheil, and W. R. Grimes, unpublished work performed at the Oak Ridge
Invariant
Mole % UCI^
in Liquid
Phase Reaction at
Type of Equilibrium
Temperature
(C)
29
33.3
430 1 0
48
L F = ^ 2 L i C l . U C I ^ + LiCI
Eutectic
415
405
f=^2LiC|.UCI^
Eutectic
:i2LiC|.UCl4+UCl4
Some data on this system were reported by C. A. Kraus in Phase Diagrams

Salts
of Uranium with Halides
of the Alkali and Alkaline
of Some
Complex
Earth Metals, M-251 (July 1, 1943).
UNCLASSIFIED
DWG 1 9 9 0 4 R
600
" ^ * ^
500
r-1r-o-o^
r
p"
300
200
_j
100
LiCI
10
20
40
50
UCL
60
(mole %)
Fig. 3.82. The System L i C I - U C I ^
132
70
90
UCl,
3.83. The System NaCI-UCl3

C. A. Kraus, unpublished work.
Preliminary diagram constructed with the author's permission from data reported in Phase
Diagrams
of Some Complex Salts of Uranium with Halides
of the Alkali
and Alkaline
Earth
Metals, M-251 (July 1, 1943).

The system N a C I - U C i , contains a single eutectic at 67 NaCI-33 UCI3 (mole %), m.p. 525C.
UNCLASSIFIED
900
300
700
600
500
10
20
9 ^
400
300
NaCl
30
Fig. 3.83.
40
50
60
UCl3 (mole %)
70
80
90
UCU
The System NaCI-UCl3.
133
3.84.
The System NaCi-UCI^
C. J . Barton, R. J . Sheil, A. B. Wilkerson, and W. R. Grimes, unpublished work performed at

the Oak Ridge National Laboratory, 1953.
.. . , . , . . _ .
Mole % U C L
^
,n L.qu.d
Invariant
Type of Equilibrium
Temperature
^,^^
Phase Reaction at Invariant Temperature
30
430 5
Eutectic
t . f = : : i N a C I + 2NaCI'UCl4
33.3
440 + 5
L^
47
370 5
Eutectic
L^
57
415+5
Peritectic
L + UCl . ^
2NaCI*UCI .
^ 2NaCI'UCI . + unidentified compound
unidentified compound
A phase diagram of this system has been reported by C. A. Kraus in Phase Diagrams of Some
Complex Salts of Uranium with Halides of the Alkali and Alkaline
Earth Metals, M-251 (July 1,
1943).
UNCLASSIFIED
DWG 21104
I
i
1
-^
^
\
^ i^n
O
^
_ri-^^^&filK n
d j
i.
Cn.
'' "
i
i
_<1-
C.J
tM
40
50
60
UCL (mole %)
Fig. 3.84. The System NaCl-UCl

4
134
'
3.85.
The System KCi-UCi^
C. J . Barton, A. B. Wilkerson, T. N. McVay, R. J . Sheil, and W. R. Grimes, unpublished work

performed at the Oak Ridge National Laboratory, 1954.
Invariant
Mole % U C I .
4
in Liquid
Te Tiperature
Phase Reaction at
Type of Equilibrium
(C)
^^
' KCI + 2KCl'UCl4
25
550
Eutectic
33.3
630
L ^
44
330
Eutectic
L ^ ^ 2 K C l ' U C l 4 + KCI-UCI^
49
345
Peritectic
L + KCI'3UCl4^=iKCI'UCl4
61
395
Peritectic
L + U C I _ , ^ ^ KCI'SUCI^
2KCI'UCL
A phase diagram of this system has been reported by C. A. Kraus in Phase Diagrams of
Some
Complex Salts
of Uranium with Halides
of the Alkali
and Alkaline
Earth Metals, M-251
(July 1, 1943).
UNCLASSIFIED
ORNL-LR-DWG 1532R
800
700
o 600
cc
3
500
<
01
400
300
UCI4 (mole 7o)
Fig. 3.85. The System KCI-UCI^.
135
3.86. The System RbCl-UCl3

C. J. Barton, R. J. Sheil, A. B. Wilkerson, and W. R. Grimes, unpublished work performed
Invariant
Mole % UCI3
Phase Reaction a t
Temperature
in L i q u i d
I n v a r i a n t Temperature
(C)
610
15
Eutectic
::i;RbCI + 3 R b C I " U C L
25
745 i
40
560 + 10
Peritectic
L + 3RbCIUCI
45.5
513 + 5
Eutectic
L^=i2RbCI'UCl3+
49
550 10
Peritectic
L + UCl3^=^RbCI'UCl3
10
^=^3RbCI'UCl3
3V-
;2RbCI'UCI
RbCIUCl3
UNCLASSIFIED
ORNL-LR-DWG
340
900
700
AN
Ld 600
/ ^
rry, VA,
C>
'
o c
O O o
-oooxf " 0 0 ^ % -
500
o o c
o
o
=)
30
F i g . 3.86.
136
ro
3
O
cc
(M
ro
20
o /
o
300
)
=
ro
[O
400
10
\
o
RbCI
l^-
N/
-Q
40
50
UCl, (mole %)
60
The System R b C I - U C I ,
70
80
90
UCU
3.87.
C.
The System C s C i - U C l ^
J. Barton, A. B. Wilkerson, and W. R. Grimes, unpublished work performed at the Oak

Invariant
Temperature
Mole % UCL
A
in Liquid
Phase Reaction at
Type of Equilibrium
(C)
20
505 5
Eutectic
L ^ = ^ C s C I + 2CsCIUCl4
33.3
657 5
L ^=::^2CsCIUCl4
58
370 + 5
Eutectic
L ^
63
382 5
Peritectic
L + UCl4-^=^CsCI2UCl4
^2CsCI-UCI^+ CsCI'2UCl4
UNCLASSIFIED
DWG 22253R
/I,
'
/
ffl
>
\
- <=M5^^)
c r-W^S-^
A
r-
^/L^^f
^^
CI
o
D
o
o
o
u
CM
40
50
60
80
90
UCL
UCL (mole %)
Fig. 3.87. The System CsCI-UCI^.
137
3.88.
The System K j C r F g - N o j C r F ^ - L l j C r F ^
B. J. Sturm, L. G. Overholser, and W. R. Grimes, unpublished work performed at the Oak

UNCLASSIFIED
138
4.
O X I D E AND H Y D R O X I D E SYSTEMS
4 . 1 . The System S i 0 2 - T h 0 2
L. A. Harris, " A Preliminary Study of the Phase Equilibria Diagram of Th02Si02," / . Ar,
Ceram. Soc. 42, 74-77 (1959).
UNCLASSIFIED
PHOTO 31087
2300
\
\
2200
\
\
Th02 + LIQUID
2100-
LIQUID
\
UJ
IT
Z)
2000-
1975 ^ 5 0
)<
IT
UJ
Q.
.
I900-
TbOj + ThOg SiOg
UJ
\
\
ThOg SiOg + LIQUID
1800
\
1700 t 10
1700
SiOy -^
LIQUID
o
ThOg SiOj + SiOj
(1600
20
ThO,
30
40
50
60
S1O2 ( WT %)
70
80
90
100
SiO,
Fig. 4 . 1 . The System SiOo-ThO,
139
4.2. The System LlOH-NoOH

C. J . Barton, J . P. Blakely, K, A. Allen, W. C. Davis, and B. S. Weaver, unpublished work
performed at the Oak Ridge National Laboratory, 1951.
A phase diagram of the system LiOHNaOH has been reported more
recently by N. A. Reshetnikov and G. M. Oonzhakov, Zhur. Neorg. Khim. 3, 1433 (1958).
Mole % L i O H
in L i q u i d
(C)
27
219
Eutectic
L ; ? : ^ NaOH
40
250
Peritectic
L-I-LiOH
180
Inversion
a-LiOH.NaOH
T y p e of
P h a s e R e a c t i o n at
Equilibrium
Invariant
Temperature
-I-a-NaOH-LiOH
^ : S ; a-LiOH-NaOH
^^-/S-LiOH.NaOH
UNCLASSIFIED
ORNL-LR-DWG
20463R
500
^
;
400
300
^
>.
\ ^
250
i
200
NaOH
\
. ^ ^
^^^
a-NaOH LiOH
1
r"""*^
'
I '
20
(^
r
/S-NaOH LiOH
30
40
50
60
LiOH (mole % )
Fig.
140
7^
4.2.
T h e System L i O H - N a O H .
70
90
LiOh
4.3. The System LiOH-KOH

C. J . Barton, J . P. Blakely, L. M. Bratcher, and W. R, Grimes, unpublished work performed
Mole % KOH
in L i q u i d
40
Phase R e a c t i o n at
C)
Incongruent m e l t i n g p o i n t of
315
3LiOH.2KOH
L + LiOH
3LiOH.2KOH
245
70
L ^^3LiOH.2KOH
Eutectic
+/3.K0H
UNCLASSIFIED
ORNL-LR-DWG 2 0 4 6 0 R
600
500
h^
400
399^
^
^
300
"
/
/
X
(3
"
/3-K0H-2
i ^
200
o
ro
100
LiOH
20
30
40
50
60
70
80
90
KOH
KOH (mole %]
Fig. 4 . 1
T h e System L i O H - K O H .
141
4.4. The System NaOH-KOH

G. von Hevesy, " T h e Binary Systems NaOH-KOH, KOH-RbOH, and RbOH-NaOH," Z.
physik. Chem. 73, 667-84 (1910).
UNCLASSIFIED
400
350
\y
\
\
300
250
LIQUIDUS DIAGRAM
y^
"~~^\
. ^
200
^
"
a--/3 PHASE
TRANS ITION DIACSRAM
150
100
KOH
(0
20
30
40
50
60
NaOH (mole % )
Fig. 4.4. The System N a O H - K O H .
142
70
80
90
NaOH
4.5. The System NoOH-RbOH

G. von Hevesy, " T h e Binary Systems NaOH-KOH, KOH-RbOH, and RbOH-NaOH," Z.
physik. Chem. 73, 667-84 (1910).
UNCLASSIFIED
320
300
280
RbOH a
\
\
\
260
240
\
220
180
RbOH
10
^ ^
\ /
20
30
\
\ \
\
.Z^''
^ ' '
Â^'"
RbOH(NaOH 2
40
50
60
70
80
90
NaOH
NaOH (mole % )
Fig.
4.5.
T h e System N a O H - R b O H .
143
4.6.
The System B a ( O H ) 2 - S r ( O H ) 2
K. A . A l l e n , W. C. D a v i s , and B. S. Weaver, u n p u b l i s h e d work performed at the Oak Ridge
National L a b o r a t o r y , 1951.
Preliminary
diagram.
The
system
Ba(0H)2Sr(0H)2
contains
single
eutectic
at
37
S r ( O H ) 2 - 6 3 B a ( 0 H ) 2 (mole % ) , m.p. 3 6 0 C .
UNCLASSIFIED
ORNL-LR-DWG 20462R
550
500
450
400
350
300
Sr(OH),
10
20
30
50
70
Fig. 4.6. The System Ba(OH)2-Sr(OH)2.
144
80
90
Ba(OH)^
5.
5.1.
AQUEOUS SYSTEMS
T h e System U O 2 - P 2 O 5 - H 2 O , 2 5 C Isotherm
J.
M, Schreyer, " T h e S o l u b i l i t y
of Uranium(IV) Orthophosphates
in Phosphoric
A c i d So-
l u t i o n s , " / . Am. Chem. Soc. 77, 2972 (1955).

T h e t r a n s i t i o n p o i n t between U ( H P 0 4 ) 2 ' 6 H 2 0 and U ( H P 0 4 ) 2 ' H 3 P 0 4 . H 2 0 as stable
was at 0.62
+ 0.02 M U (10.3 wt % U O j ) and 9.8 + 0.1 M PO^ (42.6 wt % P j O j ) ,
1.63 + 0.03 g / m l .
solids
density
The compound U ( H P 0 4 ) 2 ' H 3 P 0 4 > H 2 0 is incongruently soluble in water.
10
20
30
40
50
60
70
80
90
GRAMS OF PgOg PER 100 GRAMS OF MIXTURE
100
Fig. 5.1. The System U O j - P 2 O 5 - H 2 O , 25C Isotherm.
145
5.2.
T h e System U O 3 - H 3 P O 4 - H 2 O , 2 5 " C Isotherm

J.
M. Schreyer and C . F.
Baes, Jr.,
" T h e S o l u b i l i t y of Uranium(VI) Orthophosphates
in
Phosphoric A c i d S o l u t i o n , " / . Am. Chem. Soc. 76, 354 (1954).

The
normal
phosphate
( U 0 2 ) 3 ( P 0 4 ) 2 - 6 H 2 0 is stable
below
0.025
mole % H g P O ^ .
The
s t a b i l i t y ranges ore as f o l l o w s :
Compound
Total Phosphate Molarity
(U02)3(P04)2-6H20
<0.014
U02HP04-4H20
0.014-6.1
U02(H2P04)2'3H20
>6.1
UNCLASSIFIED
DWG 20233
60
50/
SATURATED SOLUTIONS
SLURRIES
40/
30/
C?^
U 0 , H Pq 4 H,0
20/
H,0 0
Fig. 5 . Z
146
J-
10
20
J^
2L.
T h e System U O 3 - H 3 P O 4 - H 2 O , 2 5 " C Isotherm.
U0,(HJP0^3H,C
40
50
0 - 6 0 mole % UO3, 0 - 6 0 mole % H3PO4.
60
5.3. The System U ( H P 0 4 ) 2 - C i 2 0 7 - H 2 0 , 25C Isotherm

J . M. Schreyer and L. R. Phillips, " T h e Solubility of Uranium(VI) Orthophosphates in
Perchloric Acid Solutions," / . Phys. Chem. 60, 588 (1956).
The
stable solids
U(H2P04)2(CI04)2'6H20.
sitions tested.
in this
system ore U(HP04)2-2H20,
U(H2P04)2(CI04)2-4H20,
and
Metastable anhydrous U(HP04)2 formed readily in all solution compo-
X-ray diffraction patterns indicated the existence of three polymorphic forms
of U(H2P04)2(CI04)2-6H20.
Wt.7o
UNCLASSIFIED
ORNL-LR-DWG. 6845
UOE
70
_U(HP04)2
_y ( H P 0 4 ) 2 2H2O
.U(H3P04)2 (0104)2- 4 H 2 O
_ U ( H 2 P 0 4 ) 2 (0104)2 6 H 2 O
H2O
10
15
\^ \l \l
20
25
30
\l
35
Wt.%
40
45
50
55
60
Fig. 5.3. Schreinemakers' Projection of the System UOjPjOq-CI jOyH2O at 25C.

the UOjCl_0_H.O face, plotted in rectangular coordinates.
65
70
CI2O7
A projection on
147
5.4. The System U 0 3 - N a 2 0 - C 0 2 - H 2 0 , 26C Isotherm

C. A. Blake, C. F. Coleman, K. B. Brown, D. G. H i l l , R. S. Lowrie, and J . M. Schmitt,
"Studies in the Carbonate-Uranium System," / . Am. Chem. Soc. 78, 5978 (1956).
UNCLASSIFIED
ORNL-LR-OWG 39180
COMPOSITION t %
F i g . 5.4a.
plotted
T h e System UO3Na.OCO,H j O at 2 6 C .
in weight per cent.
II,
solutions
in
equilibrium
Na2C03.7H20;
NoHCOj,
in
equilibrium
with
D,
uranyl
with
E,
Na4U02(C03)3.
angular prism represents pure water.
148
sodium
carbonate.
N a 2 C 0 3 . IOH2O;
G, U O j C O j ; H,
Compositions are
I, solutions in equilibrium with sodium uranates;

uranyl
A,
tricarbonote;
Na2C03;
B,
III,
solutions
NajCOj.HjO;
Na2CO3.NaHCO3.2H2O
(trona);
C,
F,
The entire upper face of the tri-
T h e stable u r a n i u m - c a r b o n a t e s o l i d s found were U O j C O g and N a ^ U 0 2 ( C 0 3 ) 3 .
The s o l u t i o n
composition at the t r a n s i t i o n point (not determined e x a c t l y ) was at least 26 wt % U 0 - , 5.6 w t %

KaÔ,
and 7.2 wt % C O j (mole ratio U 0 3 : N a 2 0 : C 0 2 = 1:1.0:1.8).
Further
data
on
(document No. 5079).

planes
this
system
are
available
from
the American
Documentation
Institute
T h e s e include c o m p o s i t i o n s , p H ' s , and d e n s i t i e s at points in and near the
Na20-C02-H20,
UO3-Na2O-H20,
U02C03-Na2C03-H20,
Na4U02(C03)3-NaHC03-
H j O , U 0 3 - N a 2 C 0 3 - H 2 0 , U 0 3 - N a H C 0 3 - H 2 0 , and U 0 2 C 0 3 - N a 2 0 - H 2 0 .
Related
phase e q u i l i b r i a
in the system N a 2 0 U O 3 - H 2 O at 50 and 7 5 C are reported by
J . E. R i c c i and F. J . L o p r e s t , / . Am. Chem. Soc, 77, 2119 (1955).
UNCLASSIFIED
PHOTO 24714
H2O
A . Na, UO;(CO, )3
B. NajUOj (COj )2
COMPOSITION
Na2C03
C . Na^COj lOHÔ
wt%
(B)
UO2CO3
Fig. 5.46. The Section U0 2 C 0 3 - N a 2 C 0 3 - H 2 0 at 26C.
149
5.5. Portions of the System T h 0 2 - N a 2 0 - C 0 2 - H 2 0 , 25C Isotherm

F. A. Schimmel, unpublished work performed at the Oak Ridge National Laboratory, 1955.
The stable thorium-carbonate solids found were ThOC03'8H20 and Na.Th(C03)5'12H20.
Ternary Points
Composition of Solution (wt %)

N a g T h ( C 0 3 ) 5 . 1 2 H 2 0 , N a H C 0 3 , and
ThO,
Na20
0.62
12.0
9.96
0.48
14.1
10.86
C0
N a 2 C O 3 . N a H C O 3 . 2 H 2 O (trona)
N a | j T h ( C 0 3 ) 5 . 1 2 H 2 0 , N a 2 C O 3 . 1 0 H 2 O , and trona
UNCLASSIFIED
ORNL-LR-DWG 38010
EQUILIBRIUM SOLID PHASES

a-b
b
b-c
b-d
d
d-e
d-f
g-h
z + NaHCOj
z + NaHC03 +TRONA
NaHC03+TRONA
z +TRONA
z + TRONA + NOjCOj lOHjO
TRONA + NOjCOj lOHjO
z+NajCOj (OHjO
z + ThOCOj SHÔ
(z=3Na,0 Th02 SCOj tZHjO

COMPOSITION wt %
(Na,0 CO,)
F i g . 5.5a.
150
(3Na,0 4C0J
(Na,0 2C0,)
Perspective Representation of the System T h 0 2 - N a 2 0 C O 2 H . O as a Tetrahedron.
The highest thorium solubility found was 3.35 wt % ThOj (3.06 wt % Na20, 3.60 wt % CO2)
in equilibrium with solid Na^Th(C03)g.l2H20 and Th0C03.8H20.
binary
line were not established.)
(The terminal points of this
The maximum thorium solubility
in equilibrium
with
Na4Th(C03)5.12H20 and Na2CO3.10H2O was 1.25 wt % ThOs (12.5 wt % Na20, 9.4 wt % CO2);
with Na^Th(C03)5.12H20 and trona, the highest solubility was 0.7 wt % ThOj (12.6 wt % NojO,
10.4 wt % CO2). The highest found with Na^Th(C03)5.12H20 and NaHC03 was 1.2 wt % Th02
(5.0 wt % Na20, 6.0 wt % COj), which was the most dilute NaHC03 solution tested.
UNCLASSIFIED
ORNL'LR-DWG 38013
Q-b
b
b-c
b-d
d
d-e
d-f
g-h
2+N0HCO3
z + NaHC03 +TRONA
NaHCOj + TRONA
2 + TRONA
z + TRONA + NOjCOj-IOHjO
ThOCO,
TRONA+ Na2CO3-10H20
z + Na2C03-10H20
COMPOSITION wt7o
z + ThOC03 SHjO
(z=NaeTh(C03)5-12H20)
(TRONA =NaXO,-NaHCO, 2H,0)
Na,0
NaXO,
e c TRONA
Fig. 5,56. The System ThO j - N o j O - C O j - H j O at 25C.

along radii from the H2O vertex.
Projection to the T h 0 2 - N a 2 0 - C 0 2 face
151
UNCLASSIFIED
ORNL-LR-DWG 38011
a-b
z + NciHCOj
z+NaHCOj+TRONA
b-c
NaHCOj + TRONA
b-d
z+TRONA
z + TRONA + NOjCOj lOHjG
d-e
TRONA+Na2C03 lOHÔ
d-f
z + NOjCOj lOHjO
g-h
z + ThOCOj SHjO
COMPOSITION wt 7 .
(z = 3 N a 2 0 - T h 0 2 SCOj 12H2O)
(TRONA = N a X O , NaHCO, 2H,0)
(3Na,0 4 C 0 J
Fig. 5.5c. The System T h 0 2 - N a 2 0 - C 0 2 - H 2 0 at 25C. Projection to the T h 0 2 ' C 0 2 - 3 N a 2 0 . 4 C 0 2 - H 2 0

internal plane, represented as an equivalent triangle, along radii from the CO2 vertex.
100 wt % H2O.
152
Portion from 70 to
5.6.
The System N a 2 0 - C 0 2 - H 2 0 , 2 5 C Isotherm

F. A . Schimmel, u n p u b l i s h e d work performed at the Oak Ridge N a t i o n a l Laboratory, 1955.
S i g n i f i c a n t changes from the data of Freeth [Phil.
Trans.
Roy,
Soc. London
233, 35 (1922)]
were found throughout the range; there was closer agreement in the bicarbonate range with the
data of H i l l and Bacon [/. Am. Chem. Soc. 49, 2487 ( 1 9 2 7 ) ] .
Transition Points
Comp OS ition of So lution
(wt

NajO
%)
CO2
NaOH.H20 and Na2C03
40.5
0.85
NojCOg and Na2C03.H20
31.4
0.72
Na2C03.H20 and Na2C03.7H20
18.7
6.9
Na2C03.7H20 and Na2CO3.10H2O
17.85
7.8
Na2CO3.10H2O and Na2CO3.NaHCO3.2H2O (trona)
13.7
10.35
Trona and NaHCO-
11.9
9.5
153
The System N a 2 0 - C 0 2 - H 2 0 , 25C Isotherm

Composition of Saturated Solution
(wt %)
NojO
Equilibrium Solid Phase

CO2
41.3
NaOH.H20
40.5
0.85
40.45
31.6
31.4
31.1
29.9
0.8
N<'2*^3
Na2C03
26.6
25.2
23.2
0.4
Na2C03 H2O
Na2C03 H2O
0.55
Na2C03 H2O
0.9
23.15
1.0
Na2C03 H2O
Na2C03 H2O
21.15
19.3
2.3
Na2C03 H2O
4.3
NOjCOg H j O
18.95
6.0
Na2C03 H2O
18.57
18.6
7.5
18.7
18.5
17.7
6.9
N 2 ^ 3 H2O (metastable)
'^2^3 H2O (metastable)
Na2C03 H2O and Na2C03.7H20
18.3
7.3
17.85
17.3
7.8
0.67
0.72
0.78
0.5
7.8
6.75
7.95
Na2C03 7H2O (metastable)

N 2 " 3 7H2O (metastable)
Na2C03 7H2O
8.1
Na2C03 7H2O and Na2CO3.10H2O

NOjCOg IGHjO
Na2C03 lOHjO
Na2C03 IOH2O
Na2C03 .IOH2O
13.7
8.85
Na2C03 lOHjO
13.28
9.4
13.55
14.1
13.7
10.15
'^2^3 IOH2O
N-2CO3 lOHjO
Na2C03 IOH2O (metastable)
No CO, lOH.O and trona*
Trona (metastable)
Trona (metastable)
Trona
16.1
15.6
15.1
17.0
16.7
7.88
7.9
7.92
11.0
10.35
13.0
12.7
13.8
11.9
10.35
11.55
10.5
9.3
9.4
,8.0
9.5
8.8
Trona and NaHC03

NaHC03
NaHC03
NaHC03
8.1
7.5
6.4
6.5
5.4
5.75
3.9
5.0
NaHC03
NaHC03
NoHCOg
NoHCOg
3.56
4.95
4.93
NaHCOg
NaHC03
3.47
*The formula of trona is Na2CO3.NaHCO3.2H2O.
154
Na2C03
Na2C03 and Na2C03.H20
Na,CO-.H,0
Its
(n o
8
6?
I
3
I
o
0)
CN
o
X
8I
CN
0
Z
E
M3
5.7.
Solubility of Uranyl Sulfate in Water

1. C . H. Secoy, / . Am. Chem. Soc. 72, 3343 (1950) (data above 3 0 0 C ) .
2. C . H. Secoy, / . Am. Chem. Soc. 70, 3450 (1948) (data up to 3 0 0 C ) .
3.
L.
Helmholtz
and
G.
Friedlander,
Physical
Properties
of
Uranyl
Sulfate
Solutions,
MDDC-808 (1943) (room temperature d a t a ) .

4 . C . D i t t r i c h , Z. physik.
5.
E.
Chem. 29, 449 (1899).
V . Jones and W. L . M a r s h a l l , HRP
Quar. Prog.
Rep.
March
15, 1952, O R N L . 1 2 8 0 ,
p 180-83.
6.
E.
V . Jones and W. L . M a r s h a l l ,
HRP
Quar.
Prog.
Rep.
Jan.
31,
1959,
ORNL-2696,
p210-n.
The t w o - l i q u i d - p h a s e region of t h i s system in a c t u a l i t y must be represented by the three
components UO3, SO3, and H j O .
T h e curve representing the boundary of l i q u i d - l i q u i d i m m i s c i -
b i l i t y is correct for s t o i c h i o m e t r i c s o l u t i o n s . However, the t i e lines w i t h i n the region of i m m i s c i b i l i t y do not connect t w o s o l u t i o n s c o n t a i n i n g s t o i c h i o m e t r i c U O j S O . but rather connect s o l u t i o n s c o n t a i n i n g v a r y i n g c o n c e n t r a t i o n s and ratios of UO3 and SO3 ( F i g . 5.10).
trations
A t low concen-
and high temperatures, that i s , below 0.02 m UO2SO4 and above 2 5 0 C , h y d r o l y s i s
occurs to produce a n o n s t o i c h i o m e t r i c solution phase.
T h e p o i n t of h y d r o l y s i s is dependent on
concentration and temperature (see Sec 5.13).

Note:
R e v i s e d data (ref 5) are used to construct the i m m i s c i b i l i t y boundary in the f i g u r e .
E a r l i e r data (ref 1) showed higher temperatures in t h i s region and a p o s s i b l e l i k e l i h o o d of a c i d

impurity in the s o l u t i o n s .
156
UNCLASSIFIED
ORNL-LR-DWG 844A
400
UNSATURATED SOLUTION (^2) + VAPOR

'c
350
X
TWO-LIQUID PHASES
'Û02S04-H20
\ SOLUTION
'^2>/^
300
\ "
ST
250 -
3
H
200
UNSATURATED SOLUTION
<
IT
UJ
Q_
150
U
h-
100
/
50
1 U02S04-3 H2O + SOLUTION
1
0
ICE + S O L U T I O N * N ^
-50
ICE + U02S04-3 H2O
1
2
3
4
5
6
m, moles/1000 g H2O
Fig. 5.7. The System U02SO^-H20.
157
5.8.
Two*Llquld*Phase Region of U O j S O . in Ordinary and Heavy Water

E. V . J o n e s and W. L . M a r s h a l l , HRP Quar. Prog.
Rep. March 15, i 9 5 2, O R N L - 1 2 8 0 , p 1 8 0 - 8 3 .
T h e two curves shown are boundary curves for l i q u i d - l i q u i d i m m i s c i b i l i t y obtained by observing the phase-transitional behavior of known U02S0^H2O (D2O) s o l u t i o n s in sealed tubes
as
a f u n c t i o n of temperature.
s y n t h e t i c method.
For later reference,
t h i s procedure is designated the v i s u a l -
A s was d e s c r i b e d in Sec 5.7, the concentrations and c o m p o s i t i o n s of the two
phases w i t h i n the boundary region at e q u i l i b r i u m cannot be obtained from t h i s f i g u r e .
Mixtures
w h i c h are s o l u t i o n s at lower temperatures separate into t w o l i q u i d phases as the temperature is

r a i s e d , according to the boundary c u r v e s .
158
UNCLASSIFIED
O R N L - L R - D W G 29314
310
300
UJ
cr
cr
290
UJ
CL
UJ
280
270
0
m, moles UO2SO4/IOOO gm HÔ, D2O

Fig.
5.8.
Two-Liquid-Phase
Region of U O j S O .
in Ordinary and Heavy
Water.
159
5.9. The System U O j - S O j - H j O

1. A. Colani, Bull. soc. chim. France [4] 43, 754-62 (1928).
2. J . S. G i l l ,
E. V. Jones, and C. H. Secoy, HRP Quar. Prog.
Rep. Oct. 31, 1953,
ORNL-1658, p 87.
The 25 data on the S03-rich side are those of Colani.
The higher temperature data are
those of G i l l , Jones, and Secoy, obtained by filtration techniques at temperature.
The number
and identity of the solid phases in the UOg-rich regions at 25, 100, and 175C are somewhat
uncertain.
Subsequent unpublished work of F. E. Clark and C. H. Secoy has disclosed that the
K solid is identical (x-ray diffraction) with the mineral uranopilite, 6UO3.SO3.xH2O, that the G
solid is not identifiable as any known mineral, and that at least one additional unidentified
solid phase occurs at 25 and 100. The liquidus curves for the 25 and 100 isotherms are
essentially correct as shown except that the transition points (two solid phases) occur at somewhat lower concentrations than those indicated.
UNCLASSIFIED
DWG 21934
HgO
Fig. 5.9a. The System UO3-SO3-H2O at 25C.
160
UNCLASSIFIED
DWG 21935
F = U03H20
G = G BASIC SALT
E = U02S04-3H20
Fig. 5.9b,
The System U O j - S O g - H j O at 100C.
161
UNCLASSIFIED
DWG 21936
F = UOj- H2O
G = G BASIC SALT
E = U02-S04-3H20
Fig. 5.9c. The System UO3-SO3-H2O at 175C
162
UNCLASSIFIED
DWG 21937
SOLID PHASE ^ UOj-HgO
99.75
99.50
99.25
Fig. 5.9<^. The System U O j - S O j - H j O at 2 5 0 C
163
5.10. Coexistence Curves for Two Liquid Phases in the System U O j S O ^ H 2 S O ^ - H 2 0

H. W. Wright,
W. L .
M a r s h a l l , and C. H.
Secoy,
HRP
Quar.
Prog,
Rep.
Oct.
1,
1952,
O R N L - 1 4 2 4 , p 108.
All
at
zero
curves
in t h i s f i g u r e must e x t r a p o l a t e to the c r i t i c a l
concentration
of
uranium.
These
ore
boundary
temperature of water
curves
which
were
(374.2C)
determined
by
observing sealed tubes in w h i c h i m m i s c i b i l i t y occurred in UO3SO3HjO s o l u t i o n s upon v a r y i n g

the temperature.
sitions
A s was e x p l a i n e d in Sec 5.7, they do not represent concentrations and compo-
of the t w o l i q u i d phases w i t h i n the temperature-concentration
but are lower s o l u t i o n boundary c u r v e s .
164
region of
immiscibility
UNCLASSIFIED
ORNL-LR DWG 6 5 8 6
450
425
400
350
325
300
275
(0
(5
20
25
URANIUM (wt %)
F i g . 5.10.
Coexistence Curves for Two Liquid Phases in the System U O . S O , - H - S O . - H . O .
165
5.n.
Two-Liquid-Phcse Region of the System U O j S O ^ - H j S O ^ - H j O
R. E. Leed and C. H. Secoy, Chem.

C. H. Secoy, Chem. Quar. Prog.
Quar. Prog.
Rep. Sept. 30, 1950, O R N L - 8 7 0 , p 2 9 - 3 0 ;
Rep. Dec, 31, 1949, O R N L - 6 0 7 , p 3 3 - 3 8 .
In contrast w i t h the i m m i s c i b i l i t y
curves shown in F i g . 5.10, each of these curves must
e x t r a p o l a t e to a c r i t i c a l temperature curve for SO3HjO in which a small or n e g l i g i b l e amount of

UO3 is d i s s o l v e d .
critical
Since SO3 d i s s o l v e d in H2O ( n e g l e c t i n g any d i s s o l v e d UO3) w i l l e l e v a t e the
temperature, the curves obtained from s o l u t i o n s c o n t a i n i n g a constant amount of free
H . S O . w i l l a l l extrapolate to c r i t i c a l temperatures higher than that (374.2C) for H2O a l o n e .
UNCLASSIFIED
DWG. 10085
20
Fig. 5.11.
166
30
40
50
WEIGHT PERCENT UO2SO4
80
T w o - L i q u i d - P h a s e Region of the System U O 2 S O 4 - H 2 S O 4 - H 2 O .
5.12.
Two*Liquid*Phase Coexistence Curves for U 0 3 - R i c h Solutions in the System UO3SO3

H j O With and Without HNO3
E. V . Jones and W. L . M a r s h a l l , HRP Quar, Prog,
Rep. July
1, 1952, O R N L - 1 3 1 8 , p 1 4 7 - 4 8 .
These curves have been obtained by the v i s u a l - s y n t h e t i c method mentioned in Sec 5.8.
They
are therefore boundary curves and do not describe compositions and concentrations w i t h i n the
liquid-liquid immiscibility region.
UNCLASSIFIED
DWG
16625
^ = ^ 0 0
300
290
-I
_
280
UJ
Q:
-0-
4 = ^ 2 0 ^ ^ ^
^r\^y
^s>~-
^v.
3^0/^^
\ ^ .
-^
0*
"~-o
rt--'"
270
1-
<
(E
UJ
Q.
UJ
300
290
~
--
"
\
280
270
- g ^ = 1 20 AND CONTAINING
y;
0 02//U02(N03)2
V
^
10
20
30
40
TOTAL URANIUM (wt %)

Fig. 5.12. Two-Liquid-Phase Coexistence Curves for UO3Rich Solutions
in the System UO3-SO3-H2O With and Without HNO3.
167
5.13. Solubility of UO3 in H 2 S O 4 - H 2 O Mixtures

W. L. Marshall, Anal.
Chem. 27, 1923 (1955).
The data are represented in this manner in order to show the full concentration range on one
figure and to best indicate the degree of precision.
and ^MO^'WSi
above 2 0 5 C .
The solid phase is a - U 0 3 . H 2 0 below 205C
These curves represent hydrolysis equilibria.
UNCLASSIFIED
ORNL-LR-DWG- 1840 AR
1.0
OJ
<
T W O - L I O U I D PHASE
REGION
o DIRECT UO3 AND SO4

ANALYSES
ANALYSES BASED ON
pH AT ROOM TEMPERATURE
*.* .*
hUJ
.. -
^^ '
i 0.01
o
o
<S)
0.001
0.0001
0
1.4
SOLUBILITY MOLE RATIO U O ^ / H ^ S O ^
Fig. 5.13. Solubility of UO3 in H2SO^-H20 Mixtures.
168
5.14. Effect of Excess H2S0^ on the Phase Equilibria in Very Dilute UOjSO^ Solutions
1. W. L. Marshall, Anal. Chem. 27, 1923 (1955).
2. H. W. Wright, W. L. Marshall, and C. H. Secoy, HRP Quar. Prog. Rep. Oct. 1, 1952,
ORNL-1424, p 108.
The curves were drawn by C. H. Secoy from data used for Figs. 5.10 and 5.13.
UNCLASSIFIED
ORNL-LR-DWG 19100
375
350
325
<
UJ
CL
LJ 3 0 0
275
250
1.0
URANIUM (wt 7o)
Fig, 5.14. Effect of Excess H2SO. on the Phase Equilibria in Very Dilute
UO-SO . Solutions.
5.15.
R.
Second*Liquid*Phase Temperatures of U 0 2 S O ^ - L i 2 S O . Solutions

S. Greeley, S. R. B u x t o n , and J . C . G r i e s s , " H i g h Temperature Behavior of Aqueous
U 0 2 S O ^ - L i 2 S O ^ and U 0 2 S O ^ - B e S 0 4 , " paper presented at American Nuclear Society 2nd Winter

Meeting, New York C i t y ( O c t . 1957).
lution
Corrosion
Studies
for Quarter
A l s o R. S. Greeley and J . C. G r i e s s , HRP Dynamic
Ending
July
31, 1956, O R N L C F - 5 6 - 7 - 5 2 , p 3031.
These data were obtained by the v i s u a l - s y n t h e t i c method mentioned in Sec 5.8.
UNCLASSIFIED
ORNL-LR-DWG 19101
400
380
'ir
y
*-* ^
360
/^
Zi 340
UI
cc
z>
I
320
/
/
UJ
a
UJ
^
300
/
/
y
^ ^
-0
-^
.k /,A /
/
>Li2 5U4
J
o 1.3 /77 UO2SO4 PLUS Li2S04
1
1
2 . 2 / 7 7 UO2SO4 PLUS LI2SO*
1 CONCENTRATIONS ARE UNCORRECTE D
280
260
AT ELEVATED TEMPERATURES
240
0
Fig.
lutions.
170
0.02
5.15.
0.05
0.1
0.2
Li2S04 {m)
Second-Liquid-Phase
0.5
1.0
2.0
5.0
Temperatures of UOjSO .Li-SO . So-
So-
5.16.
Second-Liquid*Phase Temperatures for U O j S O . Solutions Containing L i . S O . or BeSO.
R. S. Greeley and J. C. Griess, HRP Dynamic Solution Corrosion Studies for Quarter Ending
July 31, 1956, ORNL CF-56-7-52, p 30.
L i q u i d - l i q u i d i m m i s c i b i l i t y occurs at the boundary curves as the temperature is r a i s e d .
UNCLASSIFIED
ORNL-LR-DWG 15803
M O L A L I T Y OF UOoSO^
Fig.
5.16.
Second-Liquid-Phase Temperatures for U O . S O . Solutions Con-
taining L i 2 ^ 0 . or B e S O , .
171
5.17. Second*LiquidPhase Temperatures for BeSO^ Solutions Containing U O .

R. S. Greeley and J. C. Griess, HRP Dynamic Solution Corrosion Studies for Quarter Ending
July 31, 1956, ORNL CF-56-7-52, p 31.
Liquid-liquid immiscibility occurs at the boundary curves as the temperature is raised.
UNCLASSIFIED
ORNL-LR-DWG 15804
400
350
UJ
a:
I-
<
a:
UJ
a.
S
UJ
300
250
0.5
1.0
1.5
MOLALITY
Fig.
5.17.
taining U O , .
172
Second-Liquid-Phase
OF
2.0
2.5
3.0
BeS04
Temperatures for B e S O . Solutions Con-
5.18. The System NiSO^-UOjSO^-HjO at 25C

E. V. Jones, J . S. G i l l , and C. H. Secoy, HRP Quar. Prog. Rep. Oct. 31, 1954, ORNL-1813,
p 166-67.
Also included in the reference ore solubility data for this system at 175 and 250C.
The
data at high temperature ore not in sufficient quantity for a diagram to be presented.
UNCLASSIFIED
ORNL-LR-DWG 3713A
HgO
Fig. 5.18.
The System N i S 0 4 - U 0 2S0^-H20 at 25C.
Compositions are
plotted in weight per cent.
173
5.19.
Phase*Transition Temperatures in Solutions Containing CuSO^, UOjSO^, and H^SO^
F. E. C l a r k , J . S. G i l l , R. Slusher, and C. H. Secoy, / . Chem. Eng. Data 4, 12 (1959).

A l l data were obtained by the v i s u a l - s y n t h e t i c method mentioned in Sec 5.8 and represent
temperatures at w h i c h i m m i s c i b i l i t y occurred upon r a i s i n g the temperature.
No deductions can
be made regarding c o m p o s i t i o n s w i t h i n the t w o - l i q u i d - p h a s e r e g i o n .
UNCLASSIFIED
ORNL-LR-DWG 2 4 4 2 2 B
^^S^^^Si
325C-
^^^r--^2
UU^Û^^Vi
^ " ^
IC"
tVo)
15
?^fiR T
^
3
10
r/
5 5
o
~ ~ ~ - -~~~~~-~~-^
5
^ 3 4 0
-^.^^T^]^ "---.^
^.---'^^
/'^^..^-SSO
^ ^
(5
REGION OF BLUE-GREEN CRYSTALLINE SOLIDS
REFERENCE COMPOSITION OF
0 I m CuS04
O l m UO2SO4
-t)-
REFERENCE COMPOSITION OF HRT FUEL
-----ZI!^^;\,
OOO5/77CUSO4
0 0 4 / n UO2SO4
(PLUS CO 0 0 2 5 m H2S04)(557o)
U0,S0a(wt7,)
Fig.
174
5.19.
20
lllllllll REGION OF RED SOLIDS
--,,.,..^^^~~~~~~-~,
fr/C^=^Îff, r^^ ^ \ ^
10
U02S04(wt7o)
FOR APPEARANCE OF TWO LIQUID PHASES
31
TEMPERATURE CONTOUR LINES (isotherms)
38 75 mole % EXCESS
SULFURIC ACID
^^ 3 5 0
'
^8^"'~
0
U0,S0,(wt7o)
9?f> nole 7o EXCESS

SULFURIC ACID
Phase-Transition Temperatures in Solutions G i n t a i n i n g CuSO ., UO.SO ., and H_SO ..
5,20.
The Effect of CuSO^ ond NiSO^ on Phase.Transition Temperatures:

0.01 m H j S O ^
0.04 m UOjSO^;
C. H. Secoy et al., HRP Quar. Prog. Rep. July 31, 1957, ORNL-2379, p 163. Also additional
data:
F. Moseley, Core Solution
Corrosion
The
Product
Stability
in the Homogeneous
and Copper Concentrations,
curves for l i q u i d - l i q u i d
Reactor;
the Effect
of
HARD(C)/P-41 (May 1957).
immiscibility
s y n t h e t i c method mentioned in Sec 5 . 8 .
Aqueous
were drawn from data obtained by the v i s u a l -
Saturation temperatures for s o l i d - l i q u i d e q u i l i b r i a were
obtained by measuring s o l u t i o n concentrations as a function of temperature and determining a

break in the c u r v e .
The numbers in parentheses are temperatures at which the indicated s o l i d
phase appeared upon r a i s i n g the temperature.
Solid phases indicated in parentheses were found
in s m a l l q u a n t i t y .
UNCLASSIFIED
ORNL-LR-DWG 23014A
0 04
249\*(<249)J249)
| \T/200\ \
0 02
(Jg\
MTS)"
0 03
0 04
CuS04(/77)
Fig.
atures:
5.20.
T h e Effect of C u S O . and NiSO . on Phase-Transition
0.04 m U O j S O ^ ; 0.01
Temper-
mH^%0^.
175
5.21. The System U G j - C u O - N i O - S O g - D j O at 300C; 0.06 m SO3

J. S. G i l l , R. Slusher, and W. L. Marshall, HRP Quar. Prog. Rep. Jan. 31, 1959, ORNL-2696,
p 205-13.
The variation in solution composition in the presence of one, two, and three solid phases was
determined at 300C from 0.04 to 0.2 m SOj.
Solubility relationships at 0.06 m SO. were ob-
tained from these separate solubility curves, and the skeletal volume figure for the five-component system was drawn.
Other skeletal figures can be drawn at various SO, concentrations.
This investigation is s t i l l in progress, and the data are subject to revision.
UNCLASSIFIED
ORNL- LR-DWG. 3 5 7 i 4 A
Ternary Composition
0.014 /77 NiO
0.010 m CuO
0.025 m UO,
0.07
0.06
0.05
0.04
0.03
0.03
0.02
0.01
0.03
CuO
Fig. 5.21.
176
T h e System U 0 3 - C u O - N i O - S 0 3 - D 2 0 at 3 0 0 C ; 0.06 m SO3.
5.22. Solubility of Nd2(S04)3 in 0.02 m UOjSO^ Solution Containing 0.005 m H2SO^(180-300C)

R. E. Leuze et al., HRP Quar. Prog. Rep. April
30, 1954, ORNL-1753, p 176-79.
Also included in the reference are preliminary solubility data for rare earth sulfate mixtures
as well as Ce2(S04)3 and La2(S04)3 in 0.02 m UOjSO^, 0.005 m HjSO^.
UNCLASSIFIED
ORNL-LR-DWG 925A
10.0
5.0
V ISUAL
Of 3SERVATI ON MET^HOD
2.0
g
h-
d 1.0
j;0
aO
i/)
^
o
0.5
"RACER- FILTRATIC)N METH OD

V/-^
^
X
>
0.2
~""~~-o-
0.1
180
200
220
240
260
280
300
TEMPERATURE CC)
Fig. 5.22.
Solubility of Nd2(SO^)3 in 0.02 m UOjSO^ Solution Containing
0.005 m H2SO4 (180-300C).
177
5.23. Solubility of La2(S04)3 in UO2SO4 Solutions

E. V. J o n e s , M. H. Lietzke, and W, L. Marshall, / . Am. Chem. Soc. Ti, 267 (1957); a l s o
The
Solubility
Aqueous
of Several
Uranyl Sulfate
Experimental
Metal Sulfates
Solution,
at High Temperatures
and Pressures
in Viater and in
ORNL CF-55-7-69 (declassified Aug. 23, 1955).
data for Figs, 5.235.27 were obtained by the visual-synthetic method
described in Sec 5.8. The very large effect of UOjSO^ must be noted and indicates considerable solvation of other species by aqueous UO.SO^.
UNCLASSIFIED
DWG. '14640A
300
A TWO LIQUID PHASES

A MUTHMANN AND ROLIQ
250
o
o
UJ
CC
200
IN LZ5
m UO2SO4
h<
CC
UJ
CL
UJ
^50
- . - .
4 00
V
50
2.0
3.0
L a 2 ( S 0 4 ) 3 (wt % )
Fig. 5.23, Solubility of La2(S04)3 in U02S0^ Solutions.
178
4.0
5.24.
Solubility of CdSO^ in UO2SO4 Solutions
E. V. Jones, M. H. Lietzke, and W. L. Marshall, / . Am. Chem. Soc. 79, 267 (1957); also
The Solubility
Aqueous
of Several
Metal Sulfates
Uranyl Sulfate Solution,
and Pressures
in Water and in
See comments in Sec 5.23.
UNCLASSIFIED
DWG.
14613A
250
200-
- X
100-
CdSO^ (WT%)
F i g . 5.24.
Solubility of CdSO^ in U O j S O ^ Solutions.
179
5.25.
Solubility of C s 2 S 0 ^ in UO2SO4 Solutions
E. V, J o n e s , M. H. Lietzke, and W. L. Marshall, / . Am. Chem.

The Solubility
Aqueous
of Several
Uranyl Sulfate
Metal Sulfates
Solution,
Soc. 79, 267 (1957); a l s o
and Pressures
in Water and in
UNCLASSIFIED
DWG. 146174
300
200
CC
I-
<
CC
LU
a.
-
100
CSgSO^CWTVo)
Fig. 5.25. Solubility of Cs2S0^ in UOjSO . Solutions.
180
5.26.
Solubility of Y2(S04)3 in U 0 2 S 0 ^ Solutions
E. V. Jones, M. H, Lietzke, and W, L. Marshall, / , Am. Chem. Soc. 79, 267 (1957); also
The Solubility
Aqueous
of Several
Uranyl Sulfate
Metal Sulfates
Solution,
and Pressures
in Water and in
ORNL CF-55-7-69 (declassified Aug, 23, 1955),
UNCLASSIFIED
DWG 146354
350
300
TWO L I Q U I D
PHASES
IN 1.35/77 UO^SO^
250
IN 1.14 m UOgSO^
UJ
cr
200
150
100
2(504)3
F i g . 5.26.
(wt%;
Solubility of Y 2 ( S 0 4 ) 3 in UO2SO4 Solutions.
18
5.27. Solubility of AgjSO^ in U02S0^ Solutions

E. V. J o n e s , M. H. Lietzke, and W. L. Marshall, / . Am. Chem.
The
Solubility
Aqueous
of Several
Uranyl Sulfate
Metal Sulfates
Solution,
Soc. 79, 267 (1957); al
and Pressures
in Water and
ORNL CF.55-7-69 (declassified Aug. 23, 1955).

UNCLASSIFIED
DWG. 14615A
250
200
LU
a:
3
H
150
<
CC
UJ
Q.
UJ
100
Ag^SO^ (WT7o)
Fig. 5.27, Solubility of AgjSO^ in UOjSO^ Solutions,
182
5.28.
.
The
Solubility at 2 5 0 C of BaSO^ in U O 2 S O 4 - H 2 O Solutions
E. V. J o n e s , M. H. L i e t z k e , and W. L. Marshall, / . Am.

Solubility
Aqueous
of Several
Uranyl Sulfate
Solutions
Metal
Solutions,
were f i l t e r e d
Sulfates
at High
Temperatures
Chem.
Soc. 79, 267 (1957); a l s o
and Pressures
in Water and in
ORNL CF.55-7-69 (declassified Aug, 2 3 , 1955).
from s o l i d s at 2 5 0 C to obtain the s o l u b i l i t y
of BaSO^ in H j O .
C o u n t i n g of r a d i o a c t i v e barium was used to determine the s o l u b i l i t y c o n c e n t r a t i o n .
T h e very
large e f f e c t of U O . S O , must be noted and indicates c o n s i d e r a b l e s o l v a t i o n of other species by

aqueous U O j S O ^ ,
UNCLASSIFIED
DWG. 15530 A
^00
>
00
_l
O
CO
in
O
en
o
m
0.4
0,6
\/lV10LALITY
0,8
^.0
^.4
UO2SO4
Fig. 5.28. Solubility at 250C of BoSO^ in UOjSO^-HjO Solutions.

183
5.29.
S o l u b i l i t y of H2WO4 in 0.126 and 1.26 M UOjSO^
C. E. C o f f e y , W. L . M a r s h a l l , and G. H. C a r t l e d g e , HRP
Quar. Prog.
Rep.
Oct.
31,
1953,
ORNL-1658, p 9 6 - 9 9 .
The data shown in the figures were obtained by d i r e c t sampling of e q u i l i b r a t e d s o l u t i o n s , by
the f i l t e r bomb method, and by the s y n t h e t i c method described p r e v i o u s l y in Sec 5.8.
In 0.126 M
U O j S O . the s o l u b i l i t y of H . W O . f i r s t shows a p o s i t i v e temperature c o e f f i c i e n t of s o l u b i l i t y and

then,
above 1 0 0 C , a n e g a t i v e c o e f f i c i e n t
coefficient
form -
of s o l u b i l i t y
of s o l u b i l i t y .
is p o s i t i v e up t o 285,
In 1.26 M U O j S O , the temperature
the temperature at w h i c h t w o l i q u i d phases
a c h a r a c t e r i s t i c of U O j S O ^ - H . O s o l u t i o n s .
UNCLASSIFIED
DWG. 21760B
300
0200
en
3
<
/
H
SOLID + SOLUTION
100
2.0
SOLUBILITY (MOLARITY OF HgWO^ x 10^
3.0
Fig. 5.29a, Solubility of HjWO^ in a 126 M U02S0^,
184
UNCLASSIFIED
DWG. 21757 B
300
p 200
bJ
CC
Ui
a.
100
SOLUBILITY ( MOLARITY OF HgWO^ x 10
Fig, 5,29fe, Solubility of H2WO4 in 1,26 Al UO2SO4.
185
5.30.
C.
Phase Stability of H2WO4 in 1.26 M UO2F2

E. C o f f e y , W. L . M a r s h a l l , and G. H. C a r t l e d g e , HRP
Quar. Prog.
Rep. Oct.
31,
1953,
ORNL-1658, p 9 6 - 9 9 .
T h e methods of s o l u b i l i t y and s t a b i l i t y determination were the same as for analogous s t u d i e s
of H - W O . in U O j S O , (Sec 5.29).
hydrolytic
p r e c i p i t a t i o n of an u n i d e n t i f i e d s o l i d phase occurs from s o l u t i o n s s t a b l e at lower
temperatures.
186
T h e data on the f i g u r e as drawn show temperatures at w h i c h
UNCLASSIFIED
DWG. 21761 B
300
it.
200
SOLID + S OLUTION
LU
CC
I-
<
CC
/
y
100
SOLUTION
y
1.0
2.0
3.0
4.0
5.0
3%
SOLUBILITY (MOLARITY OF HgWO^ x lO
Fig. 5.30. Phase Stability of H2W0^ in 1.26 M UO2F2.
187
5.31. The System U02(N03)2-H20

1. Reported in full by W. L. Marshall, J . S. G i l l , and C. H. Secoy, Chem. Quar. Prog. Rep,
March 31, 1951, ORNL-1053, p 22-25.
2. Reported in part by W. L. Marshall, J . S. G i l l , and C. H. Secoy, / . Am. Chem. Soc. 73,
1867 (1951).
As in the case of the system UOjSO-H-O, hydrolysis occurs at high temperatures and low
concentrations, resulting in precipitation of UOg-HjO from stoichiometric U02(N03)2 solutions.
In addition, decomposition of N O j " occurs at elevated temperature to produce an equilibrium
vapor phase of nitrogen oxides.
Letter A represents a region of complete solution. Data at low
temperature up to point F were obtained by direct analysis of equilibrated solutions, whereas

the high-temperature data were obtained by the visual-synthetic method described in Sec 5.8.
188
UNCLASSIFIED
DWG. 10868
400
350
10
20
30
40
50
60
70
80
90
100
UO2 (N03)2 (wt %)

Fig. 5.31. The System U0 2(N03)2-H20.
189
5.32.
Phase Equilibria of UO3 and H F in Stoichiometric Concentrations (Aqueous System)
W. L . M a r s h a l l , J . S. G i l l , and C . H . Secoy, / . Am. Chem. Soc. 76, 4279 (1954).

The t w o - l i q u i d - p h a s e region and the region of " b a s i c " s o l i d s o l u t i o n + saturated s o l u t i o n
are in a c t u a l i t y segments of t h e three-component system U O , H F H . O , in which the e q u i l i b r i u m
phases are n o n s t o i c h i o m e t r i c w i t h regard to U O j F , .
T h i s system is somewhat analogous to t h e
system U O 3 - H 2 S O 4 - H 2 O (see Sec 5 . 7 ) .
UNCLASSIFIED
ORNL-LR-DWG 19098
{
1 ' 1 ' 1
SOLID + SUPER CRITICAL FLUID

AA

A
A- A - I
y UOgFg- SHgO + LIQUID I
p ,_ ^ ,
,,,.
-, E
z:B= v
.^
LIQUID I + LIQUID I K ^ ^ _ ^ - _ _ o BASIC SOLID ^yi3y-0-<2
O^^^^
0-K5
SOLUTION +
^
"^
SATURATED
/
_ SOLUTION
/
yU02F2-2H20
\+SATURATED
\ SOLUTION 1
./
*!
\
7 + ^1
' 0 0
. ^ H
S3
4
K
UNSATURATED SOLUTION
I-
OJ
0 p
c.
/
/
r~
e/.*
0 A OUR DATA
e DATA OF DEAN
- t a U02F2 2H2O
0 DATA OF KUNIN
+ SATURATED
SOLUTION
,#
|A
ICE + SATURATEDSOL'N.
- -
0.
4
,*
ICE + aUO^Fg-SHgO
i
10
20
30
40
50
60
1 1 1 11
70
80
WEIGHT PERCENT AS UO2F2
Fig. 5.32. Phase Equilibria of I-IO3 and HF in Stoichiometric Concentrations (Aqueous System).
190
90
5.33.
Solubility of Uranium Trioxide in Orthophosphoric Acid Solutions
W. L . M a r s h a l l , J . S. G i l l , and H . W. Wright, HRP Quar. Prog.

p
Rep. May 15, 1951, O R N L . 1 0 5 7 ,
112-15.
T h e data were obtained for the most part by e q u i l i b r a t i n g s o l u t i o n s of known concentration in
sealed tubes for various times at d i f f e r e n t temperatures.
Phase changes were observed v i s u a l l y .
UNCLASSIFIED
DWG 112 3 2
350
UOj
Fig. 5.3X
MOLARITY
Solubility of Uranium T r i o x i d e in Orthophosphoric Acid Solutions.
191
5.34.
Solubility of Uranium Trioxide in Phosphoric Acid at 2 5 0 C
J . S. G i l l , W . L . M a r s h a l l , and H. W. Wright, H R P Quar. Prog.
Rep. Aug. 15, i 9 5 i , 0 R N L . 1 1 2 1 ,
p 119-21.
Solution and s o l i d mixtures were equated at 2 5 0 C in sealed g l a s s tubes.
T h e tubes were
cooled r a p i d l y to room temperature, and the s o l u t i o n and s o l i d phases were a n a l y z e d .
T h e slow
r e v e r s i b i l i t y of e q u i l i b r i u m c o n d i t i o n s made t h i s procedure p o s s i b l e .
UNCLASSIFIED
DWG. 13000
A
/
O ANALYTICAL
?<
PREVIOUS SYNTHETIC
-:>/
- i /
Q/
y
'
____. ^
0
'
CONCENTRATION OF H j P O ^
F i g . 5.34.
192
()
Solubility of Uranium T r i o x i d e in Phosphoric A c i d at 250 C.
5.35.
Solubility of UO3 in H3PO4 Solution
B. J . Thamer et ah.
Homogeneous
HRP
Reactors,
Quar. Prog.
The Properties
of Phosphoric
Acid
Solutions
of Uranium
as Fuels
for
L A . 2 0 4 3 (March 6, 1956); W. L . M a r s h a l l , J . S. G i l l , and H. W. Wright,
Rep. May 15, 1951, O R N L - 1 0 5 7 , p 1 1 2 - 1 5 ; and J . S. G i l l , W. L . M a r s h a l l , and
H . W. Wright, HRP Quar. Prog.
Rep. Aug.
15, 1951, O R N L - 1 1 2 1 , p 1 1 9 - 2 1 .
T h i s f i g u r e represents a c o m p i l a t i o n from the data of B. J . Thamer et al. of L o s Alamos and

W. L . M a r s h a l l et al. of Oak R i d g e N a t i o n a l L a b o r a t o r y .
UNCLASSIFIED
O R N L - L R - D W G 29316
/
/
/
-SOLID PH/\ S F ic;
/
4H
0
1
UOgHPO^/
(2b-4C) 0 C ) ^ /
tK 0.5
- c
501J[ D PHASE IS
LJO,
\
/
t
/
\
\
DC)
^
(
25
/
/
,
(25C)
\,
\
\
V
\
\
\
/
^
0.2
/
/
0.1
1.0
10
20
PO4 MOLARITY
Fig. 5.35. Solubility of UO3 in M3P0^ Solution.
193
5.36. The System U02Cr04-H20

1. F. J . Loprest, W. L. Marshall, and C. H. Secoy, / . Am. Chem. Soc. 77, 4705 (1955).
2. W. L. Marshall, HRP Quar. Prog. Rep. March 31, 1953, ORNL-1554, p 105-6.
The solid phases are UOjCrO^'SVjHjO (A) and U02CrO^'xH20 (B).
Curve rs represents
the boundary of a region in which hydrolytic precipitation of a basic uranyl chromate occurs.
In the same concentration range the dichromate, U O j C r - O - , is stable to the critical temperature
and apparently dissolves in the supercritical fluid (ref 2).
UNCLASSIFIED
ORNL-LR-DWG 5144A
140
NON-BINARY
130 SOLID + LIQUID
120 -
Y
^
110 ~
100
_
o
^
LU
CC
H
<
'
_^ ^
\
Y ^ ^
)
r-^ i
90 _
B + LIQUID
>
LIQUID
80
70
()
DC
^
S
60
LU
H-
50
40 :
^'
30
20
10
A+ B
A + LIQUID
'Y
A +ICE 1
0
-10
0
10
20
30
F i g . 5.36.
194
40
50
60
U02Cr04(wt7o)
1
70
T h e System U O j C r O ^ - H j O .
80
90
100
5.37. Variation of Li2C03 Solubility with UO2CO3 Concentration at Constant CO2 Pressure
(250C)
1. F. J. Loprest, W. L. Marshall, and C. H. Secoy, HRP Quar. Prog. Rep. July 31, 1955,
ORNL-1943, p 227-35.
2. W. L. Marshall, F. J . Loprest, and C. H. Secoy, HRP Quar. Prog. Rep. Jan. 31. 1956,
ORNL.2057, p 131-32.
The solubility relationships in the figure indicate strong complexing of UO.CO, with L i - C O j
under C 0 pressure. The formation of HCOg"" species in solution is indicated.
UNCLASSIFIED
ORNL-LR-DWG 1 t l 8 2 A
1.000
/
1
0.800
0.600
O
o
X
6
<?y
y
/
0.400
>
Y
V
'^
SLOP ES:
3 . 3 7 moles of Li per mole of U
0.200
(L12CO3 IS SOLID PHASE)

4 . 4 4 moles of Li per mole of U
AT ISO BARIC INVAR! ANT
Fig. 5.37.
0.02
0.04
0.06
0,08
0.10
UOgCOjt/T?)
0.12
0.14
0.16
0.18
Variation of Li2C03 Solubility with UO-CO, Concentration at
Constant CO2 Pressure (250C).
195
5.38. The System L i 2 0 - U 0 3 - C 0 2 - H 2 0 at 250C and 1500 psi

1. F. J . Loprest, W. L. Marshall, and C. H. Secoy, HRP Quar. Prog. Rep. July 31, 1955,
ORNL-1943, p 227-35.
2. W. L. Marshall, F. J . Loprest, and C. H. Secoy, HRP Quar. Prog. Rep. Jan. 31, 1956,
ORNL-2057, p 131-32.
As COj pressure is increased, the area of complete solution (indicated by the shading)
increases. As temperature is increased, the solution area decreases.
UNCLASSIFIED
O R N L - L R - D W G 11342B
Fig. 5.38. The System L i j O - U O j - C O j - H j O at 250C and 1500 psi.
196
5.39. The System Th(N03)4-H20

1. Reported in full by W. L. Marshall, J . S. G i l l , and C. H. Secoy, HRP Quar. Prog. Rep.
Nov. 30, 1950, ORNL.925, p 279-90.
2. W. L. Marshall, J . S. G i l l , and C. H. Secoy, / . Am. Chem. Soc. 73, 4991 (1951).
Hydrolytic precipitation of ThOj and thermal decomposition of N O , " in this system occur in
an analogous manner to the reactions occurring in the system U02(N03)2-H20 (see Sec 5.31).
At higher temperatures the two-component system in actuality must be considered in terms of the
three components Th02, HNO3, and H j O .
UNCLASSIFIED
DWG. 9967
250
225-
200-
175
150
125
UJ
It
100
<
CC
LU
Q.
SOLUBILITY DATA
75
DECOMPOSITION PRECIPITATION
"MUSH" TEMPERATURES
SUPER COOLING
/
/
J
50
25
-25
-50
10
20
30
40
50
60
70
WEIGHT PERCENT Th(N03)4
F i g . 5.39.
T h e System T h ( N 0 3 ) ^ - H 2 0 .
80
90
100
197
5.40.
Hydrolytic Stability of Thorium NitrateNitric Acid and Uranyl Nitrate Solutions
1, W.
L. Marshall and C .
H. Secoy, HRP
Quar. Prog.
Rep.
Oct.
31,
1953,
ORNL-1658,
p 93-96.
2.
W. L . M a r s h a l l , J . S. G i l l , and C . H. Secoy, Chem.
Quar. Prog.
Rep.
March 31,
1951,
ORNL-1053, p 2 2 - 2 5 .
The data used to draw the i n d i v i d u a l curves were obtained by observations at various temperatures
of tubes that contained d i f f e r e n t s o l u t i o n s of known c o n c e n t r a t i o n .
was analogous to that used for o b t a i n i n g data for F i g . 5.33.
The procedure
The curve for h y d r o l y t i c p r e c i p i -
t a t i o n of U 0 2 ( N 0 3 ) 2 is taken from ref 2.
UNCLASSIFIED
ORNL-LR-DWG.21759B
380
N03/U=2.0
^>
340
_*-"^^
3300
0
^^"""^^^^^''^Ô^^^^
^260
[f, 220
y ^
= 5.47
^ N 0 , / T h = 6.65
Q.
^ ^ ^ ' N 0 3 / T h = 4.0
^ 8 0
140
Ann
THORIUM, URANIUM
Fig. 5.40.
2.0
^M)
Hydrolytic Stability of Thorium Nitrate-Nitric Acid and Uranyl
Nitrate Solutions.
198
1.0
5.41. The System T h O j - C r O g - H j O at 25C

1. H. T. S. Britton, / . Chem. Soc. 123, 1429 (1923).
2. W. L. Marshall, F. J . Loprest, and C. H. Secoy, HRP Quar. Prog. Rep. Jan. 31, 1955,
ORNL-1853, p 205-6.
The phase diagram at 25 was determined by Britton.
Points 17 indicate compositions
investigated at high temperature by Marshall, Loprest, and Secoy. These solution compositions
were phase stable up to 160C for point 7 and 320C for point 1.
Fig. 5.41.
The System T h O . - C r O j - H j O at 2 5 C
Compositions are in
weight per cent.
199
5.42.
Phase Stability of T h 0 2 - H 3 P 0 4 - H 2 0 Solutions at High Concentrations of T h O j
W. L . M a r s h a l l , experimental data in O R N L research notebook 2 8 8 1 , p 35 (May

Solutions of appropriate concentrations were prepared and a n a l y z e d .
1953).
T h e s e solutions were
s e a l e d in glass tubes and shaken at various temperatures for times v a r y i n g from 1 hr to several
days.
In t h i s manner the phase s t a b i l i t y boundaries w i t h respect to concentration and temper-
ature were e s t a b l i s h e d .
dissolved
A t f i r s t i n s p e c t i o n of the figure i t is s u r p r i s i n g that more T h O , can be
per liter at the lower H ^ P O ^ / T h O , ratio than at the higher r a t i o .
A c t u a l l y , there
is a p h y s i c a l volume l i m i t a t i o n due to the high f r a c t i o n a l volumes o c c u p i e d by T h O , and H ^ P O .

at these c o n c e n t r a t i o n s .
occurs.
A s any s o l u t i o n is d i l u t e d w i t h H , 0 , h y d r o l y s i s of thorium in s o l u t i o n
A t room temperature, s o l u t i o n s in which the H j P O . / T h O , r a t i o is 5:1 are g e l s , whereas
10:1 ratio s o l u t i o n s are s t i l l f l u i d .
UNCLASSIFIED
ORNL-LR-DWS
400
38529
350
/
/
^300
V
<
ir
250
HYDROLYTIC
SOLUTION
PRECiPITATIONX,' ^ S ^ ^ , ' ' ^ j '
REGION
7
REGION
PRECimAllON
V'ÛTION
RFfilON
REGION
/
BOUNDARY CURVE
FOR (OH MOLE
RATIO, H j P O ^ / T h O j
200
150
_L
100
200
_L
300
400
> /
V
500
600
>
i_
700
GRAMS Th02 PER LITER OF SOLUTION
BOUNDARY CURVE
FOR 5:( MOLE
RATIO,
H3P04/Th02
800
I
900
I
1000
(25C)
Fig. 5.42. Phase Stability of T h O j - H j P O ^ - H j O Solutions at High Concentrations of ThOy
200
ACKNOWLEDGMENT
Acknowledgment is made to the following for permission to reproduce copyrighted material:
American Ceramic Society
American Institute of Mining, Metallurgical, and Petroleum Engineers
Analytical
Chemistry
Journal of Chemical
Journal of Physical
and Engineering
Data
Chemistry
Journal of the American
Chemical
Society
U.S. Atomic Energy Commission
201
ORNL-2548
Chemistry - General
TID-4500 (15th ed.)

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PHASE DIAGRAMS OF NUCLEAR REACTOR MATERIALS

OAK RIDGE NATIONAL LABORATORY

Printed in USA. Price

. Available from the

Office of Technical Services

privately owned rights, or

of the Commission, or employee of such contractor prepares, disseminates, or

PHASE DIAGRAMS OF NUCLEAR REACTOR MATERIALS

OAK RIDGE NATIONAL LABORATORY

Sodium Metal-Sodium Halide Systems

T h e System U O j - P j O ^ - H j O , 25C Isotherm

T h e System U O j - H j P O ^ - H j O , 25C Isotherm

The System U ( H P 0 4 ) 2 - C l 2 0 7 - H 2 0 , 25C Isotherm

The System U 0 3 - N a 2 0 - C 0 2 - H 2 0 , 26C Isotherm

Portions of the System T h 0 2 - N a 2 0 - C 0 2 - H 2 0 , 25C Isotherm

The System N a 2 0 - C 0 2 - H 2 0 , 25C Isotherm

S e c o n d - L i q u i d - P h a s e Temperatures for U O . S O . Solutions C o n t a i n i n g

Phase S t a b i l i t y of H2WO4 in 1.26 M UO2F2

S o l u b i l i t y of Uranium T r i o x i d e in Orthophosphoric A c i d Solutions

S o l u b i l i t y of Uranium T r i o x i d e in Phosphoric A c i d at 250C

5 . 3 5 . S o l u b i l i t y of UO3 in H3PO4 Solution

PHASE DIAGRAMS OF NUCLEAR REACTOR MATERIALS

This document also contains diagrams originated by

phase equilibrium has been

included since excellent discussions are available in many well-known publications.

data on reactor materials available from many other sources.

For such information the reader is

referred to other recently published compilations of phase diagrams

and to the several new

works dealing specifically with nuclear reactor materials.

have been developed as a consequence of ORNL interests in reprocessing of nuclear fuels,

^ J . F . Hogerton and R. C. Grass ( e d s . ) . The Reactor

ORNL-2396 (Nov. 19, 1958).

vol 2, AECD.3646 (May 1955).

American Society for Metals, Cleveland, Ohio, 1948.

F. A. Rough and A. A. Bauer ( e d s . ) . Constitution

of Uranium and Thorium

E. M. Levin, H. F . McMurdie, and F . P . Hall, Phase

E. M. Levin, H. F . McMurdie, and F . P . Hall, Supplement

The American Ceramic

B. Y a t e s , Materials for Use m Nuclear Reactors,

B, Kopelman (ed.)# Materials

McGraw-Hill Book Co., New York, 1959.

The system was found to be characterized by two intermediate

It was found that impurities in the range 0.05% from the

DAV TWO PHASE

WHICH WERE CHEMICALLY ANALYZED FOR SILVER CONTENT

T h e System SilverZirconium in the Region 036 a t . % A g .

The System IndiumZirconium

Region 0 - 2 6 at. pet I n , " Trans.

Met. Soc. AlME 212, 3 4 0 - 4 2 (1958).

phase diagram was determined as a

study of the e f f e c t of a l l o y i n g a t r i v a l e n t B-subgroup element, indium, w i t h zirconium in group

The temperature of the a l l o t r o p i c t r a n s i t i o n was found to r i s e w i t h indium, terminating in a

p e r i t e c t o i d r e a c t i o n , |S(9.3% In) + y{22.4% In) ; ^ : : ^ - a ( 1 0 . 1 % In) at 1003C.

In this respect the

e f f e c t of indium is analogous to that of aluminum in z i r c o n i u m and titanium a l l o y s .

INDIUM (at 7o)

T h e System IndiumZirconium in the Peritectoid Region (013

The System LeadZirconium

"Zirconium Equilibrium D i a g r a m s , " p 44383 in The Metallurgy

and F. Kerze, Jr., McGraw-Hill Book C o . , New York, 1955.

The System LeadZirconium in the Peritectoid Region (012